CA2216084A1 - Stabilizers for use in oxygen-based treatments of cellulosic materials - Google Patents
Stabilizers for use in oxygen-based treatments of cellulosic materials Download PDFInfo
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- CA2216084A1 CA2216084A1 CA002216084A CA2216084A CA2216084A1 CA 2216084 A1 CA2216084 A1 CA 2216084A1 CA 002216084 A CA002216084 A CA 002216084A CA 2216084 A CA2216084 A CA 2216084A CA 2216084 A1 CA2216084 A1 CA 2216084A1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1026—Other features in bleaching processes
- D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
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Abstract
The invention is a method for ameliorating oxygen-based treatments of cellulosicmaterials in aqueous systems comprising adding to an aqueous system containing an effective stabilizing amount of a compound or a combination of compounds which may include a polymer. The invention is also three novel grafted polymers.
Description
Field of th~Ipvention The invention is a method for ameliorating oxygen-based tre~tment~ of cellulosic ~-~ materials in aqueous systems compnsing adding to an aqueous system co.~ g cellulosic m~t~ri~l~ an effective stabilizing amount of a compound or a combination of 5 compounds which may include a polymer. The invention is also three novel grafted polymers.
Ra~round of the Invention Paper is made from chemic211y produced wood pulp, which is also referred to as cellulosic pulp. In the production of paper, during the chemical pulping process, 10 cellulosic pulp undergoes chemical delignification and ble~cl ing Delignification and bleaching is part of the chemical pulping process in which the ligneous and colored materials are removed from the chemical cellulosic pulp.
The delignification and ble~ching of the pulp is accomplished in several bleaching stages. This is referred to as a multi-stage bleaching and delignification process. A
1~ bleaching stage for the purposes of this invention means a blea~lling phase starting with the addition of a bleaching chemical to the pulp and ending with the washing of the pulp.
~ ithin each bleaching stage, there are many process variables such as the amount of chemical added, time, temperature and pH. The sequence of ble~ching stages used in the bleaching and delignification process will change, as will the variables within each stage.
~O The selection of stages and variables, and the sequence of stages, is determined by several factors including:
a. the nature of the cellulosic pulp, softwood versus hardwood;
b. the pH of the pulping process used; and c. the final use for which the bleached pulp is ~eci,~n~tt~l - In an effort to achieve a suitable balance bet~,veen the co"lp~L,llg factors of pulp brightness and pulp strength (which is often ",~&~u.ed as a function of pulp viscositv).
5 bleach plants have resorted to multi-stage processes.
In the multi-stage ble~rhin~ process, the cellulosic materials, such as wood pulp.
is first digested and cooked. A first step after cooking and digestion is often brown stock washing. In brown stock washing, the pulp having pH of 11 - 13 is repeatedlv washed with water to remove some colored lignins.
The first ble~ching stage is of~.en deci~n~d to remove more ligIuns and other encrustants. One delignification and ble~hin2 stage is oxygen delignification. In oxygen delignification, oxygen-gas is mixed ~,vith the pulp. The pulp is made alkali to facilitate the reaction. The pH ofthe pulp is generally about 10 - 11. In oxygen ~elis~nification. two reactions occur. In one reaction. the oxygen gas reacts with the pulp 1~ to ma~;e the lignins soluble in water at alkali pHs. In another, less desirable reaction. the o~! ~en gas reacts with the pulp to degrade the pulp. This reduces pulp strength.
In another stage. the pulp aqueous suspension is chlorinated. The pulp is made sli ~htl! acidic (pH 2 - 4) to facilitate the reaction. Chlorination of the unbleached pulp m;l~es ~he ligneous impurities partlv soluble in water. These lignins are removed by a
Ra~round of the Invention Paper is made from chemic211y produced wood pulp, which is also referred to as cellulosic pulp. In the production of paper, during the chemical pulping process, 10 cellulosic pulp undergoes chemical delignification and ble~cl ing Delignification and bleaching is part of the chemical pulping process in which the ligneous and colored materials are removed from the chemical cellulosic pulp.
The delignification and ble~ching of the pulp is accomplished in several bleaching stages. This is referred to as a multi-stage bleaching and delignification process. A
1~ bleaching stage for the purposes of this invention means a blea~lling phase starting with the addition of a bleaching chemical to the pulp and ending with the washing of the pulp.
~ ithin each bleaching stage, there are many process variables such as the amount of chemical added, time, temperature and pH. The sequence of ble~ching stages used in the bleaching and delignification process will change, as will the variables within each stage.
~O The selection of stages and variables, and the sequence of stages, is determined by several factors including:
a. the nature of the cellulosic pulp, softwood versus hardwood;
b. the pH of the pulping process used; and c. the final use for which the bleached pulp is ~eci,~n~tt~l - In an effort to achieve a suitable balance bet~,veen the co"lp~L,llg factors of pulp brightness and pulp strength (which is often ",~&~u.ed as a function of pulp viscositv).
5 bleach plants have resorted to multi-stage processes.
In the multi-stage ble~rhin~ process, the cellulosic materials, such as wood pulp.
is first digested and cooked. A first step after cooking and digestion is often brown stock washing. In brown stock washing, the pulp having pH of 11 - 13 is repeatedlv washed with water to remove some colored lignins.
The first ble~ching stage is of~.en deci~n~d to remove more ligIuns and other encrustants. One delignification and ble~hin2 stage is oxygen delignification. In oxygen delignification, oxygen-gas is mixed ~,vith the pulp. The pulp is made alkali to facilitate the reaction. The pH ofthe pulp is generally about 10 - 11. In oxygen ~elis~nification. two reactions occur. In one reaction. the oxygen gas reacts with the pulp 1~ to ma~;e the lignins soluble in water at alkali pHs. In another, less desirable reaction. the o~! ~en gas reacts with the pulp to degrade the pulp. This reduces pulp strength.
In another stage. the pulp aqueous suspension is chlorinated. The pulp is made sli ~htl! acidic (pH 2 - 4) to facilitate the reaction. Chlorination of the unbleached pulp m;l~es ~he ligneous impurities partlv soluble in water. These lignins are removed by a
2() sli ~htl! ~cid water wash. After chlorination. the portions of the lignins not readily soluhle in water are removed bv an ~ line solution, such as dilute sodium hydroxide, about pH 8 ~
Following a tre~trn~nt with sodium hydroxide and ~ubse~luent washes of the pulp, the alkaline extract pulp may be further chlorinated with chemicals such as calcium or - sodium hypochlorite. During this stage, the pH is m~int~in~d at between 10 - 11. After washing, the pulp may then be further chlorinated in another stage with aqueous chlorine 5 dioxide, and washed again.
In some bleach plants, the final blç~ching stage is a hydrogen peroxide bleaching stage. The main purpose of this stage is to stabilize the final ble~ching brightness and perhaps to raise the brightn~s~ The pH of the hydrogen peroxide ble~hing stage is m~int~ined at from 9 - 12.
Bleaching often adversely affects pulp strength. For example, the chlorination stage converts most of the colored lignin which remains after the initial pulping or digestive process to chlorinated lignin derivatives which are partially soluble in acidic chlorine solution and particularly soluble in alkaline extraction liquors. Such stages are also referred to as a delignification stage. Nevertheless, destructive oxidation also occurs hich reduces the length of the cellulosic molecule; and, accordingly, reduces the strength and the viscosity of the pulp. The competition between brightnes~ and pulp strength (often measured as pulp viscosity) has been of particular concern in the paper hldustry and has been primarily responsible for the proliferation of the various bleaching se~uences. Brightness can be increased by increasing either the number of bleaching ~() stel~s used or by increasing the arnount of bleaching chemical used. Among treatments for increasing brightness include thiourea dioxide as disclosed in U.S. Patent No.
4.~ 14.780 and poly(acrylic acid) as disclosed in U.S. Patent No. 4,255,233. However, this results in a decrease of pulp strength and an increase in the cost of chemicals used.
Furthermore, as will be ~liscll~sed below, increasing the number of chlorination stages presents the paper m~nllf~c~tllrer with a potential environm~nt~l hazard.
- Regardless of the sequence used, the buL~ of cellulose ble~hing still is performed using some combination of chlorination and ~lk~lin~- extraction. However, chlorination is S not an environment~lly friendly process. Chlorination produces dioxin which is considered by many local and national agencies to be a toxic substance which is hazardous to the environrnent. In fact, extremely strict controls have been placed on the discharge of dioxin into the environment. Accordingly, many paper producers are looking to chlorine-free blç~clling processes.
To further complicate the delignification and ble~hing process, metal cont~min~tion, such as iron, m~ng~n.ose and copper illlelrt le with several of ble~ching stages, such as, peroxide ble~ching, chlorine ble~ching, chlorine dioxide ble~hing, and oxygen delignification. For example, in oxygen delignification and peroxide ble~ehing, not only does the iron form color bodies under ~Ik~line conditions, but the iron catalyses I ~ the decomposition of the cellulose.
Currently, a number of chemicals are being used to remove these metals from the cellulosic pulp. Particularly, chelating amines have been used to improve pulp brightness through the removal of metallic impurities. United States Patent No. 4,298,428 discloses se~eral chelating amines for accomplishing this. Other chelating compounds used in the 20 industry include nitrilotriacetic acid (NTA). ethylene~ minetetraacetic acid (EDTA), and diethylenetriaminepentaacetic acid (DTPA). These chemicals, often referred to as chelants. are added immediately before the bleaching stage, but after the aqueous pulp slurry has been acidified. The pulp must be acidified since the chelating chemicals presently used in the industry, such as EDTA, NTA and DTPA, will not remove metal h~ ies at alk~line pHs, particularly above pH 8. NTA is considered by some authorities to be hazardous and its discharge into the environment is closely controlled.
Since these chel~ting chemicals do not function above a pH of about 8, several 5 problems are created for the industry. The first problem is that an additional acidification step is always necess~ry when these chelating chemicals are added after an alkaline extraction, but before the next ble~ching stage. This additional acidifying step is costly to the paper producer. Moreover, the acidifying chemicals are potentially hazardous to paper mill workers.
A second problem caused by these chelating chemicals is that they prevent the paper-making industry from switching to a chlorine-free b1earlling process. In more detail. chlorination is acidic and these prior art chelating chemicals are only effective in an acidic medium. In contrast, the chlorine-free ble~ching stages, such as oxygen deli~nification, and hydrogen peroxide ble~ching, are ~lk~lin~ . Since c~~ ly available I j chelating chemicals do not work well in ~lk~line environments, additional acidifying steps must be added to the process. Even with the addition acidifying steps, these prior art chelant chemicals do not work throughout the entirety of the process since the non-chlorine processes are conducted under alkaline conditions. Accordingly, new treatments are necessary for removing metals from chemically produced pulp.
~0 ln light of the disadvantages of the prior art, it would advantageous to provide an agent which would increase brightness by removing the metallic hl~pul;~ies in the pulp at an alkaline pH above 7. It would be further advantageous to provide a treatment which would increase brightness and also increase pulp strength, as measured by viscosity. It would be a still further advantage to provide a tre~tmrl t which would elimin~te the need for chlorine ble~rhing stages.
- Snmm~ry of the Invpntion The invention is a method for ameliorating oxygen-based treatments of cellulosic 5 materials in aqueous systems compri~ing adding to an aqueous system cont~ining cellulosic materials an effective stabilizing amount of a compound or a combination of compounds which may include a polymer. The invention is also three novel grafted polymers.
Description of the Invention The invention is a method for ameliorating oxygen-based treatments of cellulosic materials in aqueous systems comprising adding to an aqueous system cont~ining cellulosic materials an effective oxygen-based treatment stabilizing amount of a compound selected from the group consisting of tris(hydroxymethyl)aminomethane, N-alkyl dimethyl benzyl ammonium chloride, N-dialkyl methyl benzyl ammoniurn chloride 15 and combinations thereof.
The oxygen-based treatment may be selected from the group con~i~ting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide ble~çhing and pressurized peroxide bleaching. The aqueous system may be a pulp and paper system. From about 0.0001 to about 2.0 percent by 20 weight of compound may be added based on the dry weight of the cellulosic material.
Preferably. from about 0.01 to about 1.0 percent by weight of compound may be added based on the dry weight of the cellulosic material. Most preferably, from about 0.1 to about 0.8 percent by weight of compound may be added based on the dry weight of the cellulosic material.
~-~ The invention is also a method for ameliorating oxygen-based treatments of cellulosic m~tPri~l~ in aqueous systems compri~ing adding to an aqueous system 5 co~ g cellulosic materials an effective oxygen-based tre~tm~nt stabilizing amount of a combination of:
a) diethylenetriaminepent~etic acid and b) a second compound selected from the group co~ tiny of citric acid, sodium gluconate, sodium glucoheptonate, ethylen~ acetic acid, tris 10 (hydroxymethyl)aminomethane, and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride.
The oxygen-based tre~tment may be selected from the group con~i~ting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide ble~ching and ples~u~ized peroxide ble~ching The aqueous I ~ svstem may be a pulp and paper system. The mole ratio of diethylenetri~minepentaacetic acid to the second compound may be from 0.001: 99.999 to 99.999:0.001. Preferably, the ratio may be 0.1 to 99.9 to 99.9 to 0.1. Most preferably, the ratio may be 1.0 to 99 to 99 to ]Ø
The invention is also a method for ameliorating oxygen-based treatments of ~0 cellulosic materials in aqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based tre~tm~nt stabilizing amount of a combination of:
a) citric acid and b) a second compound selected from the group con~i~tin~ of sodium gluconate, sodium glucoheptonate, ethylen~ minPt~l~dac~lic acid, tris-(hydroxymethyl)aminomethane, and a combination of N-alkyl dimethyl benzyl 5 ammonium chloride and N-dialkyl methyl benzyl ammonium chloride.
The oxygen-based treatment may be selected from the group con~i~ting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide ble~hing and l~les~ul;zed peroxide ble~ching The aqueous system may be a pulp and paper system. The mole ratio of citric acid to the second compound may be from 0.001:99.999 to 99.999:0.001. Preferably, the ratio may be 0.1 to 99.9 to 99.9 to 0.1. Most preferably, the ratio may be 1.0 to 99 to 99 to 1Ø
The invention is also a method for ameliorating oxygen-based tre~tm~nt~ of cellulosic materials in aqueous systems compri~ing adding to an aqueous system containing cellulosic materials an effective oxygen-based treatment stabilizing amount of 15 a combination of:
a) sodium gluconate and b) a second compound selected from the group consisting of sodium glucoheptonate, ethylene~ minetetraacetic acid, tris(hydroxymethyl)aminomethane, and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl ~0 henzyl ammonium chloride.
The oxygen-based treatment may be selected from the group consisting of oxygen delignification oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide bleaching and pressurized peroxide ble~ching The aqueous system may be a pulp and paper system. The mole ratio of sodium gluconate to the second compound may be from 0.001: 99.999 to 99.999: 0.001. Preferably, the ratio - may be 0.1 to 99.9 to 99.9 to 0.1. Most preferably, the ratio may be 1.0 to 99 to 99 to 1Ø
The invention is also a method for ameliorating oxygen-based tre~tmentc of -5 cellulosic materials in aqueous systems compri~ing adding to an aqueous system containing cellulosic materials an effective oxygen-based Ll~ .,.rnt stabilizing amount of a combination of:
a) ethylçn~ nninetetraaceticacid, and b) tris(hydroxymethyl)alllh~ lethane, and a combination of N-alkyl dimethyl 10 benzyl ammonium chloride and N-dialkyl methyl ammonium chloride.
The oxygen-based treatment may be selected from the group consisting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-~ided extraction, peroxide ble~ching and pressurized peroxide ble~c-hing. The aqueous system may be a pulp and paper system. The mole ratio of ethylene ~ mine tetraacetic 1~ acid to the second compound may be from 0.001: 99.999 to 99.999:0.001. Preferably, the ratio may be 0.1 to 99.9 to 99.9 to 0.1. Most preferably, the ratio may be 1.0 to 99 to )~ to 1 0 The invention is also a method for stabilizing peroxide treatments in aqueous p;lper production streams containing kraft pulp, peroxide, m~n~n~se and iron comprising ~() the step of adding to the aqueous paper production stream co~ h.g kraft pulp, peroxide, manganese and iron. wherein an equal or greater amount of iron is present than manganese. an effective peroxide-stabilizing amount of a combination selected from the group consisting of: poly(acrylamide/sodium acrylatelN-(trishydroxymethyl)methyl acrylamide)/diethylenetri~minepent~etic acid, poly(acrylamide/sodium acrylatelN-(trishydroxymethyl)methyl acrylamide)/citric acid, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, 5 poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/ethylenPtli~minetetraacetic acid, diethylenet,;al"inepentaacetic acid/a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, diethylenetriall,hlep~ cetic acid/
ethylene~ minetetraacetic acid, citric acid/a combination of N-alkyl dimethyl benzyl 10 ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, citric acid/sodium glucoheptonate, citric acid/ethylenP~ mil-eteLIdacetic acid, sodium gluconate/sodium glucoheptonate, sodium gluconate/ethylenP~ minetetraacetic acid and a combination of N~-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride/sodium glucoheptonate.
I ~ The invention is also a method for stabilizing peroxide treatments in aqueous paper production streams cont~ining peroxide, kraft pulp, m~ng~nPse and iron comprising the step of adding to the aqueous paper production stream cont~ining peroxide, kraft pulp, manganese and iron, wherein an equal amount or lower of iron is present than manganese. an effective peroxide-stabilizing amount of a combination selected from the ~0 group consisting of: poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)tdiethylenetriaminepentaacetic acid, poly(acrylamide/sodium acrylatetN-(trishydroxymethyl)methyl acrylamide)/a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, poly(aspartic acid)/citric acid, poly(aspartic acid)/sodium glucoheptonate, poly(aspartic acid)/ethylene~i~minPtetraacetic acid, diethylenetri;.."i"cpent~r,etic acid/citric acid and diethylenetri~minPpent~retic acid /sodium gluconate.
The invention is also a method for stabilizing peroxide tre~tment~ in aqueous 5 paper production streams col~ g peroxide, mechanical pulp, m~ng~nPse and iron, compri~inp the step of adding to the aqueous paper production streams cont~ining peroxide, mechanical pulp, m~ng~nPse and iron, wh~reill an equal or greater amount of iron is present than m~ng~nese, an effective peroxide-stabilizing amount of a combination selected from the group consisting of: poly(acrylamide/sodium acrylate/N-l O (trishydroxymethyl)methyl acrylamide)/sodiurn gluconate, poly(acrylamide/sodiumacrylate/N-(trishydroxymethyl)methyl acrylamide)/sodium glucoheptonate, diethylenetriaminepentaacetic acid/sodium gluconate, diethylenetri~mil,~pclll~acetic acid /a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, diethylenetriaminepentaacetic acid/sodiurn glucoheptonate, I ~ citric acid/a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, citric acid/sodium glucoheptonate, sodium s.luconate/sodium glucoheptonate, sodiurn gluconate/ethylene~ minetetraacetic acid and ~ combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl henzyvl ammonium chloride/ethylene~ minetetraacetic acid.
~O The invention is also a method for stabilizing peroxide treatments in aqueous paper production streams cont~ining peroxide, mechanical pulp, m~ng~nPse and iron, comprising the step of adding to the aqueous paper production stream cont~ining peroxide. mechanical pulp, m~ng~nese and iron, wherein an equal or lower amount of iron is present than m~ng~nese, an effective peroxide-stabiliziIrg arnount of a combination selected from the group con~i~ting of: poly(acrylarr.ude/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/sodium gluconate, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/a combination of N-alkyl dimethyl 5 benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylarnide)/ethylen~ minetetraacetic acid, poly(aspartic acid)/ethylene.li~mintotetraacetic acid, diethylenetriaminep~nt~.etic acid /citric acid, diethylenetriarninepentaacetic acid/sodium gluconate, diethylenetriaminepentaacetic 10 acid/a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, diethylenetriaminep~nt~cetic acid/sodium glucoheptonate, citric acid/ethylene.1i~minetetraacetic acid and sodium gluconate/a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzvl ammonium chloride.
The invention is also a method for ameliorating oxygen-based treatments of cellulosic materials in aqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based tre~tment stabilizing amount of a water-soluble polymer selected from the group consisting of poly(aspartic acid), poly(dithiocarbamate), poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl ~0 acrvlamide), poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate). poly(sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), poly(sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate) and poly(acrylamide/sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate).
- The oxygen-based treatment may be selected from the group consisting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-5 aided extraction, peroxide bleaching and pres~ ed peroxide ble~rhing. From about 0.001 to about 2 percent by weight of water-soluble polymer may be added based on the dry weight of the cellulosic material. The aqueous system may be a pulp and paper system.
The water-soluble polymer may be poly(acrylarnide/sodium acrylate/N-10 (trishydroxymethyl)methyl acrylamide), and the mole ratio of acrylamide to sodiumacrylate to N-(trishydroxymethyl)methyl acrylamide may be from 0:1:99 to 10:60:30 and the molecular weight may be from 1,000 to 10,000,000. The water-soluble polymer may be poly(acrylamide/ sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate) and the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(3,4-I ~ dihvdroxyphenyl) methane sulfonate may be from 0:10:90 to 10:60:30 and the molecular ~-eight may be from 1,000 to 10,000,000. The water-soluble polymer may be r)oly(acrylamide/sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate and the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(2-hydroxyphenyl) methane sulfonate may be from 0:10:90 to 10:60:30 and the molecular ~0 ~eight may be from 1.000 to 10,000,000.
The invention is also a method for ameliorating oxygen-based treatments of cellulosic materials in aqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based tre~tm~nt stabilizing amount of:
a) a compound selected from the group con~i~ting of diethylenetti~minPpent~cetic acid, citric acid, sodium gluc~n~te, sodium glucoheptonate, ethylene~ minetetraacetic acid, tris(hydroxymethyl)aminometh~ne, a combination of N-alkyl dimethyl ben7yl ammonium chloride and N-dialkyl methyl benzyl ammonium 5 chloride and b) a water-soluble polymer selected from the group consisting of poly(aspartic acid), poly(dithiocarbamate), poly(acrylamide/sodium acrylate/N-(tris-hydroxymethyl)methyl acrylamide), poly(acrylamide/sodium acrylate/sodium acrylarnido(3,4-dihydroxyphenyl) methane sulfonate), poly(sodium acrylate/sodium 10 acrylamido(2-hydroxyphenyl) meth~ne sulfonate), poly(sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), poly(sodium acrylate/N-(tris-hydroxymethyl)methyl acrylarnide) and poly(acrylamide/sodium acrylate/sodium acrylamido(2-hydroxyphenyl) meth~ sulfonate).
The oxygen-based treatment may be selected from the group consisting of oxygen 15 delignification. oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide ble~ching and pressurized peroxide ble~ching. The aqueous system may be a pulp and paper system. The mole ratio of the compound to the water-soluble polymer may be from about 0.00001: 99.99999 to about 99.99999: 0.00001.
Preferably. the ratio may be 0.1 to 99.9 to 99.9 to 0.1. Most preferably, the ratio may be ~0 1.0 to 99 to 99 to 1Ø The water-soluble polymer may be poly(acrylamide/sodium acrvlate/N-(trishydroxymethyl)methyl acrylamide) and the mole ratio of acrylamide to sodium acrylate to N-(trishydroxymethyl)methyl acrylamide may be from 0:1:99 to 10:60:30 and the molecular weight may be from 1,000 to 10,000,000. The water-soluble polymer may be poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate) and the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(3,4-dihydroxyphenyl) meth~ne sulfonate may be from 0:1:99 to 10:30:60 and the molecular weight may be from 1,000 to 10,000,000. The water-soluble 5 polymer may be poly(acrylamide/sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate) and the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(2-hydroxyphenyl) methane sulfonate may be from 0:1:99 to 10:30:60 and the molecular weight may be from 1,000 to 10,000,000.
The invention is also a water-soluble polymer of the formula 10 poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate). Preferably, the polymer may have a mole ratio of acrylamide to sodium acrvlate to sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate of from 0:1:99 to 10:30:60 and the molecular weight may be from 1,000 to 10,000,000.
The invention is also a water-soluble polymer of the formula 1~ poly(acrvlamide/sodium acrylate/sodium acrylamidomethyl(2-hydroxyphenyl) sulfonate).
Preferably. the polymer may have a mole ratio of acrylamide to sodium acrylate to so dium acrvlamido(2-hydroxyphenyl) methane sulfonate of from 0:1:99 to 10:30:60 and the molecular weight may be from 1,000 to 10,000,000.
The invention is also a water-soluble polymer of the formula poly(sodium '() acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate). Preferably, the polymer may have a mole ratio of sodium acrylate to sodium acrylamido(2-hydroxyphenyl ) methane sulfonate of from 99:1 to 60:40 and the molecular weight may be from 1.000 to 10~000,000.
The invention is also a water-soluble polymer of the formula poly(sodium acrylate/N-(trishydroxymethyl)methyl acrylamide). Preferably, the polymer may have a mole ratio of sodium acrylate to N-(trishydroxymethyl)methyl acrylamide of from 99:1 to 60:40 and the molecular weight may be from 1,000 to 10,000,000.
The invention is also a water-soluble polymer of the formula poly(sodium acrylate/acrylamido(3,4-dihydroxyphenyl) methane sulfonate). Preferably, the polymer may have a mole ratio of sodium acrylate to acrylamido(3,4-dihydroxyphenyl) methane sulfonate of from 99:1 to 60:40 and the molecular weight may be from 1,000 to 10,000,000.
l O . The invention is also a method for ameliorating oxygen-based treatments of cellulosic materials in aqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based treatment stabilizing amount of a combination of sodium glucoheptonate and xylanase enzyme. The oxygen-based treatment may be selected from the group consisting of oxygen delignification, oxygen-l ~ aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide bleaching and pressurized peroxide bleaching.
The compounds of this invention may be added to pulp and paper systems at ~!arious points, including but not limited to at the brown stock washers, the oxygen delignification stage, the chlorine stage, the chlorine dioxide stage, the Q-step, the extraction stage. the oxygen-aided extraction stage, the peroxide-aided extraction stage, the oxygen/peroxide-aided extraction stage, the peroxide stage, after the peroxide stage to prevent reversion on the way to the paper machine, in the refiners of the pulp mill and the paper mill, in the showers to prevent plugging, and at the sodium dithionite bleaching stage.
-~ I:lle ~i~h Moleclllar We~ht Water Soluble Flocculan~~
The polymeric flocculants employed in the process of the present invention can be 5 prepared by a variety of methods. The polymers of the subject invention can be conveniently prep~ed by amidation or transamidation reactions on an existing polymer, by polymenzation of a trishydroxymethyl CO~ .g monomer, or by reaction with bisulfite, aldehyde and AcAm/NaAc polymers. It is pleselllly ~ler~,l,ed to prepare the polymers of the instant invention from water soluble copolymers of acrylamide and 10 acrylic acid or its water soluble alkali metal or ammonium salts by tr~n~m~ tion of the amide functionality on the acrylamide mer units of the polymer. The polymers useful as starting materials will generally contain from as little as l mole percent acrylamide to as high as 50 mole percent acrylamide. Preferably, the polymer will contain from 5-40 mole percent acrylamide, and most preferably, from 10-30 mole percent acrylamide. While a 15 copolvmer of acrylamide, acrylic acid and its water soluble alkali metal or ammonium salts is preferred, copolymers of methacrylamide and acrylic acid, or its alkali metal salts may also be lltili7f~d While in a presently preferred embodiment of the invention a copolymer of acrylarnide and acrylic acid is used as a starting material, other anionic or nonionic monomers can be incorporated into the starting polymer chain. Monomers of ~0 this type include but are not limited to acrylamido~lopane sulfonic acid, vinylformamide, vinyl acetate, and vinyl sulfonate. Polymers which have been derivitized in accordance with U.S. Patent 4,680,339 to include sulfonate groups may also be employed so long as sufficient unreacted amide functionality remains for the tr~n~mid~tion reaction which produces the desired functionality. Like~,vise, the polymer may be modified to include hydroxamic acid groups as taught in U.S. 4,767,540 to - Spitzer et al.
Vinyl addition polymers comprised of anionic acrylate mer units andlor N-5 sulfoalkyl (meth)acrylamide mer units, optionally together with (meth)acrylamide merunits, may be directly synthesized from the corresponding monomers by kno~vn techniques, for instance using as the sulfonate-cc,..~ g monomer the 2-acrylamido-2-methylpropane sulfonic acid, or the methacrylamide version thereof. N-sulfoalkyl (meth)acrylamide mer units can also be incorporated into an existing polymer by post-polymerization derivatization, for instance by one of the methods described in U. S.
Patent No. 4,762,894 (Fong et al.) issued Aug. 9, 1988, U. S. Patent No. 4,680,339 (Fong) issued July 14, 1987, U. S. Patent No. 4,795,789 (Fong et al.) issued Jan. 3, 1989, and U. S. Patent No. 4,604,431 (Fong et al.) issued Aug. 5, 1986, the disclosures of all of which are hereby incorporated hereinto. The sulfonated mer units of such post-polymerization derivatized polymers are generally of the sulfonate N-alkyl substituted (meth)acrylamide type.
U. S. Patent No. 5,395,897 (Hurlock et al.) issued March 7, 1995 discloses a method to post derivatized poly(acrylic acids) which can also can be used to prepare polymeric systems of this invention described herein.
U. S . Patent No. 4,678,840 (Fong et al.) issued July 7, 1987, describes a method for preparation of acrylamide polymers having ionizable phosphonate groups, and the disclosures of this patent are incorporated herein by reference. Phosphonate-cont~iring acrylamide polymers that meet the p,~fe,l.,d molecular weight ranges may possibly be ~
active in the present process ~ other anionic acrylamide polymers described above.
Non-hl~lre~;ng mer units other than (meth)acrylamide may be used, such ~
methylol acrylamide or other nonionic but polar mer units, and even nonpolar mer units 5 may be used to the extent that the presence of such mer units does not hlt~.rere with the water solubility of the polymeric flocculant. The polymeric flocculant generally should have a weight average molecular weight of at le~t about 500,000, and preferably at least about 1,000,000, and even more preferably at least about 4,000,000, or 5,000,000. The polymeric flocculant has no standard molecular weight ceiling for the purposes of the present invention, and some flocculants having molecular weights of 15,000,000 or higher may be highly useful for the present invention so long as the polymer remains water soluble or substantially water dispersible. A particularly pr~,rt;l~c;d high molecular weight water soluble anionically charged flocculant for use in this invention is polyacrylic acid in either its sodium or ammonium salt forms having a molecular weight greater than about 10,000,000.
The polymeric flocculant employed in the present invention should be water ~oluble. The water solubility characteristic preferably is defined in terms of fluidity of aqueous solutions of the polymer. By "water soluble" is meant herein, and generally, that all aqueous solution of the polymer, at the polymer actives concentration at which it is ~0 char~ed to the primary settler feed is reasonably fluid, and preferably h~ a viscosity of no more than about 5,000 to 20,000 cps Brookfield, at ambient room temperature (from about 23~ to about 26~C.). Such water solubility characteristic generally does not create a molecular weight ceiling because even an acrylamide homopolymer, substantially free of any electrolytic groups, meets such a standard at the high molecular weights that can now be provided by conventional synthesis techniques, provided the polymer is substantially Iinear. Hence the highly anionic polymeric flocculants employed in the present invention will generally be even more water soluble at a given molecular weight.
High molecular weight polymeric flocc~ nt.c of the type described above are commonly synthesized and commercially supplied in the form of water-in-oil emulsion form. Water-in-oil emulsions of the high molecular weight anionically charged polymers useful in this invention are available commercially from a variety of sources. The water-in-oil emulsion form for these types of polymers is ~l~fell~;d bec~use it permits the 10 polymer to be prepared and shipped at reasonably high concentrations (and the polymer therein is readily dispersible in water upon inversion of such emulsion by knowntechniques, which is desirable for many use applications). Water-in-oil emulsions of vinyl addition polymers are well known and are described, for instance, in U. S. Patent No. 3.284,393, Vanderhoff, and U. S. Patent No. Re. 28,474, Anderson-Frisque, and the 15 disclosures of these patents are incorporated herein by reference. The use of high molecular weight water soluble polymeric flocculants supplied in dry powder form is of course not excluded, and the prel)ald~ion of a solution from dry powder elimin~tes the presence of the oil constituent present in the latex form.
The synthesis of multifunctionally hydroxylated poly(acrylamides) has been 20 disclosed in Macromolecules, 1996, 29, 313-319. Terpolymers of acrylic acid/acrvlamide/N-hydroxyalkylacrylamide have been disclosed in U.S. Patent No.
4.610.305.
The following examples are presented to describe pl.,f~l~d embo-limentc and utilities of the invention and are not meant to limit the invention unless otherwise stated in the claims appended hereto.
Example 1 A partially neutralized poly(acrylic acid) backbone may be prepared in various levels of neutralization by using ~p~ l;ate amounts of caustic. Specifically, a backbone wherein the neutralization of acrylic acid is about 50% was prepared as follows using reactants in the following amounts:
React~t Amollnt (g) Escaid 110 304.000 Span 80 30.000 ~rk~mid NOA 15.000 Hypermer P~246 3.000 Acrylic Acid 229.940 Deionized Water 277.690 Versene 0.100 Sodium Formate 0.030 Sodium Hydroxide (50%)127.660 Vazo 64 0.580 ~() To prepare the polymer, a 1.5 liter polymerization reactor was equipped with a mechanical stirrer, an addition funnel, a nitrogen inlet, a thermocouple, and a condenser tltted with a nitrogen outlet. Escaid 110 (available from Exxon in New Jersey), ~5 I l! permer (available from ICI Americas in Wilmington, Delaware), and ~l~rk~rnid NOA
(a~ailable from Mclntyre Group Ltd, in University Park, Illinois) and Span 80 (available from ICI Americas in Wilmington, Delaware) were weighted out in a beaker and warmed to 45~C. After 10 - 15 minutes a clear solution was obtained, and it was transferred into the polymerization reactor. Acrylic acid and deionized water were taken in a beaker and cooled to 5~C.
To the cooled and stirred solution of monomers, caustic was added dropwise, while the t~ .c.dLulc was ,~ ed below 25~C. Neutralization of acrylic acid was 5 continued until the pH was about 3.5 - 4Ø Next, the monomer solution was transferred into the reactor and stirred at 1200 rpm for 30 minlltes and the reactor was heated to 33-36~C. After 30 minutes stirring, the reactor was heated to 43-44~C. Versene (available from Dow Chemicals in Midland, Michigan) and Vazo 64 (available from DuPont in Wilmington, Delaware) were added. The reactor was held at 4445~C for four hours and 10 then at 60-63~C for l hour. The reactor was then cooled and the product transferred to storage.
The product formed had the following characteristics:
Polymer Composition of NaAc/AA 50/50 mole %
RSV (~ 0.045% in 1 M NaNO3 20-40 dL/g Example 2 A 20/80 mole % AcAm/NaAc (acrylamide/sodium acrylate) copolymer backbone may be prepared in various levels of neutralization by using ~lol,l;ate amounts of 20 caustic. Specifically, a backbone wherein the neutralization of acrylic acid is about 50%
was prepared as follows using reactants in the following amounts:
Reactant ~mollnt (~,) Escaid 110 271.819 Span 80 12.910 ~l~r~mid NOA 12.910 Hypermer 2.640 Acrylamide (48%) 97.440 Acrylic Acid 187.690 Deionized Water 280.830 Versene 0.190 Sodium Formate (10%)0.300 Boric Anhydride 2.620 Sodium Hydroxide (50%)130.360 Vazo 64 0.275 Vazo 52 0.016 To prepare the polymer, a 1.5-liter polymerization reactor was equipped with a mechanical stirrer, an addition funnel, a nitrogen inlet, a thermocouple, and a condenser fitted with a nitrogen outlet. Escaid 110, Hypermer, Span 80 and ~ mid NOA
(available from McIntyre Group Limited in Ul~iv~l~ily Park, Illinois) were weighed out in a beaker and warmed to 45~C. After 10 - 15 minl~tt?c, a clear solution was obtained, and 15 it was transferred into the polymerization reactor. Next, an acrylamide solution, acrylic acid, and deionized water were taken in a beaker and cooled to 5~C. To the cooled and stirred solution of monomers, caustic was added dropwise, while the telll~ldl~e was maintained below 25~C. Neutralization of acrylic acid was continued until the pH was about 5.1 - 5.3. Subsequently, the monomer solution was transferred into the reactor and ' 0 stirred at 1200 rpm for 30 minutes while the reactor was heated to 33 - 36~C. After 30 minutes stirring, the reactor was heated to 43 - 44~C. Versene, boric anhydride, Vazo 52, ~nd Vazo 64 were added. The reactor was held at 44 - 45~C for four hours and then at 60 - 6 ~~C for I hour. The reactor was then cooled and the product transferred to storage.
The product formed has the following characteristics:
~5 Polymer Composition NaAc/AcAm 80/20 mole %
RSV ~ 0.045% in lM NaNO3 40 - 70 dL/g Example 3 A 10/90 mole % AcAmlNaAc copolymer backbone may be plepa,ed in various levels of neutralization by using app,ol,liate amounts of caustic. Specifically, a backbone - - wherein the neutralization of acrylic acid is about 50% was ~,epdled as follows ~ltili7ing reactants in the following amounts:
React~nt ~monnt (~) Escaid 110 278.92 Span 80 13.20 ~r~mid NOA 13.20 Hypermer 2.640 Acrylarnide (48.6%)47.358 Acrylic Acid 217.259 Deionized Water 289.259 Versene 0.190 Sodium Formate (10%)0.300 Boric Anhydride 2.000 Sodium Hydroxide (50%)130.360 Vazo 52 0.028 Vazo 64 0.280 30% Sodium Thiosulfate10.00 To prepare the polymer, a 1.5 liter polymerization reactor was equipped with a mechanical stirrer, an addition funnel, a nitrogen inlet, a thermocouple, and a condenser fitted with a nitrogen outlet. Escaid 110, Hypermer, Span 80 and ~r~mid NOA wereweighed out in a beaker and warmed to 45~C. After 10 - 15 minntes, a clear solution was obtained, which was transferred into the polymerization reactor. Next, an acrylamide solution. acrylic acid, and deionized water were taken in a beaker and cooled to 5~C. To the cooled and stirred solutlon of monomers, caustic was added dropwise, while the temperature was m~int~in~d below 25~C. Neutralization of acrylic acid was continued until the pH was about 5.1 - 5.3. Subsequently, the monomer solution was transferred into the reactor and stirred at 1200 rpm for 30 minutes while the reactor was heated to 33 - 36~C. After 30 mim-tes of stirring, the reactor was heated to 43 - 44~C. Versene, boric anhydride, Vazo 52, and Vazo 64 were added. The reactor was held at 44 - 45~C for four hours and then at 60-- 63~C for 1 hour. Lastly, the reactor was cooled and the product transferred to storage. The product formed had the following characteristics:
Polymer Composition NaAc/AcAm 90/10 mole percent RSV ((~ 0.045 % in 1 M NaNO3 40 - 70 dL/g Example 4 The synthesis of AcAm/NaAc/N-(trishydroxymethyl)methyl acrylamide terpolymer was effected with the following reactants in the following amounts:
React~nt ,~molmt (P) Poly(AcAm/NaAc), 10/90 mole % latex of Example 3 100.00 Tris-hydroxymethylaminomethane 10.00 Escaid 110 20.00 Brij 93 1.00 Span 80 2.50 Deionized Water 25.00 Sodium Hydroxide (50%) 0.50 o To prepare the polymer, Escaid 110, Span 80, and Brij 93 (available from ICI
Americas in Wilmington, Delaware) were mixed in a beaker. AcAm/NaAc latex formed according to the procedure described in Example 3 was added into the beaker and stirred f'c)r 15 minutes. Next, Tris-hydroxymethylaminomethane (available from Angus '5 Chemical Co.. in Buffalo Grove, Illinois) was powdered and added into DI water kept ~ell stirred at 25~C. The stirring was continued until a clear solution was obtained (about 5 - 10 minutes). Then, an aqueous solution of Tris-hydroxymethylaminomethane was added dropwise into the AcAm/NaAc latex mixture with vigorous stirring over a period of 15 minutes. Afterwards, the solution was stirred for another 15 minlltes The pH of the reaction mixture was measured using water-wet pH strips. Aqueous caustic was added to adjust ~e pH to about 5.5. Next, ~e reaction ~ c was transferred into a 300 mL Parr reactor with a pressure rating of at least 800 psi. The reactor then was assembled and purged with nitrogen for 60 minnt~s. The Parr reactor was then slowly heated to 5 1 30~C (or above, as the case may be) and held at that te~llp~,laLu~e for 4 hours.
Afterwards, the reactor was cooled to room tcl~ cl~ and the ~cs~ule released. The product was then transferred to storage.
13C NMR confirmed product formation. The content of N-(trishydroxymethyl)methyl AcAm was 7 mole %. The product composition of the 10 AcAm/N-(trishydroxymethyl)methyl acrylamide/NaAc terpolymer was 1/7/92 mole %, referred to as Polymer B.
Example 5 The synthesis of a NaAc/N-(trishydroxymethyl)methyl acrylamide copolymer was 15 effected in the following manner with the reactants in the amounts listed below:
Reactant Amol-nt (~) Poly(Acrylic Acid) ' of Example 1 100.00 Tris-hydroxymethylaminomethane1 0.00 ~0 Escaid 110 20.00 Brij 93 1.00 Span 80 2.50 Deionized Water 25.00 Sodium Hydroxide (50%) 1.5 To prepare the copolymer, Escaid 110, Span 80, and Brij 93 were mixed in a beaker. Then, poly(acrylic acid) latex formed according to the procedure described in Example 1 was added into the beaker and stirred for 15 mimltes Tris-hydroxymethylaminomethane was powdered and added into DI water kept well stirred at ~-~ 25~C. The stirring was continued until a clear solution was obtained (about 5 -10 minutes). The aqueous solution of Tris-hy~llo~ylllethylaminom~th~n~ was then added 5 dropwise into the poly(acrylic acid) lllixLule with vigorous stirring over a period of 15 mimltes Afterwards, it was stirred for another 15 minllt~s The pH of the reaction llliX~ was measured using water-wet pH strips.
Aqueous caustic was added to adjust the pH to about 5.5. The reaction ~lliX~ was next transferred into a 300mL Parr reactor with a pl~S~ rating of at least 800 psi. The 10 reactor was assembled and purged with nitrogen for 60 ...i....l~s, then slowly heated to 1 40~C (or above, as the case may be) and held at that l~ p~ e for 2 hrs (or more, as - the case may be). Afterwards, the reactor was cooled to room temperature and the pressure released. The product was then transferred to storage.
C13 NMR analysis confirmed the product structure. The product composition of 15 the NaAc/N-(trishydroxymethyl)methyl acrylarnide copolymer was 94/6 mole percent.
Example 6 The synthesis of an AcAm/NaAc/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate terpolymer was effected in the following manner with reactants u~ilized in the following amounts:
React~nt Amol-nt (g,) 90/10 mole % NaAc/AcArn of Example 3 150.0
Following a tre~trn~nt with sodium hydroxide and ~ubse~luent washes of the pulp, the alkaline extract pulp may be further chlorinated with chemicals such as calcium or - sodium hypochlorite. During this stage, the pH is m~int~in~d at between 10 - 11. After washing, the pulp may then be further chlorinated in another stage with aqueous chlorine 5 dioxide, and washed again.
In some bleach plants, the final blç~ching stage is a hydrogen peroxide bleaching stage. The main purpose of this stage is to stabilize the final ble~ching brightness and perhaps to raise the brightn~s~ The pH of the hydrogen peroxide ble~hing stage is m~int~ined at from 9 - 12.
Bleaching often adversely affects pulp strength. For example, the chlorination stage converts most of the colored lignin which remains after the initial pulping or digestive process to chlorinated lignin derivatives which are partially soluble in acidic chlorine solution and particularly soluble in alkaline extraction liquors. Such stages are also referred to as a delignification stage. Nevertheless, destructive oxidation also occurs hich reduces the length of the cellulosic molecule; and, accordingly, reduces the strength and the viscosity of the pulp. The competition between brightnes~ and pulp strength (often measured as pulp viscosity) has been of particular concern in the paper hldustry and has been primarily responsible for the proliferation of the various bleaching se~uences. Brightness can be increased by increasing either the number of bleaching ~() stel~s used or by increasing the arnount of bleaching chemical used. Among treatments for increasing brightness include thiourea dioxide as disclosed in U.S. Patent No.
4.~ 14.780 and poly(acrylic acid) as disclosed in U.S. Patent No. 4,255,233. However, this results in a decrease of pulp strength and an increase in the cost of chemicals used.
Furthermore, as will be ~liscll~sed below, increasing the number of chlorination stages presents the paper m~nllf~c~tllrer with a potential environm~nt~l hazard.
- Regardless of the sequence used, the buL~ of cellulose ble~hing still is performed using some combination of chlorination and ~lk~lin~- extraction. However, chlorination is S not an environment~lly friendly process. Chlorination produces dioxin which is considered by many local and national agencies to be a toxic substance which is hazardous to the environrnent. In fact, extremely strict controls have been placed on the discharge of dioxin into the environment. Accordingly, many paper producers are looking to chlorine-free blç~clling processes.
To further complicate the delignification and ble~hing process, metal cont~min~tion, such as iron, m~ng~n.ose and copper illlelrt le with several of ble~ching stages, such as, peroxide ble~ching, chlorine ble~ching, chlorine dioxide ble~hing, and oxygen delignification. For example, in oxygen delignification and peroxide ble~ehing, not only does the iron form color bodies under ~Ik~line conditions, but the iron catalyses I ~ the decomposition of the cellulose.
Currently, a number of chemicals are being used to remove these metals from the cellulosic pulp. Particularly, chelating amines have been used to improve pulp brightness through the removal of metallic impurities. United States Patent No. 4,298,428 discloses se~eral chelating amines for accomplishing this. Other chelating compounds used in the 20 industry include nitrilotriacetic acid (NTA). ethylene~ minetetraacetic acid (EDTA), and diethylenetriaminepentaacetic acid (DTPA). These chemicals, often referred to as chelants. are added immediately before the bleaching stage, but after the aqueous pulp slurry has been acidified. The pulp must be acidified since the chelating chemicals presently used in the industry, such as EDTA, NTA and DTPA, will not remove metal h~ ies at alk~line pHs, particularly above pH 8. NTA is considered by some authorities to be hazardous and its discharge into the environment is closely controlled.
Since these chel~ting chemicals do not function above a pH of about 8, several 5 problems are created for the industry. The first problem is that an additional acidification step is always necess~ry when these chelating chemicals are added after an alkaline extraction, but before the next ble~ching stage. This additional acidifying step is costly to the paper producer. Moreover, the acidifying chemicals are potentially hazardous to paper mill workers.
A second problem caused by these chelating chemicals is that they prevent the paper-making industry from switching to a chlorine-free b1earlling process. In more detail. chlorination is acidic and these prior art chelating chemicals are only effective in an acidic medium. In contrast, the chlorine-free ble~ching stages, such as oxygen deli~nification, and hydrogen peroxide ble~ching, are ~lk~lin~ . Since c~~ ly available I j chelating chemicals do not work well in ~lk~line environments, additional acidifying steps must be added to the process. Even with the addition acidifying steps, these prior art chelant chemicals do not work throughout the entirety of the process since the non-chlorine processes are conducted under alkaline conditions. Accordingly, new treatments are necessary for removing metals from chemically produced pulp.
~0 ln light of the disadvantages of the prior art, it would advantageous to provide an agent which would increase brightness by removing the metallic hl~pul;~ies in the pulp at an alkaline pH above 7. It would be further advantageous to provide a treatment which would increase brightness and also increase pulp strength, as measured by viscosity. It would be a still further advantage to provide a tre~tmrl t which would elimin~te the need for chlorine ble~rhing stages.
- Snmm~ry of the Invpntion The invention is a method for ameliorating oxygen-based treatments of cellulosic 5 materials in aqueous systems compri~ing adding to an aqueous system cont~ining cellulosic materials an effective stabilizing amount of a compound or a combination of compounds which may include a polymer. The invention is also three novel grafted polymers.
Description of the Invention The invention is a method for ameliorating oxygen-based treatments of cellulosic materials in aqueous systems comprising adding to an aqueous system cont~ining cellulosic materials an effective oxygen-based treatment stabilizing amount of a compound selected from the group consisting of tris(hydroxymethyl)aminomethane, N-alkyl dimethyl benzyl ammonium chloride, N-dialkyl methyl benzyl ammoniurn chloride 15 and combinations thereof.
The oxygen-based treatment may be selected from the group con~i~ting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide ble~çhing and pressurized peroxide bleaching. The aqueous system may be a pulp and paper system. From about 0.0001 to about 2.0 percent by 20 weight of compound may be added based on the dry weight of the cellulosic material.
Preferably. from about 0.01 to about 1.0 percent by weight of compound may be added based on the dry weight of the cellulosic material. Most preferably, from about 0.1 to about 0.8 percent by weight of compound may be added based on the dry weight of the cellulosic material.
~-~ The invention is also a method for ameliorating oxygen-based treatments of cellulosic m~tPri~l~ in aqueous systems compri~ing adding to an aqueous system 5 co~ g cellulosic materials an effective oxygen-based tre~tm~nt stabilizing amount of a combination of:
a) diethylenetriaminepent~etic acid and b) a second compound selected from the group co~ tiny of citric acid, sodium gluconate, sodium glucoheptonate, ethylen~ acetic acid, tris 10 (hydroxymethyl)aminomethane, and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride.
The oxygen-based tre~tment may be selected from the group con~i~ting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide ble~ching and ples~u~ized peroxide ble~ching The aqueous I ~ svstem may be a pulp and paper system. The mole ratio of diethylenetri~minepentaacetic acid to the second compound may be from 0.001: 99.999 to 99.999:0.001. Preferably, the ratio may be 0.1 to 99.9 to 99.9 to 0.1. Most preferably, the ratio may be 1.0 to 99 to 99 to ]Ø
The invention is also a method for ameliorating oxygen-based treatments of ~0 cellulosic materials in aqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based tre~tm~nt stabilizing amount of a combination of:
a) citric acid and b) a second compound selected from the group con~i~tin~ of sodium gluconate, sodium glucoheptonate, ethylen~ minPt~l~dac~lic acid, tris-(hydroxymethyl)aminomethane, and a combination of N-alkyl dimethyl benzyl 5 ammonium chloride and N-dialkyl methyl benzyl ammonium chloride.
The oxygen-based treatment may be selected from the group con~i~ting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide ble~hing and l~les~ul;zed peroxide ble~ching The aqueous system may be a pulp and paper system. The mole ratio of citric acid to the second compound may be from 0.001:99.999 to 99.999:0.001. Preferably, the ratio may be 0.1 to 99.9 to 99.9 to 0.1. Most preferably, the ratio may be 1.0 to 99 to 99 to 1Ø
The invention is also a method for ameliorating oxygen-based tre~tm~nt~ of cellulosic materials in aqueous systems compri~ing adding to an aqueous system containing cellulosic materials an effective oxygen-based treatment stabilizing amount of 15 a combination of:
a) sodium gluconate and b) a second compound selected from the group consisting of sodium glucoheptonate, ethylene~ minetetraacetic acid, tris(hydroxymethyl)aminomethane, and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl ~0 henzyl ammonium chloride.
The oxygen-based treatment may be selected from the group consisting of oxygen delignification oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide bleaching and pressurized peroxide ble~ching The aqueous system may be a pulp and paper system. The mole ratio of sodium gluconate to the second compound may be from 0.001: 99.999 to 99.999: 0.001. Preferably, the ratio - may be 0.1 to 99.9 to 99.9 to 0.1. Most preferably, the ratio may be 1.0 to 99 to 99 to 1Ø
The invention is also a method for ameliorating oxygen-based tre~tmentc of -5 cellulosic materials in aqueous systems compri~ing adding to an aqueous system containing cellulosic materials an effective oxygen-based Ll~ .,.rnt stabilizing amount of a combination of:
a) ethylçn~ nninetetraaceticacid, and b) tris(hydroxymethyl)alllh~ lethane, and a combination of N-alkyl dimethyl 10 benzyl ammonium chloride and N-dialkyl methyl ammonium chloride.
The oxygen-based treatment may be selected from the group consisting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-~ided extraction, peroxide ble~ching and pressurized peroxide ble~c-hing. The aqueous system may be a pulp and paper system. The mole ratio of ethylene ~ mine tetraacetic 1~ acid to the second compound may be from 0.001: 99.999 to 99.999:0.001. Preferably, the ratio may be 0.1 to 99.9 to 99.9 to 0.1. Most preferably, the ratio may be 1.0 to 99 to )~ to 1 0 The invention is also a method for stabilizing peroxide treatments in aqueous p;lper production streams containing kraft pulp, peroxide, m~n~n~se and iron comprising ~() the step of adding to the aqueous paper production stream co~ h.g kraft pulp, peroxide, manganese and iron. wherein an equal or greater amount of iron is present than manganese. an effective peroxide-stabilizing amount of a combination selected from the group consisting of: poly(acrylamide/sodium acrylatelN-(trishydroxymethyl)methyl acrylamide)/diethylenetri~minepent~etic acid, poly(acrylamide/sodium acrylatelN-(trishydroxymethyl)methyl acrylamide)/citric acid, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, 5 poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/ethylenPtli~minetetraacetic acid, diethylenet,;al"inepentaacetic acid/a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, diethylenetriall,hlep~ cetic acid/
ethylene~ minetetraacetic acid, citric acid/a combination of N-alkyl dimethyl benzyl 10 ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, citric acid/sodium glucoheptonate, citric acid/ethylenP~ mil-eteLIdacetic acid, sodium gluconate/sodium glucoheptonate, sodium gluconate/ethylenP~ minetetraacetic acid and a combination of N~-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride/sodium glucoheptonate.
I ~ The invention is also a method for stabilizing peroxide treatments in aqueous paper production streams cont~ining peroxide, kraft pulp, m~ng~nPse and iron comprising the step of adding to the aqueous paper production stream cont~ining peroxide, kraft pulp, manganese and iron, wherein an equal amount or lower of iron is present than manganese. an effective peroxide-stabilizing amount of a combination selected from the ~0 group consisting of: poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)tdiethylenetriaminepentaacetic acid, poly(acrylamide/sodium acrylatetN-(trishydroxymethyl)methyl acrylamide)/a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, poly(aspartic acid)/citric acid, poly(aspartic acid)/sodium glucoheptonate, poly(aspartic acid)/ethylene~i~minPtetraacetic acid, diethylenetri;.."i"cpent~r,etic acid/citric acid and diethylenetri~minPpent~retic acid /sodium gluconate.
The invention is also a method for stabilizing peroxide tre~tment~ in aqueous 5 paper production streams col~ g peroxide, mechanical pulp, m~ng~nPse and iron, compri~inp the step of adding to the aqueous paper production streams cont~ining peroxide, mechanical pulp, m~ng~nPse and iron, wh~reill an equal or greater amount of iron is present than m~ng~nese, an effective peroxide-stabilizing amount of a combination selected from the group consisting of: poly(acrylamide/sodium acrylate/N-l O (trishydroxymethyl)methyl acrylamide)/sodiurn gluconate, poly(acrylamide/sodiumacrylate/N-(trishydroxymethyl)methyl acrylamide)/sodium glucoheptonate, diethylenetriaminepentaacetic acid/sodium gluconate, diethylenetri~mil,~pclll~acetic acid /a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, diethylenetriaminepentaacetic acid/sodiurn glucoheptonate, I ~ citric acid/a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, citric acid/sodium glucoheptonate, sodium s.luconate/sodium glucoheptonate, sodiurn gluconate/ethylene~ minetetraacetic acid and ~ combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl henzyvl ammonium chloride/ethylene~ minetetraacetic acid.
~O The invention is also a method for stabilizing peroxide treatments in aqueous paper production streams cont~ining peroxide, mechanical pulp, m~ng~nPse and iron, comprising the step of adding to the aqueous paper production stream cont~ining peroxide. mechanical pulp, m~ng~nese and iron, wherein an equal or lower amount of iron is present than m~ng~nese, an effective peroxide-stabiliziIrg arnount of a combination selected from the group con~i~ting of: poly(acrylarr.ude/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/sodium gluconate, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/a combination of N-alkyl dimethyl 5 benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylarnide)/ethylen~ minetetraacetic acid, poly(aspartic acid)/ethylene.li~mintotetraacetic acid, diethylenetriaminep~nt~.etic acid /citric acid, diethylenetriarninepentaacetic acid/sodium gluconate, diethylenetriaminepentaacetic 10 acid/a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, diethylenetriaminep~nt~cetic acid/sodium glucoheptonate, citric acid/ethylene.1i~minetetraacetic acid and sodium gluconate/a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzvl ammonium chloride.
The invention is also a method for ameliorating oxygen-based treatments of cellulosic materials in aqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based tre~tment stabilizing amount of a water-soluble polymer selected from the group consisting of poly(aspartic acid), poly(dithiocarbamate), poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl ~0 acrvlamide), poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate). poly(sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), poly(sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate) and poly(acrylamide/sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate).
- The oxygen-based treatment may be selected from the group consisting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-5 aided extraction, peroxide bleaching and pres~ ed peroxide ble~rhing. From about 0.001 to about 2 percent by weight of water-soluble polymer may be added based on the dry weight of the cellulosic material. The aqueous system may be a pulp and paper system.
The water-soluble polymer may be poly(acrylarnide/sodium acrylate/N-10 (trishydroxymethyl)methyl acrylamide), and the mole ratio of acrylamide to sodiumacrylate to N-(trishydroxymethyl)methyl acrylamide may be from 0:1:99 to 10:60:30 and the molecular weight may be from 1,000 to 10,000,000. The water-soluble polymer may be poly(acrylamide/ sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate) and the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(3,4-I ~ dihvdroxyphenyl) methane sulfonate may be from 0:10:90 to 10:60:30 and the molecular ~-eight may be from 1,000 to 10,000,000. The water-soluble polymer may be r)oly(acrylamide/sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate and the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(2-hydroxyphenyl) methane sulfonate may be from 0:10:90 to 10:60:30 and the molecular ~0 ~eight may be from 1.000 to 10,000,000.
The invention is also a method for ameliorating oxygen-based treatments of cellulosic materials in aqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based tre~tm~nt stabilizing amount of:
a) a compound selected from the group con~i~ting of diethylenetti~minPpent~cetic acid, citric acid, sodium gluc~n~te, sodium glucoheptonate, ethylene~ minetetraacetic acid, tris(hydroxymethyl)aminometh~ne, a combination of N-alkyl dimethyl ben7yl ammonium chloride and N-dialkyl methyl benzyl ammonium 5 chloride and b) a water-soluble polymer selected from the group consisting of poly(aspartic acid), poly(dithiocarbamate), poly(acrylamide/sodium acrylate/N-(tris-hydroxymethyl)methyl acrylamide), poly(acrylamide/sodium acrylate/sodium acrylarnido(3,4-dihydroxyphenyl) methane sulfonate), poly(sodium acrylate/sodium 10 acrylamido(2-hydroxyphenyl) meth~ne sulfonate), poly(sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), poly(sodium acrylate/N-(tris-hydroxymethyl)methyl acrylarnide) and poly(acrylamide/sodium acrylate/sodium acrylamido(2-hydroxyphenyl) meth~ sulfonate).
The oxygen-based treatment may be selected from the group consisting of oxygen 15 delignification. oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide ble~ching and pressurized peroxide ble~ching. The aqueous system may be a pulp and paper system. The mole ratio of the compound to the water-soluble polymer may be from about 0.00001: 99.99999 to about 99.99999: 0.00001.
Preferably. the ratio may be 0.1 to 99.9 to 99.9 to 0.1. Most preferably, the ratio may be ~0 1.0 to 99 to 99 to 1Ø The water-soluble polymer may be poly(acrylamide/sodium acrvlate/N-(trishydroxymethyl)methyl acrylamide) and the mole ratio of acrylamide to sodium acrylate to N-(trishydroxymethyl)methyl acrylamide may be from 0:1:99 to 10:60:30 and the molecular weight may be from 1,000 to 10,000,000. The water-soluble polymer may be poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate) and the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(3,4-dihydroxyphenyl) meth~ne sulfonate may be from 0:1:99 to 10:30:60 and the molecular weight may be from 1,000 to 10,000,000. The water-soluble 5 polymer may be poly(acrylamide/sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate) and the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(2-hydroxyphenyl) methane sulfonate may be from 0:1:99 to 10:30:60 and the molecular weight may be from 1,000 to 10,000,000.
The invention is also a water-soluble polymer of the formula 10 poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate). Preferably, the polymer may have a mole ratio of acrylamide to sodium acrvlate to sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate of from 0:1:99 to 10:30:60 and the molecular weight may be from 1,000 to 10,000,000.
The invention is also a water-soluble polymer of the formula 1~ poly(acrvlamide/sodium acrylate/sodium acrylamidomethyl(2-hydroxyphenyl) sulfonate).
Preferably. the polymer may have a mole ratio of acrylamide to sodium acrylate to so dium acrvlamido(2-hydroxyphenyl) methane sulfonate of from 0:1:99 to 10:30:60 and the molecular weight may be from 1,000 to 10,000,000.
The invention is also a water-soluble polymer of the formula poly(sodium '() acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate). Preferably, the polymer may have a mole ratio of sodium acrylate to sodium acrylamido(2-hydroxyphenyl ) methane sulfonate of from 99:1 to 60:40 and the molecular weight may be from 1.000 to 10~000,000.
The invention is also a water-soluble polymer of the formula poly(sodium acrylate/N-(trishydroxymethyl)methyl acrylamide). Preferably, the polymer may have a mole ratio of sodium acrylate to N-(trishydroxymethyl)methyl acrylamide of from 99:1 to 60:40 and the molecular weight may be from 1,000 to 10,000,000.
The invention is also a water-soluble polymer of the formula poly(sodium acrylate/acrylamido(3,4-dihydroxyphenyl) methane sulfonate). Preferably, the polymer may have a mole ratio of sodium acrylate to acrylamido(3,4-dihydroxyphenyl) methane sulfonate of from 99:1 to 60:40 and the molecular weight may be from 1,000 to 10,000,000.
l O . The invention is also a method for ameliorating oxygen-based treatments of cellulosic materials in aqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based treatment stabilizing amount of a combination of sodium glucoheptonate and xylanase enzyme. The oxygen-based treatment may be selected from the group consisting of oxygen delignification, oxygen-l ~ aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide bleaching and pressurized peroxide bleaching.
The compounds of this invention may be added to pulp and paper systems at ~!arious points, including but not limited to at the brown stock washers, the oxygen delignification stage, the chlorine stage, the chlorine dioxide stage, the Q-step, the extraction stage. the oxygen-aided extraction stage, the peroxide-aided extraction stage, the oxygen/peroxide-aided extraction stage, the peroxide stage, after the peroxide stage to prevent reversion on the way to the paper machine, in the refiners of the pulp mill and the paper mill, in the showers to prevent plugging, and at the sodium dithionite bleaching stage.
-~ I:lle ~i~h Moleclllar We~ht Water Soluble Flocculan~~
The polymeric flocculants employed in the process of the present invention can be 5 prepared by a variety of methods. The polymers of the subject invention can be conveniently prep~ed by amidation or transamidation reactions on an existing polymer, by polymenzation of a trishydroxymethyl CO~ .g monomer, or by reaction with bisulfite, aldehyde and AcAm/NaAc polymers. It is pleselllly ~ler~,l,ed to prepare the polymers of the instant invention from water soluble copolymers of acrylamide and 10 acrylic acid or its water soluble alkali metal or ammonium salts by tr~n~m~ tion of the amide functionality on the acrylamide mer units of the polymer. The polymers useful as starting materials will generally contain from as little as l mole percent acrylamide to as high as 50 mole percent acrylamide. Preferably, the polymer will contain from 5-40 mole percent acrylamide, and most preferably, from 10-30 mole percent acrylamide. While a 15 copolvmer of acrylamide, acrylic acid and its water soluble alkali metal or ammonium salts is preferred, copolymers of methacrylamide and acrylic acid, or its alkali metal salts may also be lltili7f~d While in a presently preferred embodiment of the invention a copolymer of acrylarnide and acrylic acid is used as a starting material, other anionic or nonionic monomers can be incorporated into the starting polymer chain. Monomers of ~0 this type include but are not limited to acrylamido~lopane sulfonic acid, vinylformamide, vinyl acetate, and vinyl sulfonate. Polymers which have been derivitized in accordance with U.S. Patent 4,680,339 to include sulfonate groups may also be employed so long as sufficient unreacted amide functionality remains for the tr~n~mid~tion reaction which produces the desired functionality. Like~,vise, the polymer may be modified to include hydroxamic acid groups as taught in U.S. 4,767,540 to - Spitzer et al.
Vinyl addition polymers comprised of anionic acrylate mer units andlor N-5 sulfoalkyl (meth)acrylamide mer units, optionally together with (meth)acrylamide merunits, may be directly synthesized from the corresponding monomers by kno~vn techniques, for instance using as the sulfonate-cc,..~ g monomer the 2-acrylamido-2-methylpropane sulfonic acid, or the methacrylamide version thereof. N-sulfoalkyl (meth)acrylamide mer units can also be incorporated into an existing polymer by post-polymerization derivatization, for instance by one of the methods described in U. S.
Patent No. 4,762,894 (Fong et al.) issued Aug. 9, 1988, U. S. Patent No. 4,680,339 (Fong) issued July 14, 1987, U. S. Patent No. 4,795,789 (Fong et al.) issued Jan. 3, 1989, and U. S. Patent No. 4,604,431 (Fong et al.) issued Aug. 5, 1986, the disclosures of all of which are hereby incorporated hereinto. The sulfonated mer units of such post-polymerization derivatized polymers are generally of the sulfonate N-alkyl substituted (meth)acrylamide type.
U. S. Patent No. 5,395,897 (Hurlock et al.) issued March 7, 1995 discloses a method to post derivatized poly(acrylic acids) which can also can be used to prepare polymeric systems of this invention described herein.
U. S . Patent No. 4,678,840 (Fong et al.) issued July 7, 1987, describes a method for preparation of acrylamide polymers having ionizable phosphonate groups, and the disclosures of this patent are incorporated herein by reference. Phosphonate-cont~iring acrylamide polymers that meet the p,~fe,l.,d molecular weight ranges may possibly be ~
active in the present process ~ other anionic acrylamide polymers described above.
Non-hl~lre~;ng mer units other than (meth)acrylamide may be used, such ~
methylol acrylamide or other nonionic but polar mer units, and even nonpolar mer units 5 may be used to the extent that the presence of such mer units does not hlt~.rere with the water solubility of the polymeric flocculant. The polymeric flocculant generally should have a weight average molecular weight of at le~t about 500,000, and preferably at least about 1,000,000, and even more preferably at least about 4,000,000, or 5,000,000. The polymeric flocculant has no standard molecular weight ceiling for the purposes of the present invention, and some flocculants having molecular weights of 15,000,000 or higher may be highly useful for the present invention so long as the polymer remains water soluble or substantially water dispersible. A particularly pr~,rt;l~c;d high molecular weight water soluble anionically charged flocculant for use in this invention is polyacrylic acid in either its sodium or ammonium salt forms having a molecular weight greater than about 10,000,000.
The polymeric flocculant employed in the present invention should be water ~oluble. The water solubility characteristic preferably is defined in terms of fluidity of aqueous solutions of the polymer. By "water soluble" is meant herein, and generally, that all aqueous solution of the polymer, at the polymer actives concentration at which it is ~0 char~ed to the primary settler feed is reasonably fluid, and preferably h~ a viscosity of no more than about 5,000 to 20,000 cps Brookfield, at ambient room temperature (from about 23~ to about 26~C.). Such water solubility characteristic generally does not create a molecular weight ceiling because even an acrylamide homopolymer, substantially free of any electrolytic groups, meets such a standard at the high molecular weights that can now be provided by conventional synthesis techniques, provided the polymer is substantially Iinear. Hence the highly anionic polymeric flocculants employed in the present invention will generally be even more water soluble at a given molecular weight.
High molecular weight polymeric flocc~ nt.c of the type described above are commonly synthesized and commercially supplied in the form of water-in-oil emulsion form. Water-in-oil emulsions of the high molecular weight anionically charged polymers useful in this invention are available commercially from a variety of sources. The water-in-oil emulsion form for these types of polymers is ~l~fell~;d bec~use it permits the 10 polymer to be prepared and shipped at reasonably high concentrations (and the polymer therein is readily dispersible in water upon inversion of such emulsion by knowntechniques, which is desirable for many use applications). Water-in-oil emulsions of vinyl addition polymers are well known and are described, for instance, in U. S. Patent No. 3.284,393, Vanderhoff, and U. S. Patent No. Re. 28,474, Anderson-Frisque, and the 15 disclosures of these patents are incorporated herein by reference. The use of high molecular weight water soluble polymeric flocculants supplied in dry powder form is of course not excluded, and the prel)ald~ion of a solution from dry powder elimin~tes the presence of the oil constituent present in the latex form.
The synthesis of multifunctionally hydroxylated poly(acrylamides) has been 20 disclosed in Macromolecules, 1996, 29, 313-319. Terpolymers of acrylic acid/acrvlamide/N-hydroxyalkylacrylamide have been disclosed in U.S. Patent No.
4.610.305.
The following examples are presented to describe pl.,f~l~d embo-limentc and utilities of the invention and are not meant to limit the invention unless otherwise stated in the claims appended hereto.
Example 1 A partially neutralized poly(acrylic acid) backbone may be prepared in various levels of neutralization by using ~p~ l;ate amounts of caustic. Specifically, a backbone wherein the neutralization of acrylic acid is about 50% was prepared as follows using reactants in the following amounts:
React~t Amollnt (g) Escaid 110 304.000 Span 80 30.000 ~rk~mid NOA 15.000 Hypermer P~246 3.000 Acrylic Acid 229.940 Deionized Water 277.690 Versene 0.100 Sodium Formate 0.030 Sodium Hydroxide (50%)127.660 Vazo 64 0.580 ~() To prepare the polymer, a 1.5 liter polymerization reactor was equipped with a mechanical stirrer, an addition funnel, a nitrogen inlet, a thermocouple, and a condenser tltted with a nitrogen outlet. Escaid 110 (available from Exxon in New Jersey), ~5 I l! permer (available from ICI Americas in Wilmington, Delaware), and ~l~rk~rnid NOA
(a~ailable from Mclntyre Group Ltd, in University Park, Illinois) and Span 80 (available from ICI Americas in Wilmington, Delaware) were weighted out in a beaker and warmed to 45~C. After 10 - 15 minutes a clear solution was obtained, and it was transferred into the polymerization reactor. Acrylic acid and deionized water were taken in a beaker and cooled to 5~C.
To the cooled and stirred solution of monomers, caustic was added dropwise, while the t~ .c.dLulc was ,~ ed below 25~C. Neutralization of acrylic acid was 5 continued until the pH was about 3.5 - 4Ø Next, the monomer solution was transferred into the reactor and stirred at 1200 rpm for 30 minlltes and the reactor was heated to 33-36~C. After 30 minutes stirring, the reactor was heated to 43-44~C. Versene (available from Dow Chemicals in Midland, Michigan) and Vazo 64 (available from DuPont in Wilmington, Delaware) were added. The reactor was held at 4445~C for four hours and 10 then at 60-63~C for l hour. The reactor was then cooled and the product transferred to storage.
The product formed had the following characteristics:
Polymer Composition of NaAc/AA 50/50 mole %
RSV (~ 0.045% in 1 M NaNO3 20-40 dL/g Example 2 A 20/80 mole % AcAm/NaAc (acrylamide/sodium acrylate) copolymer backbone may be prepared in various levels of neutralization by using ~lol,l;ate amounts of 20 caustic. Specifically, a backbone wherein the neutralization of acrylic acid is about 50%
was prepared as follows using reactants in the following amounts:
Reactant ~mollnt (~,) Escaid 110 271.819 Span 80 12.910 ~l~r~mid NOA 12.910 Hypermer 2.640 Acrylamide (48%) 97.440 Acrylic Acid 187.690 Deionized Water 280.830 Versene 0.190 Sodium Formate (10%)0.300 Boric Anhydride 2.620 Sodium Hydroxide (50%)130.360 Vazo 64 0.275 Vazo 52 0.016 To prepare the polymer, a 1.5-liter polymerization reactor was equipped with a mechanical stirrer, an addition funnel, a nitrogen inlet, a thermocouple, and a condenser fitted with a nitrogen outlet. Escaid 110, Hypermer, Span 80 and ~ mid NOA
(available from McIntyre Group Limited in Ul~iv~l~ily Park, Illinois) were weighed out in a beaker and warmed to 45~C. After 10 - 15 minl~tt?c, a clear solution was obtained, and 15 it was transferred into the polymerization reactor. Next, an acrylamide solution, acrylic acid, and deionized water were taken in a beaker and cooled to 5~C. To the cooled and stirred solution of monomers, caustic was added dropwise, while the telll~ldl~e was maintained below 25~C. Neutralization of acrylic acid was continued until the pH was about 5.1 - 5.3. Subsequently, the monomer solution was transferred into the reactor and ' 0 stirred at 1200 rpm for 30 minutes while the reactor was heated to 33 - 36~C. After 30 minutes stirring, the reactor was heated to 43 - 44~C. Versene, boric anhydride, Vazo 52, ~nd Vazo 64 were added. The reactor was held at 44 - 45~C for four hours and then at 60 - 6 ~~C for I hour. The reactor was then cooled and the product transferred to storage.
The product formed has the following characteristics:
~5 Polymer Composition NaAc/AcAm 80/20 mole %
RSV ~ 0.045% in lM NaNO3 40 - 70 dL/g Example 3 A 10/90 mole % AcAmlNaAc copolymer backbone may be plepa,ed in various levels of neutralization by using app,ol,liate amounts of caustic. Specifically, a backbone - - wherein the neutralization of acrylic acid is about 50% was ~,epdled as follows ~ltili7ing reactants in the following amounts:
React~nt ~monnt (~) Escaid 110 278.92 Span 80 13.20 ~r~mid NOA 13.20 Hypermer 2.640 Acrylarnide (48.6%)47.358 Acrylic Acid 217.259 Deionized Water 289.259 Versene 0.190 Sodium Formate (10%)0.300 Boric Anhydride 2.000 Sodium Hydroxide (50%)130.360 Vazo 52 0.028 Vazo 64 0.280 30% Sodium Thiosulfate10.00 To prepare the polymer, a 1.5 liter polymerization reactor was equipped with a mechanical stirrer, an addition funnel, a nitrogen inlet, a thermocouple, and a condenser fitted with a nitrogen outlet. Escaid 110, Hypermer, Span 80 and ~r~mid NOA wereweighed out in a beaker and warmed to 45~C. After 10 - 15 minntes, a clear solution was obtained, which was transferred into the polymerization reactor. Next, an acrylamide solution. acrylic acid, and deionized water were taken in a beaker and cooled to 5~C. To the cooled and stirred solutlon of monomers, caustic was added dropwise, while the temperature was m~int~in~d below 25~C. Neutralization of acrylic acid was continued until the pH was about 5.1 - 5.3. Subsequently, the monomer solution was transferred into the reactor and stirred at 1200 rpm for 30 minutes while the reactor was heated to 33 - 36~C. After 30 mim-tes of stirring, the reactor was heated to 43 - 44~C. Versene, boric anhydride, Vazo 52, and Vazo 64 were added. The reactor was held at 44 - 45~C for four hours and then at 60-- 63~C for 1 hour. Lastly, the reactor was cooled and the product transferred to storage. The product formed had the following characteristics:
Polymer Composition NaAc/AcAm 90/10 mole percent RSV ((~ 0.045 % in 1 M NaNO3 40 - 70 dL/g Example 4 The synthesis of AcAm/NaAc/N-(trishydroxymethyl)methyl acrylamide terpolymer was effected with the following reactants in the following amounts:
React~nt ,~molmt (P) Poly(AcAm/NaAc), 10/90 mole % latex of Example 3 100.00 Tris-hydroxymethylaminomethane 10.00 Escaid 110 20.00 Brij 93 1.00 Span 80 2.50 Deionized Water 25.00 Sodium Hydroxide (50%) 0.50 o To prepare the polymer, Escaid 110, Span 80, and Brij 93 (available from ICI
Americas in Wilmington, Delaware) were mixed in a beaker. AcAm/NaAc latex formed according to the procedure described in Example 3 was added into the beaker and stirred f'c)r 15 minutes. Next, Tris-hydroxymethylaminomethane (available from Angus '5 Chemical Co.. in Buffalo Grove, Illinois) was powdered and added into DI water kept ~ell stirred at 25~C. The stirring was continued until a clear solution was obtained (about 5 - 10 minutes). Then, an aqueous solution of Tris-hydroxymethylaminomethane was added dropwise into the AcAm/NaAc latex mixture with vigorous stirring over a period of 15 minutes. Afterwards, the solution was stirred for another 15 minlltes The pH of the reaction mixture was measured using water-wet pH strips. Aqueous caustic was added to adjust ~e pH to about 5.5. Next, ~e reaction ~ c was transferred into a 300 mL Parr reactor with a pressure rating of at least 800 psi. The reactor then was assembled and purged with nitrogen for 60 minnt~s. The Parr reactor was then slowly heated to 5 1 30~C (or above, as the case may be) and held at that te~llp~,laLu~e for 4 hours.
Afterwards, the reactor was cooled to room tcl~ cl~ and the ~cs~ule released. The product was then transferred to storage.
13C NMR confirmed product formation. The content of N-(trishydroxymethyl)methyl AcAm was 7 mole %. The product composition of the 10 AcAm/N-(trishydroxymethyl)methyl acrylamide/NaAc terpolymer was 1/7/92 mole %, referred to as Polymer B.
Example 5 The synthesis of a NaAc/N-(trishydroxymethyl)methyl acrylamide copolymer was 15 effected in the following manner with the reactants in the amounts listed below:
Reactant Amol-nt (~) Poly(Acrylic Acid) ' of Example 1 100.00 Tris-hydroxymethylaminomethane1 0.00 ~0 Escaid 110 20.00 Brij 93 1.00 Span 80 2.50 Deionized Water 25.00 Sodium Hydroxide (50%) 1.5 To prepare the copolymer, Escaid 110, Span 80, and Brij 93 were mixed in a beaker. Then, poly(acrylic acid) latex formed according to the procedure described in Example 1 was added into the beaker and stirred for 15 mimltes Tris-hydroxymethylaminomethane was powdered and added into DI water kept well stirred at ~-~ 25~C. The stirring was continued until a clear solution was obtained (about 5 -10 minutes). The aqueous solution of Tris-hy~llo~ylllethylaminom~th~n~ was then added 5 dropwise into the poly(acrylic acid) lllixLule with vigorous stirring over a period of 15 mimltes Afterwards, it was stirred for another 15 minllt~s The pH of the reaction llliX~ was measured using water-wet pH strips.
Aqueous caustic was added to adjust the pH to about 5.5. The reaction ~lliX~ was next transferred into a 300mL Parr reactor with a pl~S~ rating of at least 800 psi. The 10 reactor was assembled and purged with nitrogen for 60 ...i....l~s, then slowly heated to 1 40~C (or above, as the case may be) and held at that l~ p~ e for 2 hrs (or more, as - the case may be). Afterwards, the reactor was cooled to room temperature and the pressure released. The product was then transferred to storage.
C13 NMR analysis confirmed the product structure. The product composition of 15 the NaAc/N-(trishydroxymethyl)methyl acrylarnide copolymer was 94/6 mole percent.
Example 6 The synthesis of an AcAm/NaAc/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate terpolymer was effected in the following manner with reactants u~ilized in the following amounts:
React~nt Amol-nt (g,) 90/10 mole % NaAc/AcArn of Example 3 150.0
3,4-dihydroxy benzyldehyde 5.0 Escaid 110 30.0 Brij 93 -2.00 Span 80 3.00 Deionized Water 25.00 Sodium bisulfite 7.00 To prepare the desired terpolymer, Escaid 110, Span 80, and Brij 93 were mixed in a beaker. Then an AcAm/NaAc latex formed according to the procedure in Example 3 was added into the beaker and stirred for 15 minrltes Separately, 3,4-dihydroxy benzyldehyde (available from Aldrich Chemical Co. in Milwaukee, Wisconsin) was 15 powdered and added into DI water kept well stirred at 85~C. The stirring was continued until a clear solution was obtained (about S - 10 minutes). Then sodium bisulfite was added and stirring continued for 5 minutes.
The above benzaldehyde solution was added dropwise into the latex mixture with vigorous stirring over a period of 15 minutes. Afterwards, it was stirred for another 15 20 minutes. The pH of the reaction mixture was measured using water-wet pH strips.
Aqueous caustic was added to adjust the pH to about 5.8. The reaction mixture was next transferred into a 300 mL Parr reactor with a plessu~e rating of at least 800 psi. The reactor was assembled and purged with nitrogen for 60 minutes, then slowly heated to l 50~C (or above, as the case may be) and held at that temperature for 4 hours (or more, as 25 the case may be). Afterwards, the reactor was cooled to room temperature, the pressure released and the product was then transferred to storage.
Cl3 - NMR analysis indicated the product as a NaAc/AcAm/sodium acryamido(3,4-dihydroxy~h~l,yl) methane sulfonate terpolymer having an 8712/l l mole % ratio, referred to as Polymer A.
Example 7 The synthesis of a NaAc/sodium acrylamido(2-hydroxyphenyl) methane sulfonate copolymer was effected in the following marmer with the reactants in the following amounts:
React~nt Amo--nt (~) 90/lO mole % AcAm/NaAc latex l 0 of Example 3 l 00.00 Salicylaldehyde 6.2 Escaid l lO 30.00 Brij 93 2.00 Span 80 3.00 Deionized Water 40.00 Sodium Bisulfite 7.80 To prepare the polymer, Escaid l l 0, Span 80, and Brij 93 were mixed in a beaker.
Then. a NaAc/AcAm latex prepared according to the procedure of Example 3 was added into the beaker and stirred for l 5 minutes. Salicylaldehyde (available from Aldrich 20 Chemical Co. in Milwaukee, Wisconsin) was added into DI water kept well stirred at '0~C. Sodium bisulfite was added to that solution and stirring continued for l 5 minutes.
Ne~;t. the above solution of salicylaldehyde was added dropwise into the latex mixture with v igorous stirring over a period of l 5 minutes. Afterwards, it was stirred for another l 5 minutes. The pH of the reaction mixture was then measured using water-wet pH
25 strips. Aqueous caustic was added to adjust the pH to about 5.4. Next, the reaction mixture was transferred into a 300 mL Parr reactor with a pres~we rating of at least 800 psi. The reactor was assembled and purged with nitrogen for 60 minl1tes, then slowly heated to 140~C (or above, as the case may be) and held at that t~n~el~L Ire for 4 hours (or more, as the case may be). An~ v~ds, the reactor was cooled to room temperature, the pressure released and the product was then transferred to storage.
The product was identified by C13 NMR as NaAc/sodium acrylamido(2-5 hydroxyphenyl) methane sulfonate 90/10, mole %, referred to as Polymer C.
Example 8 The synthesis of an AcAm/NaAc/sodium acrylamido(2-hydroxyphenyl) methane sulfonate terpolymer was effected in the following manner with the reactants in the following amounts:
Reactant .Ammlnt(g~
80/20 mole % NaAc/AcAm polymer of Example 2 (50% acrylic acid neutralized) 100.00 Escaid 110 20.00 Brij 93 1.00 Span 80 2.50 Deionized Water 25.00 Sodium m-bisulfite 8.00 Salicylaldehyde 8.20 To form the terpolymer. Escaid I 10, Span 80, and Brij 93 were mixed in a beaker.
Then the NaAc/AcAm lattice prepared according to Example 2 was added into the beaker and stirred for 15 minutes. Separately, sodium m-bisulfite was taken in DI water, and stirred well at ambient temperature. Salicylaldehyde was then added dropwise to the 25 bisulfite solution over a period of 5 minutes. The stirring was continued until a clear solution was obtained (about 5-10 minutes). This salicylaldehyde/sodium bisulfite adduct solution was then added dropwise into the NaAc/AcAm oil mixture with vigorous stirring over a period of 15 minutes. Afterwards, it was stirred for another 15 minllte while the pH of the reaction ~ Lul~ was measured using water-wet pH strips and - adjusted to about 5.5 Next, the reaction mixture was transferred into a 300 mL Parr reactor with a ~ S~ e rating of at least 800 psi and was purged with nitrogen for 60 S minutes, followed by slowly heated to 140~C and holding at that temperature for 4 hours.
Afterwards, the reactor was cooled to room temperature and the ~les~ e released.
NMR characterization indicated the composition of the product to be NaAc/AcArn/sodium acrylamido(2-hydroxyphenyl) methane sulfonate in an 82/2/16 mole %. The RSV was 18.3 dL/g in 1 M NaNO3 for 0.045 % polymer.
10 Example 9 The synthesis of N-(trishydroxy methyl)methyl acrylamide/sodium acrylate (10/90 mole %) copolymer was effected in the following manner with the reactants in the followin~ amounts:
Reactant Amount(g) Escaid 110 156.00 Span 80 7.41 M~ck~mid NOA 1.51 Hypermer 7.41 N-(trishydroxymethyl)21.28 ~() methyl acrylamide Acrylic Acid 78.72 Deionized Water 148.18 Versene (10%) 0.50 Sodium Formate (10%)0.10 " Sodium Hydroxide (50%)78.72 Vazo 64 0.15 Vazo 52 0.02 To form the copolymer, a 1.0-liter polyrnen7~tion reactor was equipped with a mechanical stirrer, an addition funnel, a nitrogen inlet, a thermocouple, and a condenser fitted with a nitrogen outlet. Escaid 110, Hypermer, Span 80 and ~ mide NOA were weighed out in a beaker and warmed to 45~C. After 10 - 15 minl-tes, a clear solution was 5 obtained, and it was transferred into the polym~n7~tion reactor. Separately, N-(trishydroxymethyl)methyl acrylamide, acrylic acid, and deionized water were taken in a beaker and cooled to 5~C. To that cooled and stirred solution of monomers, caustic was added dropwise, while the temperature was m~int~ined below 25~C. Neutralization of acrylic acid was continued and the pH measured.
The monomer solution was transferred into the reactor and stirred at 1200 rpm for 30 minutes, followed by heating of the reactor to 33-36~C. After 30 minutes of stirring, the reactor was heated to 43-44~C, and Versene, boric anhydride, Vazo 52, and Vazo 64 were added. The reactor was held at 4445~C for four hours and then at 60-63~C for one hour. Finally, the reactor was then cooled and the product transferred to storage.
The resultant polymer had the following characteristics:
RSV: 11.33 dL/g For 0.045% polymer in lM NaNO3 Polymer solids: 20%
Polymer Composition: NaAc/ N-(trishydroxymethyl)methyl AcAm 90/10 mole %. The unique aspect of this synthesis was that the functional group of interest was 20 incorporated by polymerization, not in a post-polymerization modification procedure as indicated in the other Examples.
Example 10 To determine the effectiveness of various compounds as stabilizers, the following solutions were prepared:
A. No. 13 Water: water made by adding 208.5g CaCl2 (2H2O), 174.8g MgSO4 (7H2O), and 1 74.9g NaHCO3 to 250 gallons of DI water, to make a standard solution cont:~ining 150 ppm calcium, 75 ppm m~gn~sium, and 110 ppm alkalinity (all as calcium carbonate).
B. 10 ppm Mn Solution: made by adding one milliliter of a 10,000 ppm Mn solutionto a one liter volumetric flask using volumetric pipettes (+0.006) and diluting to one liter with No. 13 water.
l O C. 10 ppm Fe Solution: made by adding one milliliter of 10,000 ppm Fe solution to a liter volumetric flask using volumetric pipettes (+0.006) and diluting to one liter with No.
1 3 water.
D. 100 ppm Fe Solution: made by adding ten milliliters of 10,000 ppm Fe solutionto a one liter volumetric flask using volumetric pipettes (+0.006) and diluting to one liter l~ ~ ith No. 13 water.
E. Actives Solutions formed from forty 1% solutions were prepared. The solutionswere prepared by adding the appropriate amounts of the ingredients and diluting with 49.0 g of No. 13 water.
Solutions prepared above were utilized to evaluate effectiveness according to the ~0 l'ollov~ing procedure. Ninety-two grams of 10 ppm Mn solution, 0.5g sodium hydroxide solution. 3.0 g of the 1% active solution containing the specific compound to be tested, and 4.0 g hydrogen peroxide were added. The mixture was stirred for 30 seconds and then three rnilliliters of the solution were removed and the peroxide residual determined as described below. After 30 min. three more milliliters were removed and the peroxide residual deterrnin~cl again the same way.
- A titration was utilized to ~lçtçnnine the amount of peroxide residual according to the following procedure. Three milliliters of the filtrate were pipeted into a solution cont~ining 100 ml 1% potassium iodide, 3 milliliters acetic acid, and 3 drops 5%ammonium molybdate. Next, the solution was titrated with 0.1 N sodium thiosulfate.
Just before the final end-point, 5 drops of starch indicator were added. Peroxide residual was calculated according to the following formula:
g/L peroxide residual= 17 x 0.1 x rnl of thiosl-lf~t~ co~nn~ed l O ml filtrate For the purposes of these tests, a smaller decrease in peroxide (lower value) indicates that the compound is more effective as a peroxide stabilizer. The results of Table I illustrate the effectiveness of various compounds.
TABLE I
Peroxide Stability in the Presence of 10 ppm Mn Treatment % dc~. ~ase in peroxide pH
none 52.8 10.9 diethylenetriaminepenta-26.7 10.8 acetic acid polymer A' 28.9 11.1 poly(aspartic acid) 34.8 10.8 polymer B 35.2 11.0 citric acid 37.7 10.8 versene 1004 39.3 10.8 polymer C~ 40.6 10.9 poly(acrylamide/acrylic43.5 10.8 acid), 77/23 mole ratio tris(hydroxymethyl)arnino-50.7 10.9 methane poly(dithiocarbamate) 59.9 10.8 sodium gluconate 65.1 10.8 sodium glucoheptonate 67.2 10.8 I = Poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), 5 ~/871 11 mole ratio = Poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide),1192/7 mole ratio = Poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate),90/lO mole ratio ~ = avaiiable from Dow Chemical Company in Midland, Michigan 10 Example 11 The procedure described in Exarnple 10 was utilized to obtain the results of Table ith the following modifications. Ninety-two grams of 10 ppm Fe solution, 0.5g sodium hydroxide solution, 3.0 g of the l % active solution cont~inin~ the treatment chemical to be tested, and 4.0 g hydrogen peroxide were combined to form the test 15 solution.
TABLE II
Peroxide Stability in the Presence of 10 ppm Fe Tr~at~nt % dc., ~f ~e in peroxide pH
none 21.65 10.9 diethylenetri~minPpenta- 2.44 10.8 acetic acid polymer Al 1.46 10.9 poly(aspartic acid) 1.78 10.8 polymer B' 7.32 11.0 citric acid 0.97 10.7 versene 1004 1.47 10.8 polymer C' 40.56 10.9 poly(acrylamide/acrylic 0.65 10.9 acid), 77/23 mole ratio tris(hydroxymethyl) amino 0.98 10.8 methane poly(dithiocarbamate) 20.27 10.8 sodium gluconate 7.04 10.8 sodium glucoheptonate 1.34 10.7 I = Poly(acrylamide/sodium acrylate/sodium acrylarnido(3,4-dihydroxyphenyl) methane sulfonate), 5 ' 87 ' 1 I mole ratio ' = Poly(acrylamide/sodium acrylaterN-(trishydroxymethyl)methyl acrylarnide), 1192/7 mole ratio . -- Poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate), 90/10 mole ratio ~ = Available from Dow Chemical Company in Midland, Michigan 1() F.~am~)le 12 To obtain the results of Table III, one gram of oven dried kraft pulp (3.5 g wet pulp ) was placed in a 250 milliliter tripour beaker. The kraft pulp was obtained after the poin~ of' o~;ygen delignification in a Southeastern paper mill. The pulp was washed with 1 ~ ~o I . ~ater at 1% consistency (with #13 water), and filtered through a Buchner funnel unlil the first stages of drying were evident. The pulp was then covered and left under ~ acuum f or 15 minutes. Consistency of the resultant pulp was measured, and then the pulp was autoclaved for 30 minutes to destroy any bacteria.
Then 89.0 g of 10 ppm Mn solution, 0.5g sodium hydroxide solution, 3.0 g of the 1% active solution co"t~ ing the trç~tment compound to be tested, and 4.0 g hydrogen peroxide were added to form a pulp slurry and mixed 30 min. The pulp solids were then separated from the pulp slurry on a glass funnel, and ~e peroxide residual ~lçtennined on 5 the filtrate as described in Example 10.
TABLE III
Peroxide Stability in the ~ns~nce of 10 ppm Mn and Kraft Pulp Treatment % decrease in peroxide none 63.8 diethylene triamine penta- 34.5 acetic acid polymer A' 34.4 citric acid 50.7 polymer B 30.6 poly(aspartic acid) 50.7 - versene 100' 57.2 polymer C' 39.6 poly(acrylamide/acrylic 53.1 acid), 77/23 mole ratio tris(hydroxymethyl) amino- 47.0 methane poly(dithiocarbamate) 72.5 sodium gluconate 69.6 sodium glucoheptonate 77.5 quaternary ammonium 54.4 salts4 I = Poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), I 0 ' 87 ' 11 mole ratio ' - Polv(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), 1/9217 mole ratio , = Poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate), 90/10 mole ratio
The above benzaldehyde solution was added dropwise into the latex mixture with vigorous stirring over a period of 15 minutes. Afterwards, it was stirred for another 15 20 minutes. The pH of the reaction mixture was measured using water-wet pH strips.
Aqueous caustic was added to adjust the pH to about 5.8. The reaction mixture was next transferred into a 300 mL Parr reactor with a plessu~e rating of at least 800 psi. The reactor was assembled and purged with nitrogen for 60 minutes, then slowly heated to l 50~C (or above, as the case may be) and held at that temperature for 4 hours (or more, as 25 the case may be). Afterwards, the reactor was cooled to room temperature, the pressure released and the product was then transferred to storage.
Cl3 - NMR analysis indicated the product as a NaAc/AcAm/sodium acryamido(3,4-dihydroxy~h~l,yl) methane sulfonate terpolymer having an 8712/l l mole % ratio, referred to as Polymer A.
Example 7 The synthesis of a NaAc/sodium acrylamido(2-hydroxyphenyl) methane sulfonate copolymer was effected in the following marmer with the reactants in the following amounts:
React~nt Amo--nt (~) 90/lO mole % AcAm/NaAc latex l 0 of Example 3 l 00.00 Salicylaldehyde 6.2 Escaid l lO 30.00 Brij 93 2.00 Span 80 3.00 Deionized Water 40.00 Sodium Bisulfite 7.80 To prepare the polymer, Escaid l l 0, Span 80, and Brij 93 were mixed in a beaker.
Then. a NaAc/AcAm latex prepared according to the procedure of Example 3 was added into the beaker and stirred for l 5 minutes. Salicylaldehyde (available from Aldrich 20 Chemical Co. in Milwaukee, Wisconsin) was added into DI water kept well stirred at '0~C. Sodium bisulfite was added to that solution and stirring continued for l 5 minutes.
Ne~;t. the above solution of salicylaldehyde was added dropwise into the latex mixture with v igorous stirring over a period of l 5 minutes. Afterwards, it was stirred for another l 5 minutes. The pH of the reaction mixture was then measured using water-wet pH
25 strips. Aqueous caustic was added to adjust the pH to about 5.4. Next, the reaction mixture was transferred into a 300 mL Parr reactor with a pres~we rating of at least 800 psi. The reactor was assembled and purged with nitrogen for 60 minl1tes, then slowly heated to 140~C (or above, as the case may be) and held at that t~n~el~L Ire for 4 hours (or more, as the case may be). An~ v~ds, the reactor was cooled to room temperature, the pressure released and the product was then transferred to storage.
The product was identified by C13 NMR as NaAc/sodium acrylamido(2-5 hydroxyphenyl) methane sulfonate 90/10, mole %, referred to as Polymer C.
Example 8 The synthesis of an AcAm/NaAc/sodium acrylamido(2-hydroxyphenyl) methane sulfonate terpolymer was effected in the following manner with the reactants in the following amounts:
Reactant .Ammlnt(g~
80/20 mole % NaAc/AcAm polymer of Example 2 (50% acrylic acid neutralized) 100.00 Escaid 110 20.00 Brij 93 1.00 Span 80 2.50 Deionized Water 25.00 Sodium m-bisulfite 8.00 Salicylaldehyde 8.20 To form the terpolymer. Escaid I 10, Span 80, and Brij 93 were mixed in a beaker.
Then the NaAc/AcAm lattice prepared according to Example 2 was added into the beaker and stirred for 15 minutes. Separately, sodium m-bisulfite was taken in DI water, and stirred well at ambient temperature. Salicylaldehyde was then added dropwise to the 25 bisulfite solution over a period of 5 minutes. The stirring was continued until a clear solution was obtained (about 5-10 minutes). This salicylaldehyde/sodium bisulfite adduct solution was then added dropwise into the NaAc/AcAm oil mixture with vigorous stirring over a period of 15 minutes. Afterwards, it was stirred for another 15 minllte while the pH of the reaction ~ Lul~ was measured using water-wet pH strips and - adjusted to about 5.5 Next, the reaction mixture was transferred into a 300 mL Parr reactor with a ~ S~ e rating of at least 800 psi and was purged with nitrogen for 60 S minutes, followed by slowly heated to 140~C and holding at that temperature for 4 hours.
Afterwards, the reactor was cooled to room temperature and the ~les~ e released.
NMR characterization indicated the composition of the product to be NaAc/AcArn/sodium acrylamido(2-hydroxyphenyl) methane sulfonate in an 82/2/16 mole %. The RSV was 18.3 dL/g in 1 M NaNO3 for 0.045 % polymer.
10 Example 9 The synthesis of N-(trishydroxy methyl)methyl acrylamide/sodium acrylate (10/90 mole %) copolymer was effected in the following manner with the reactants in the followin~ amounts:
Reactant Amount(g) Escaid 110 156.00 Span 80 7.41 M~ck~mid NOA 1.51 Hypermer 7.41 N-(trishydroxymethyl)21.28 ~() methyl acrylamide Acrylic Acid 78.72 Deionized Water 148.18 Versene (10%) 0.50 Sodium Formate (10%)0.10 " Sodium Hydroxide (50%)78.72 Vazo 64 0.15 Vazo 52 0.02 To form the copolymer, a 1.0-liter polyrnen7~tion reactor was equipped with a mechanical stirrer, an addition funnel, a nitrogen inlet, a thermocouple, and a condenser fitted with a nitrogen outlet. Escaid 110, Hypermer, Span 80 and ~ mide NOA were weighed out in a beaker and warmed to 45~C. After 10 - 15 minl-tes, a clear solution was 5 obtained, and it was transferred into the polym~n7~tion reactor. Separately, N-(trishydroxymethyl)methyl acrylamide, acrylic acid, and deionized water were taken in a beaker and cooled to 5~C. To that cooled and stirred solution of monomers, caustic was added dropwise, while the temperature was m~int~ined below 25~C. Neutralization of acrylic acid was continued and the pH measured.
The monomer solution was transferred into the reactor and stirred at 1200 rpm for 30 minutes, followed by heating of the reactor to 33-36~C. After 30 minutes of stirring, the reactor was heated to 43-44~C, and Versene, boric anhydride, Vazo 52, and Vazo 64 were added. The reactor was held at 4445~C for four hours and then at 60-63~C for one hour. Finally, the reactor was then cooled and the product transferred to storage.
The resultant polymer had the following characteristics:
RSV: 11.33 dL/g For 0.045% polymer in lM NaNO3 Polymer solids: 20%
Polymer Composition: NaAc/ N-(trishydroxymethyl)methyl AcAm 90/10 mole %. The unique aspect of this synthesis was that the functional group of interest was 20 incorporated by polymerization, not in a post-polymerization modification procedure as indicated in the other Examples.
Example 10 To determine the effectiveness of various compounds as stabilizers, the following solutions were prepared:
A. No. 13 Water: water made by adding 208.5g CaCl2 (2H2O), 174.8g MgSO4 (7H2O), and 1 74.9g NaHCO3 to 250 gallons of DI water, to make a standard solution cont:~ining 150 ppm calcium, 75 ppm m~gn~sium, and 110 ppm alkalinity (all as calcium carbonate).
B. 10 ppm Mn Solution: made by adding one milliliter of a 10,000 ppm Mn solutionto a one liter volumetric flask using volumetric pipettes (+0.006) and diluting to one liter with No. 13 water.
l O C. 10 ppm Fe Solution: made by adding one milliliter of 10,000 ppm Fe solution to a liter volumetric flask using volumetric pipettes (+0.006) and diluting to one liter with No.
1 3 water.
D. 100 ppm Fe Solution: made by adding ten milliliters of 10,000 ppm Fe solutionto a one liter volumetric flask using volumetric pipettes (+0.006) and diluting to one liter l~ ~ ith No. 13 water.
E. Actives Solutions formed from forty 1% solutions were prepared. The solutionswere prepared by adding the appropriate amounts of the ingredients and diluting with 49.0 g of No. 13 water.
Solutions prepared above were utilized to evaluate effectiveness according to the ~0 l'ollov~ing procedure. Ninety-two grams of 10 ppm Mn solution, 0.5g sodium hydroxide solution. 3.0 g of the 1% active solution containing the specific compound to be tested, and 4.0 g hydrogen peroxide were added. The mixture was stirred for 30 seconds and then three rnilliliters of the solution were removed and the peroxide residual determined as described below. After 30 min. three more milliliters were removed and the peroxide residual deterrnin~cl again the same way.
- A titration was utilized to ~lçtçnnine the amount of peroxide residual according to the following procedure. Three milliliters of the filtrate were pipeted into a solution cont~ining 100 ml 1% potassium iodide, 3 milliliters acetic acid, and 3 drops 5%ammonium molybdate. Next, the solution was titrated with 0.1 N sodium thiosulfate.
Just before the final end-point, 5 drops of starch indicator were added. Peroxide residual was calculated according to the following formula:
g/L peroxide residual= 17 x 0.1 x rnl of thiosl-lf~t~ co~nn~ed l O ml filtrate For the purposes of these tests, a smaller decrease in peroxide (lower value) indicates that the compound is more effective as a peroxide stabilizer. The results of Table I illustrate the effectiveness of various compounds.
TABLE I
Peroxide Stability in the Presence of 10 ppm Mn Treatment % dc~. ~ase in peroxide pH
none 52.8 10.9 diethylenetriaminepenta-26.7 10.8 acetic acid polymer A' 28.9 11.1 poly(aspartic acid) 34.8 10.8 polymer B 35.2 11.0 citric acid 37.7 10.8 versene 1004 39.3 10.8 polymer C~ 40.6 10.9 poly(acrylamide/acrylic43.5 10.8 acid), 77/23 mole ratio tris(hydroxymethyl)arnino-50.7 10.9 methane poly(dithiocarbamate) 59.9 10.8 sodium gluconate 65.1 10.8 sodium glucoheptonate 67.2 10.8 I = Poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), 5 ~/871 11 mole ratio = Poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide),1192/7 mole ratio = Poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate),90/lO mole ratio ~ = avaiiable from Dow Chemical Company in Midland, Michigan 10 Example 11 The procedure described in Exarnple 10 was utilized to obtain the results of Table ith the following modifications. Ninety-two grams of 10 ppm Fe solution, 0.5g sodium hydroxide solution, 3.0 g of the l % active solution cont~inin~ the treatment chemical to be tested, and 4.0 g hydrogen peroxide were combined to form the test 15 solution.
TABLE II
Peroxide Stability in the Presence of 10 ppm Fe Tr~at~nt % dc., ~f ~e in peroxide pH
none 21.65 10.9 diethylenetri~minPpenta- 2.44 10.8 acetic acid polymer Al 1.46 10.9 poly(aspartic acid) 1.78 10.8 polymer B' 7.32 11.0 citric acid 0.97 10.7 versene 1004 1.47 10.8 polymer C' 40.56 10.9 poly(acrylamide/acrylic 0.65 10.9 acid), 77/23 mole ratio tris(hydroxymethyl) amino 0.98 10.8 methane poly(dithiocarbamate) 20.27 10.8 sodium gluconate 7.04 10.8 sodium glucoheptonate 1.34 10.7 I = Poly(acrylamide/sodium acrylate/sodium acrylarnido(3,4-dihydroxyphenyl) methane sulfonate), 5 ' 87 ' 1 I mole ratio ' = Poly(acrylamide/sodium acrylaterN-(trishydroxymethyl)methyl acrylarnide), 1192/7 mole ratio . -- Poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate), 90/10 mole ratio ~ = Available from Dow Chemical Company in Midland, Michigan 1() F.~am~)le 12 To obtain the results of Table III, one gram of oven dried kraft pulp (3.5 g wet pulp ) was placed in a 250 milliliter tripour beaker. The kraft pulp was obtained after the poin~ of' o~;ygen delignification in a Southeastern paper mill. The pulp was washed with 1 ~ ~o I . ~ater at 1% consistency (with #13 water), and filtered through a Buchner funnel unlil the first stages of drying were evident. The pulp was then covered and left under ~ acuum f or 15 minutes. Consistency of the resultant pulp was measured, and then the pulp was autoclaved for 30 minutes to destroy any bacteria.
Then 89.0 g of 10 ppm Mn solution, 0.5g sodium hydroxide solution, 3.0 g of the 1% active solution co"t~ ing the trç~tment compound to be tested, and 4.0 g hydrogen peroxide were added to form a pulp slurry and mixed 30 min. The pulp solids were then separated from the pulp slurry on a glass funnel, and ~e peroxide residual ~lçtennined on 5 the filtrate as described in Example 10.
TABLE III
Peroxide Stability in the ~ns~nce of 10 ppm Mn and Kraft Pulp Treatment % decrease in peroxide none 63.8 diethylene triamine penta- 34.5 acetic acid polymer A' 34.4 citric acid 50.7 polymer B 30.6 poly(aspartic acid) 50.7 - versene 100' 57.2 polymer C' 39.6 poly(acrylamide/acrylic 53.1 acid), 77/23 mole ratio tris(hydroxymethyl) amino- 47.0 methane poly(dithiocarbamate) 72.5 sodium gluconate 69.6 sodium glucoheptonate 77.5 quaternary ammonium 54.4 salts4 I = Poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), I 0 ' 87 ' 11 mole ratio ' - Polv(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), 1/9217 mole ratio , = Poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate), 90/10 mole ratio
4=498~~o N-alkyl dimethyl benyl ammonium chloride and 0.2% N-dialkyl methyl benyl ammonium chloride in aqueous solution 15 5 = available from Dow Chemical Co. in Midland Michigan Example 13 To obtain the results of Table IV, one gram of oven dried kraft pulp (3.5 g wet pulp) was placed in a 250 milliliter tripour beaker. Then 89.0 g of l O ppm Fe solution, 0.5g sodium hydroxide solution, 3.0 g of the 1% active solution co.-1~inil-~ the treatment
5 compound to be tested, and 4.0 g hydrogen peroxide were added to form a pulp slurry and mixed 30 min. The pulp solids were then separated from the pulp slurry on a glass funnel, and the peroxide residual detennined on the filtrate as described in Example l O.
TABLE IV
Peroxide Stability in the Presence of 100 ppm Fe and Kraft Pulp -Treatment % de~ Ae in peroxide - none 30.9 ~
diethylenetriaminepenta- 42.2 acetic acid polymer A' 28.4 poly(aspartic acid) 36.6 polymer B' 24.4 citric acid 31.4 versene 100' 26.5 polymer C~ 38.4 poly(acrylamide/acrylic 33.1 acid), 77/23 mole ratio tris(hydroxymethyl)amino- 34.5 methane sodium gluconate 27.8 sodium glucoheptonate 36.7 ql~tern~ry ammonium 31.2 salts4 5 1 = Poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), 2/871 11 mole ratio = Polv(acrvlamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), 1/9217 mole ratio , = Poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate), 90/10 mole ratio 4 = 49.8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium 10 chloride in aqueous solution = available from Dow Chemical Co. in Midland, Michigan Example 14 To obtain the results of Table V, one gram of oven dried mechanical pulp (3.4 g 15 wet pulp) was placed in a 250 milliliter tripour beaker. The mechanical pulp was obtained and prepared according to the procedure described in Example 12. Then 89.1 g of 10 ppm Mn solution, 0.5g sodium hydroxide solution, 3.0 g of the 1% active solution containing the treatment compound to be tested, and 4.0 g hydrogen peroxide were added to form a pulp slurry and mixed 30 min. The pulp solids were ~en separated from the pulp slurry on a glass funnel, and thë peroxide residual clet~rmin~d on the filtrate as - described in Example 10.
TABLE V
Peroxide Stability in the Presence of 10 ppm Mn and Mechanical Pulp Treatment ~/O dc., ~a~e in peroxide none 64.23 diethylenetriaminepenta- 40.97 acetic acid polymer A' 47.58 polymer B 43.49 citric acid 74.19 versene 100~ 72.77 polymer C~ 45.54 poly(acrylamide/acrylic 74.03 acid), 77/23 mole ratio tris(hydroxymethyl)- 65.21 aminomethane sodium glucoheptonate 79.38 polymer D' 47.43 sodium gluconate 75.29 poly(aspartic acid),1 OK 51.68 poly(aspartic acid), 18K 65.69 quaternary ammonium 78.44 salts4 I = Poly(acrvlamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), ' '87 ' 11 mole ratio ' = Polv(acrvlamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylarnide), 1/9217 mole ratio 1 () . - Poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate), 90/10 mole ratio ~ 9.8~/o N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl arnmonium chloride in aqueous solution ~ - pol~(acrylamide/sodium acrylate/acrylic acid), 20/70/10 mole ratio
TABLE IV
Peroxide Stability in the Presence of 100 ppm Fe and Kraft Pulp -Treatment % de~ Ae in peroxide - none 30.9 ~
diethylenetriaminepenta- 42.2 acetic acid polymer A' 28.4 poly(aspartic acid) 36.6 polymer B' 24.4 citric acid 31.4 versene 100' 26.5 polymer C~ 38.4 poly(acrylamide/acrylic 33.1 acid), 77/23 mole ratio tris(hydroxymethyl)amino- 34.5 methane sodium gluconate 27.8 sodium glucoheptonate 36.7 ql~tern~ry ammonium 31.2 salts4 5 1 = Poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), 2/871 11 mole ratio = Polv(acrvlamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), 1/9217 mole ratio , = Poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate), 90/10 mole ratio 4 = 49.8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium 10 chloride in aqueous solution = available from Dow Chemical Co. in Midland, Michigan Example 14 To obtain the results of Table V, one gram of oven dried mechanical pulp (3.4 g 15 wet pulp) was placed in a 250 milliliter tripour beaker. The mechanical pulp was obtained and prepared according to the procedure described in Example 12. Then 89.1 g of 10 ppm Mn solution, 0.5g sodium hydroxide solution, 3.0 g of the 1% active solution containing the treatment compound to be tested, and 4.0 g hydrogen peroxide were added to form a pulp slurry and mixed 30 min. The pulp solids were ~en separated from the pulp slurry on a glass funnel, and thë peroxide residual clet~rmin~d on the filtrate as - described in Example 10.
TABLE V
Peroxide Stability in the Presence of 10 ppm Mn and Mechanical Pulp Treatment ~/O dc., ~a~e in peroxide none 64.23 diethylenetriaminepenta- 40.97 acetic acid polymer A' 47.58 polymer B 43.49 citric acid 74.19 versene 100~ 72.77 polymer C~ 45.54 poly(acrylamide/acrylic 74.03 acid), 77/23 mole ratio tris(hydroxymethyl)- 65.21 aminomethane sodium glucoheptonate 79.38 polymer D' 47.43 sodium gluconate 75.29 poly(aspartic acid),1 OK 51.68 poly(aspartic acid), 18K 65.69 quaternary ammonium 78.44 salts4 I = Poly(acrvlamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), ' '87 ' 11 mole ratio ' = Polv(acrvlamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylarnide), 1/9217 mole ratio 1 () . - Poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate), 90/10 mole ratio ~ 9.8~/o N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl arnmonium chloride in aqueous solution ~ - pol~(acrylamide/sodium acrylate/acrylic acid), 20/70/10 mole ratio
6 = available from Dow Chemical Company in Midland, Michigan Example 15 To obtain the results of Table VI, one gram of oven dried mechanical pulp (3.4 g - wet pulp) was placed in a 250 milliliter tripour beaker. Then 89.1 g of 100 ppm ~e solution, 0.5g sodium hydroxide solution, 3.0 g of the 1% active solution cont~ining the 5 compound to be tested, and 4.0 g hydrogen peroxide were added to form a pulp slurry and mixed 30 min. The pulp solids were then separated from the pulp slurry on a glass funnel, and the peroxide residual d~ lined on the filtrate as described in Example 10.
-TABLE VI
Peroxide Stability in the Presence of 100 ppm Fe and Mechanical Pulp Treatment % decrease in peroxide none 37.23 diethylenetriaminepenta 18.94 -acetic acid polymer A' 27.59 polymer B 31.84 citric acid 27.44 versene 100~ 43.02 polymer C~ 30.11 poly(acrylamide/acrylic 36.41 acid), 77/23 mole ratio tris(hydroxymethyl)- 38.45 aminomethane sodium glucoheptonate 34.52 polymer D' 26.18 sodium gluconate 32.47 poly(aspartic acid), lOK 28.06 poly(aspartic acid), 18K 29.48 quaternary ammonium 33.73 salts4 I = Poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), ' 87 I I mole ratio Poly(acrvlamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), 119217 mole ratio . - I'ol!(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate), 90/10 mole ratio ~ = ~19.8~/o N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium I () chloride in aqueous solution poly(acrylamide/sodium acrylate/acrylic acid). 20/70/10 mole ratio ~- ~vailable from Dow Chemical Co. in Midland, Michigan F.~ample 16 l ~ To obtain the results of Table VII, one gram of oven dried mechanical pulp (3.14 et pulp) was placed in a 250 milliliter tripour beaker. Then 89.3g of high iron solution (one milliliter of 10,000 ppm Mn solution and ten milliliters of 10,000 ppm Fe solution added to a one liter volumetric flask using volumetric pipettes (+0.006) and diluted to one liter with No. 13 water), 0.5 g sodium hydroxide solution, 3.0 g of each of the 1% active solution Co~ -g the tre~t~n~nt compound to be tested, and 4.0 g - - hydrogen peroxide were added to form a pulp slurry and mixed 30 min. The pulp solids were then separated from the pulp slurry on a glass funnel, and the peroxide residual 5 determined described in Example 10.
TABLE VII
Peroxide Stability in the Presence of 10 ppm Mn, 100 ppm Fe and Mechanical Pulp Treatment ~/0 s~c~ in peroxide none 84.0 diethylenetriaminepent~cetic acid 47.1 polymer Al 46.6 polymer B' 46.8 polymer C~ 51.0 sodium gluconate 63.8 sodium glucoheptonate 76.2 poly(aspartic acid), 1 OK 59.2 poly(aspartic acid), 18K 51.8 quaternary ammonium salts~ 89.9 l O I = Poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfionate), ~ '8711 I mole ratio 2 = Poly(acrylamide/sodium acrylaterN-(trishydroxymethyl)methyl acrylamide), 1/92/7 mole ratio 3 = Poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate), so/lo mole ratio 1 = 49 8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium l S chloride in aqueous solution -Example 17 To obtain the results of Table VIII, the procedure described in Example l 7 was t1 ,7~
TABLE VIII
5Mechanical Pulp High Iron Content Compound 1 Compound 2g/L p~. uAide I . 1 1 DTPA ' --- 2.52 NaGH' --- 1.79 polymer B' --- 2.4 sodium NaGH' 4.82 glllt on~
Quats4 NaGH' 2.49 sodium EDTA~ 3.94 glllrcln ~
polymerB~ sodium 3.02 gl~ .
Citric acid Quats4 2.13 Citric acid NaGH' 2.97 DTPA' NaGH' 2.47 DTPA' Quats4 1.42 DTPA ' sodium 2.1 gll-ron ~
polymer B~ NaGH' 2.46 poly(aspartic none 2.85 acid) I = diethylenetri~ninep~nt~etic acid = poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), 119217 mole ratio ~ = ~9 8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium 1 () chloride in aqueous solution ~ = sodium nlucoheptonate 6 = elhylenediaminetetraacetic acid . CA 02216084 1997-09-22 Example 18 To obtain the results of Table IX, one g of oven dried mechanical pulp (3.14 g wet pulp) was placed in a 250 milliliter tripour beaker. Then 89.3 g of low iron solution, (one milliliter of 1 0,Q00 ppm Fe solution added to a one liter volumetric flask using 5 volumetric pipettes (i0.006) and diluted to one liter. One milliliter of this solution was added to a one liter volumetric flask with one milliliter of 10,000 ppm Mn and diluted to one liter with No. 13 water), 0.5g sodium hydroxide solution, 3.0 g of each of the 1%
active solution co.ll~ini~-g the treatment compound to be tested, and 4.0 g hydrogen peroxide were added to form a pulp slurry and mixed 30 min. The pulp solids were then 10 separated from the pulp slurry on a glass funnel, and the peroxide residual determined on the filtrate as described in Example 10.
TABLE IX
Mechanical Pulp Low Iron Content Compound I Cc ,: ~ 2 g/L p~ .v,idc . 5.40 DTPA' --- 5.95 NaGH' --- 5.16 DTPAI Citric acid 7.74 DTPA' sodium 7.16 sodium Quats4 6.99 gluconate DTPA' Quats4 6.89 polymer B' sodium 6.65 g~
polymer B' EDTAb 6.40 Poly(aspartic Quats4 6.33 acid) Poly(aspartic DTPA' 6.25 acid) polymer B' NaGH' 6.20 DTPA' sodium 6.14 gl~ron tl Poly(aspartic EDTA~ 6.06 acid) Poly(aspartic NaGH' 5.72 acid) Poly(aspartic EDTA" 5.65 acid) sodium EDTAb 5.02 gll-~orl~t~
Citric acid EDTA~ 6.01 polymer B~ ------ 5.57 I = diethvlenet~ l..i..c~ retic acid , = poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylarnide), 119217 mole ratio 1 = 49.8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium chioride in aqueous solution ~ = sodium glucoheptonate 6 = ethvlene~ rll~celic acid Example 19 - To obtain the results of Table X, one g of oven dried kraft pulp (3.14 g wet pulp) - was placed in a 250 milliliter tripour beaker. Then 89.3 g of high iron solution (one milliliter of 10,000 ppm Mn solution and ten milliliters of 10,000 ppm Fe solution were S added to a one liter volumetric flask using volumetric pipettes (+0.006) and diluted to one liter with No. 13 water), 0.5 g sodium hydroxide solution, 3.0 g of each of the 1% active solution co~ ining the tre~tm~rlt compound to be tested, and 4.0 g hydrogen peroxide were added to form a pulp slurry and mixed 30 min. The pulp solids were then separated from the pulp slurry on a glass funnel, and the peroxide residual de~ d on the filtrate 10 as described in Example 10.
TABLE X
Kraft Pulp High Iron Content Cl rorr~ 1 Compound2 g/Lp~.uAide 1 .13 DTPA ' --- 1.47 NaGH' --- 0.57 Poly(aspartic EDTA~ 2.32 acid) Poly(aspartic Citric acid 2.3 acid) polyrner B' DTPA' 2.91 polymer B' Quats~ 1.42 DTPA' sodium 1.42 gl~
DTPA' Citric acid 1.53 Poly(aspartic NaGH' 1.08 acid) Poly(aspartic - 3.74 acid) I = diethylccllia,ic~ r~tic acid 3 = poly(acrylamide/sodium acrylate/l~-(trishydroxymethyl)methyl acrylamide), 1192/7 mole ratio 4 = 49.8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium chloride in aqueous solution 5 = sodium glucoh~Jt~JIlale 6 = ethylenediami..~t~.,aacetic acid Example 20 To obtain the results of Table ~, one g of oven dried mechanical pulp (3.14 wet pulp) was placed in a 250 milliliter tripour beaker. Than 89.3 g of low iron solution (one milliliter of 10,000 ppm Fe solution added to a one liter volumetric flask using 5 volumetric pipettes (+0.006) and diluted to one liter. One milliliter of this solution was added to a one liter volumetric flask with one milliliter of 10,000 ppm Mn and diluted to one liter with No. 13 water), 0.5 g sodium hydroxide solution, 3.0 g of each of the 1%
active solution cont~ining the tre~trn~n~ compound to be tested, and 4.0 hydrogen peroxide were added to form a pulp slurry and mixed 30 min. The pulp solids were then 10 separated from the pulp slurry on a glass funnel, and the peroxide residual determined on the filtrate as described in Example 10.
TABLE XI
Kraft Pulp Low Iron Content Compound 1 Compound 2 g/L F ~ u-i~e - ----- 2.59 DTPA' --- 2.52 NaGH' --- 1.93 sodium EDTA~ 2.22 ~h~f Qns~t~
polymer B~ DTPA' 3.53 Citric acid EDTA~ 2.27 citric acid Quats4 2.23 citric acid NaGH' 2.32 DTPA ' EDTA~ 2.49 Quats4 NaGH' 2.23 polymer B~ Quats4 3.43 polymer B' DTPAI 3.53 polymer BJCitric acid 2.51 polymer B' EDTA~ 2.36 DTPA' Quats4 2.41 sodium NaGH' 2.29 F;IUCollZltf' I = diethylenetriami~ f~ic acid , = poiy[acrylamide/sodium acrylateiN-(trishydroxymethyl)methyl acrylamide], 1/92/7 mole ratio 4 = 49.8% N-alkyi dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium chloride in aqueous solution ~ = sodium glucoheptonate 6 = ethylenediaminetetraacetic acid Example 21 The experimental results of Examples 10 - 20 were statistically analyzed to further emphasize the synergistic effect of the combinations of certain compounds as stabilizers.
l ~ The ra-~ data itself is indicative of synergism, as the amount of peroxide increases when the combination treatment is added, as compared to single component treatments. This ra~ data was further manipulated using standard statistical techniques to generate a model which mathematically predicts the residual peroxide based on what active or two acti~ es are present. A coefficient which is a multiplication factor was calculated for each ~0 combination. A positive calculated coefficient for the combination of actives is further .
evidence that the combination has a greater than expected ability to preserve peroxide.
T~his positive coefficlent for the combination of actives is the proof of synergy, and is ~- indicated in the table as a "yes" if synergy exists according to the calculations, as indicated in Table-XII.
TABLE XII
Synergy Ca5- l~tions for Me~ ir~l Pulp Under High Iron Conditions Tr. ': t Re~ults Residual Compound 1 Compound2 Peroxide(g/L) Synergy 1.11 Polymer B' --- 2.4 ---Poly(aspartic acid) --- 2.85 ---DTPA ' --- 2.52 ---Citric Acid --- 3.08 ---Sodium Gluconate --- 1.38 ---QuatsV --- 0.61 ---NaGH' --- 1.79 EDTA~ 1.98 ---PolymerB~ Sodium Gluconate 3.02 yes Polymer B' NaGH' 2.46 yes DTPA' Sodium Gluconate 2.1 yes DTPA ' Quats4 1.42 yes DTPA ' NaGH' 2.47 yes Citric Acid Quats 2.13 yes Citric Acid NaGH' 2.97 yes Sodium Gluconate NaGH' 4.82 yes Sodium Gluconate EDTA" 3.94 yes Quats4 NaGH' 2.49 yes I = diethylenetriam.. ,e~ ic acid 3 = polv(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylarnide), 1/92/7 mole ratio 10 4 = 49.8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium chloride in aqueous solution ~ = sodium glucohc~,lordt~
6 = ethvlenediaminetetraacetic acid 15 Example 22 The procedure of Example 21 was utilized to obtain the results of Table XIII.
- TABLE XIII
Synergy Calculations for Mechanical Pulp Under Low Iron Conditions Treatment Results Residual Compound 1 Compound 2 P~ e (g/L)Synergy 5.4 Polyrner B' --- 5.57 ---Poly(aspartic acid) --- 5.02 DTPA ' --- 5 95 Citric Acid --- 3.63 ---Sodium Gluconate --- 3.32 ---Q ats4 3.51 ~~~
NaGH' --- 5.16 ---EDTA~ 4.82 ---PolymerB~ Sodium Gluconate 6.65 yes PolymerB' Quats4 6.20 yes Polymer B' EDTA~ 6.4 yes Poly(aspartic acid) DTPA' 6.25 yes Poly(aspartic acid) Citric Acid 6.06 yes Poly(aspartic acid) Quats4 6.33 yes Poly(aspartic acid) NaGH' 5.65 yes Poly(aspartic acid) EDTA~ 5.72 yes DTPA' Citric Acid 7.74 yes DTPA' Sodium Gluconate 7.16 yes DTPA I Quats~ 6.89 yes DTPA ' NaGH' 6.14 yes Citric Acid EDTA~ 6.01 yes ~iodium Gluconate Quats4 6.99 yes ~iod ium G luconate EDTA~ 5.02 ---I = diethvlenetriami"~ tic acid 5 8 = poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), 1/92/7 mole ratio 9.8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl chloride in aqueous solution = sodium glucoheptonate ~ - cthvlenediaminetetraacetic acid 1() Example 23 The procedure of Exarnple 21 was utilized to obtain the results of Table XIV.
TABLE XIV
Synergy Calculations for Kra~t Pulp Under High Iron Conditions ~- Tr~ --t Results Residual CG . -_lld 1Compound 2 P~ JA (g/I.) SyDergy - - - - - - 1.13 - - -Polymer B' --- 0.89 ---Poly(aspartic acid) --- 3.74 ---DTPA' --- 1.47 ---Citric Acid --- 1.96 ---Sodium Gluconate --- 2.63 ---Q ats4 0.94 ~~~
NaGH' --- 0.57 ---EDTA~ --- 1.13 yes Polymer B' DTPA' 2.91 yes Polymer B' Citric Acid 1.53 yes Polymer B' Quats4 1.42 yes Polymer B' EDTA~ 1.13 yes DTPA ' Quats4 1.47 yes DTPA ' EDTA~ 1.79 yes Citric Acid Quats 2.12 yes Citric Acid NaGH' 2.04 yes Citric Acid EDTA~ 2.83 yes Sodium Gluconate NaGH' 2.12 yes Sodium Gluconate EDTA~ 3.1 yes Quats4 NaGH' 1.45 yes I = diethvlenetriaminepe~qqAetic acid 3 = poly(acrylamide/sodium acrylateAN-(trishydroxymethyl)methyl acrylamide), 1/9217 mole ratio 4 = 49.8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium chloride in aqueous solution ~ = sodium glucoheptonate 6 = ethylenediamin~l~L-aacetic acid .
Example 24 The procedure of Example 21 was utilized to obtain the results of Table XV.
- TABLE XV
Synergy Calculations for Kraft Pulp Under Low Iron Conditions Treatment Results Residual Compound 1 Compound 2 Peroxide(g/L) Synergy 2.59 Polymer B' --- 2.53 ---Poly(aspartic acid) --- 2.11 ---DTPA' --- 2.52 ---Citric Acid --- 2.1 ---Sodium Gluconate --- 3.18 ---Quatsq --- 2.83 ---NaGH' --- 1.93 ---EDTA~ --- 3.15 ---Polymer B' DTPA' 3.53 yes Polymer B~ Quats4 3.43 yes Poly(aspartic acid) Citric Acid 3.87 yes Polv(aspartic acid) NaGH' 2.74 yes Poly(aspartic acid) EDTA~ 4.27 yes DTPA' Citric Acid 3.15 yes DTPA' Sodium Gluconate 3.32 yes -l = diethvlenetri~rninepent~retic acid = poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), 1/92/7 mole ratio ~ - ~9.8~/o ~-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium chloride in aqueous solution 1() ~=sodium~ lucoheptonate ~- ethylenediaminetetraacetic acid F.?;~ml~le 2~
Oven dried pulp, also referred to as bone dry pulp and abbreviated as ODP, is I 5 tormed under moisture-free condition. It is usually forrned by drying a known sample to a constant ~eight in a completely dry atmosphere at a t~lllpeldlule of 100~C to 105~C.
T~-o units/g oven dried pulp of xylanse and 0.1% (based on ODP) of sodium glucoheptonate would be added to a solution as described in Example 10 at pH 4.0 and let to react for 30 min in the presence and absence of metal tlcA~ nt and washed.
- Subsequently, the pH of the pulp would be adjusted to 1 1.1 and the pulp would be bleached with 1.5% peroxide on ODP for one hour. The-pulp would be washed and 5 brightn~ measured.
Changes can be made in the composition, operation and arrangement of the method of the present invention described herein without departing from the concept and scope of the invention as defined in the following claims:
-TABLE VI
Peroxide Stability in the Presence of 100 ppm Fe and Mechanical Pulp Treatment % decrease in peroxide none 37.23 diethylenetriaminepenta 18.94 -acetic acid polymer A' 27.59 polymer B 31.84 citric acid 27.44 versene 100~ 43.02 polymer C~ 30.11 poly(acrylamide/acrylic 36.41 acid), 77/23 mole ratio tris(hydroxymethyl)- 38.45 aminomethane sodium glucoheptonate 34.52 polymer D' 26.18 sodium gluconate 32.47 poly(aspartic acid), lOK 28.06 poly(aspartic acid), 18K 29.48 quaternary ammonium 33.73 salts4 I = Poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), ' 87 I I mole ratio Poly(acrvlamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), 119217 mole ratio . - I'ol!(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate), 90/10 mole ratio ~ = ~19.8~/o N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium I () chloride in aqueous solution poly(acrylamide/sodium acrylate/acrylic acid). 20/70/10 mole ratio ~- ~vailable from Dow Chemical Co. in Midland, Michigan F.~ample 16 l ~ To obtain the results of Table VII, one gram of oven dried mechanical pulp (3.14 et pulp) was placed in a 250 milliliter tripour beaker. Then 89.3g of high iron solution (one milliliter of 10,000 ppm Mn solution and ten milliliters of 10,000 ppm Fe solution added to a one liter volumetric flask using volumetric pipettes (+0.006) and diluted to one liter with No. 13 water), 0.5 g sodium hydroxide solution, 3.0 g of each of the 1% active solution Co~ -g the tre~t~n~nt compound to be tested, and 4.0 g - - hydrogen peroxide were added to form a pulp slurry and mixed 30 min. The pulp solids were then separated from the pulp slurry on a glass funnel, and the peroxide residual 5 determined described in Example 10.
TABLE VII
Peroxide Stability in the Presence of 10 ppm Mn, 100 ppm Fe and Mechanical Pulp Treatment ~/0 s~c~ in peroxide none 84.0 diethylenetriaminepent~cetic acid 47.1 polymer Al 46.6 polymer B' 46.8 polymer C~ 51.0 sodium gluconate 63.8 sodium glucoheptonate 76.2 poly(aspartic acid), 1 OK 59.2 poly(aspartic acid), 18K 51.8 quaternary ammonium salts~ 89.9 l O I = Poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfionate), ~ '8711 I mole ratio 2 = Poly(acrylamide/sodium acrylaterN-(trishydroxymethyl)methyl acrylamide), 1/92/7 mole ratio 3 = Poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate), so/lo mole ratio 1 = 49 8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium l S chloride in aqueous solution -Example 17 To obtain the results of Table VIII, the procedure described in Example l 7 was t1 ,7~
TABLE VIII
5Mechanical Pulp High Iron Content Compound 1 Compound 2g/L p~. uAide I . 1 1 DTPA ' --- 2.52 NaGH' --- 1.79 polymer B' --- 2.4 sodium NaGH' 4.82 glllt on~
Quats4 NaGH' 2.49 sodium EDTA~ 3.94 glllrcln ~
polymerB~ sodium 3.02 gl~ .
Citric acid Quats4 2.13 Citric acid NaGH' 2.97 DTPA' NaGH' 2.47 DTPA' Quats4 1.42 DTPA ' sodium 2.1 gll-ron ~
polymer B~ NaGH' 2.46 poly(aspartic none 2.85 acid) I = diethylenetri~ninep~nt~etic acid = poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), 119217 mole ratio ~ = ~9 8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium 1 () chloride in aqueous solution ~ = sodium nlucoheptonate 6 = elhylenediaminetetraacetic acid . CA 02216084 1997-09-22 Example 18 To obtain the results of Table IX, one g of oven dried mechanical pulp (3.14 g wet pulp) was placed in a 250 milliliter tripour beaker. Then 89.3 g of low iron solution, (one milliliter of 1 0,Q00 ppm Fe solution added to a one liter volumetric flask using 5 volumetric pipettes (i0.006) and diluted to one liter. One milliliter of this solution was added to a one liter volumetric flask with one milliliter of 10,000 ppm Mn and diluted to one liter with No. 13 water), 0.5g sodium hydroxide solution, 3.0 g of each of the 1%
active solution co.ll~ini~-g the treatment compound to be tested, and 4.0 g hydrogen peroxide were added to form a pulp slurry and mixed 30 min. The pulp solids were then 10 separated from the pulp slurry on a glass funnel, and the peroxide residual determined on the filtrate as described in Example 10.
TABLE IX
Mechanical Pulp Low Iron Content Compound I Cc ,: ~ 2 g/L p~ .v,idc . 5.40 DTPA' --- 5.95 NaGH' --- 5.16 DTPAI Citric acid 7.74 DTPA' sodium 7.16 sodium Quats4 6.99 gluconate DTPA' Quats4 6.89 polymer B' sodium 6.65 g~
polymer B' EDTAb 6.40 Poly(aspartic Quats4 6.33 acid) Poly(aspartic DTPA' 6.25 acid) polymer B' NaGH' 6.20 DTPA' sodium 6.14 gl~ron tl Poly(aspartic EDTA~ 6.06 acid) Poly(aspartic NaGH' 5.72 acid) Poly(aspartic EDTA" 5.65 acid) sodium EDTAb 5.02 gll-~orl~t~
Citric acid EDTA~ 6.01 polymer B~ ------ 5.57 I = diethvlenet~ l..i..c~ retic acid , = poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylarnide), 119217 mole ratio 1 = 49.8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium chioride in aqueous solution ~ = sodium glucoheptonate 6 = ethvlene~ rll~celic acid Example 19 - To obtain the results of Table X, one g of oven dried kraft pulp (3.14 g wet pulp) - was placed in a 250 milliliter tripour beaker. Then 89.3 g of high iron solution (one milliliter of 10,000 ppm Mn solution and ten milliliters of 10,000 ppm Fe solution were S added to a one liter volumetric flask using volumetric pipettes (+0.006) and diluted to one liter with No. 13 water), 0.5 g sodium hydroxide solution, 3.0 g of each of the 1% active solution co~ ining the tre~tm~rlt compound to be tested, and 4.0 g hydrogen peroxide were added to form a pulp slurry and mixed 30 min. The pulp solids were then separated from the pulp slurry on a glass funnel, and the peroxide residual de~ d on the filtrate 10 as described in Example 10.
TABLE X
Kraft Pulp High Iron Content Cl rorr~ 1 Compound2 g/Lp~.uAide 1 .13 DTPA ' --- 1.47 NaGH' --- 0.57 Poly(aspartic EDTA~ 2.32 acid) Poly(aspartic Citric acid 2.3 acid) polyrner B' DTPA' 2.91 polymer B' Quats~ 1.42 DTPA' sodium 1.42 gl~
DTPA' Citric acid 1.53 Poly(aspartic NaGH' 1.08 acid) Poly(aspartic - 3.74 acid) I = diethylccllia,ic~ r~tic acid 3 = poly(acrylamide/sodium acrylate/l~-(trishydroxymethyl)methyl acrylamide), 1192/7 mole ratio 4 = 49.8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium chloride in aqueous solution 5 = sodium glucoh~Jt~JIlale 6 = ethylenediami..~t~.,aacetic acid Example 20 To obtain the results of Table ~, one g of oven dried mechanical pulp (3.14 wet pulp) was placed in a 250 milliliter tripour beaker. Than 89.3 g of low iron solution (one milliliter of 10,000 ppm Fe solution added to a one liter volumetric flask using 5 volumetric pipettes (+0.006) and diluted to one liter. One milliliter of this solution was added to a one liter volumetric flask with one milliliter of 10,000 ppm Mn and diluted to one liter with No. 13 water), 0.5 g sodium hydroxide solution, 3.0 g of each of the 1%
active solution cont~ining the tre~trn~n~ compound to be tested, and 4.0 hydrogen peroxide were added to form a pulp slurry and mixed 30 min. The pulp solids were then 10 separated from the pulp slurry on a glass funnel, and the peroxide residual determined on the filtrate as described in Example 10.
TABLE XI
Kraft Pulp Low Iron Content Compound 1 Compound 2 g/L F ~ u-i~e - ----- 2.59 DTPA' --- 2.52 NaGH' --- 1.93 sodium EDTA~ 2.22 ~h~f Qns~t~
polymer B~ DTPA' 3.53 Citric acid EDTA~ 2.27 citric acid Quats4 2.23 citric acid NaGH' 2.32 DTPA ' EDTA~ 2.49 Quats4 NaGH' 2.23 polymer B~ Quats4 3.43 polymer B' DTPAI 3.53 polymer BJCitric acid 2.51 polymer B' EDTA~ 2.36 DTPA' Quats4 2.41 sodium NaGH' 2.29 F;IUCollZltf' I = diethylenetriami~ f~ic acid , = poiy[acrylamide/sodium acrylateiN-(trishydroxymethyl)methyl acrylamide], 1/92/7 mole ratio 4 = 49.8% N-alkyi dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium chloride in aqueous solution ~ = sodium glucoheptonate 6 = ethylenediaminetetraacetic acid Example 21 The experimental results of Examples 10 - 20 were statistically analyzed to further emphasize the synergistic effect of the combinations of certain compounds as stabilizers.
l ~ The ra-~ data itself is indicative of synergism, as the amount of peroxide increases when the combination treatment is added, as compared to single component treatments. This ra~ data was further manipulated using standard statistical techniques to generate a model which mathematically predicts the residual peroxide based on what active or two acti~ es are present. A coefficient which is a multiplication factor was calculated for each ~0 combination. A positive calculated coefficient for the combination of actives is further .
evidence that the combination has a greater than expected ability to preserve peroxide.
T~his positive coefficlent for the combination of actives is the proof of synergy, and is ~- indicated in the table as a "yes" if synergy exists according to the calculations, as indicated in Table-XII.
TABLE XII
Synergy Ca5- l~tions for Me~ ir~l Pulp Under High Iron Conditions Tr. ': t Re~ults Residual Compound 1 Compound2 Peroxide(g/L) Synergy 1.11 Polymer B' --- 2.4 ---Poly(aspartic acid) --- 2.85 ---DTPA ' --- 2.52 ---Citric Acid --- 3.08 ---Sodium Gluconate --- 1.38 ---QuatsV --- 0.61 ---NaGH' --- 1.79 EDTA~ 1.98 ---PolymerB~ Sodium Gluconate 3.02 yes Polymer B' NaGH' 2.46 yes DTPA' Sodium Gluconate 2.1 yes DTPA ' Quats4 1.42 yes DTPA ' NaGH' 2.47 yes Citric Acid Quats 2.13 yes Citric Acid NaGH' 2.97 yes Sodium Gluconate NaGH' 4.82 yes Sodium Gluconate EDTA" 3.94 yes Quats4 NaGH' 2.49 yes I = diethylenetriam.. ,e~ ic acid 3 = polv(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylarnide), 1/92/7 mole ratio 10 4 = 49.8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium chloride in aqueous solution ~ = sodium glucohc~,lordt~
6 = ethvlenediaminetetraacetic acid 15 Example 22 The procedure of Example 21 was utilized to obtain the results of Table XIII.
- TABLE XIII
Synergy Calculations for Mechanical Pulp Under Low Iron Conditions Treatment Results Residual Compound 1 Compound 2 P~ e (g/L)Synergy 5.4 Polyrner B' --- 5.57 ---Poly(aspartic acid) --- 5.02 DTPA ' --- 5 95 Citric Acid --- 3.63 ---Sodium Gluconate --- 3.32 ---Q ats4 3.51 ~~~
NaGH' --- 5.16 ---EDTA~ 4.82 ---PolymerB~ Sodium Gluconate 6.65 yes PolymerB' Quats4 6.20 yes Polymer B' EDTA~ 6.4 yes Poly(aspartic acid) DTPA' 6.25 yes Poly(aspartic acid) Citric Acid 6.06 yes Poly(aspartic acid) Quats4 6.33 yes Poly(aspartic acid) NaGH' 5.65 yes Poly(aspartic acid) EDTA~ 5.72 yes DTPA' Citric Acid 7.74 yes DTPA' Sodium Gluconate 7.16 yes DTPA I Quats~ 6.89 yes DTPA ' NaGH' 6.14 yes Citric Acid EDTA~ 6.01 yes ~iodium Gluconate Quats4 6.99 yes ~iod ium G luconate EDTA~ 5.02 ---I = diethvlenetriami"~ tic acid 5 8 = poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), 1/92/7 mole ratio 9.8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl chloride in aqueous solution = sodium glucoheptonate ~ - cthvlenediaminetetraacetic acid 1() Example 23 The procedure of Exarnple 21 was utilized to obtain the results of Table XIV.
TABLE XIV
Synergy Calculations for Kra~t Pulp Under High Iron Conditions ~- Tr~ --t Results Residual CG . -_lld 1Compound 2 P~ JA (g/I.) SyDergy - - - - - - 1.13 - - -Polymer B' --- 0.89 ---Poly(aspartic acid) --- 3.74 ---DTPA' --- 1.47 ---Citric Acid --- 1.96 ---Sodium Gluconate --- 2.63 ---Q ats4 0.94 ~~~
NaGH' --- 0.57 ---EDTA~ --- 1.13 yes Polymer B' DTPA' 2.91 yes Polymer B' Citric Acid 1.53 yes Polymer B' Quats4 1.42 yes Polymer B' EDTA~ 1.13 yes DTPA ' Quats4 1.47 yes DTPA ' EDTA~ 1.79 yes Citric Acid Quats 2.12 yes Citric Acid NaGH' 2.04 yes Citric Acid EDTA~ 2.83 yes Sodium Gluconate NaGH' 2.12 yes Sodium Gluconate EDTA~ 3.1 yes Quats4 NaGH' 1.45 yes I = diethvlenetriaminepe~qqAetic acid 3 = poly(acrylamide/sodium acrylateAN-(trishydroxymethyl)methyl acrylamide), 1/9217 mole ratio 4 = 49.8% N-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium chloride in aqueous solution ~ = sodium glucoheptonate 6 = ethylenediamin~l~L-aacetic acid .
Example 24 The procedure of Example 21 was utilized to obtain the results of Table XV.
- TABLE XV
Synergy Calculations for Kraft Pulp Under Low Iron Conditions Treatment Results Residual Compound 1 Compound 2 Peroxide(g/L) Synergy 2.59 Polymer B' --- 2.53 ---Poly(aspartic acid) --- 2.11 ---DTPA' --- 2.52 ---Citric Acid --- 2.1 ---Sodium Gluconate --- 3.18 ---Quatsq --- 2.83 ---NaGH' --- 1.93 ---EDTA~ --- 3.15 ---Polymer B' DTPA' 3.53 yes Polymer B~ Quats4 3.43 yes Poly(aspartic acid) Citric Acid 3.87 yes Polv(aspartic acid) NaGH' 2.74 yes Poly(aspartic acid) EDTA~ 4.27 yes DTPA' Citric Acid 3.15 yes DTPA' Sodium Gluconate 3.32 yes -l = diethvlenetri~rninepent~retic acid = poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), 1/92/7 mole ratio ~ - ~9.8~/o ~-alkyl dimethyl benzyl ammonium chloride and 0.2% N-dialkyl methyl benzyl ammonium chloride in aqueous solution 1() ~=sodium~ lucoheptonate ~- ethylenediaminetetraacetic acid F.?;~ml~le 2~
Oven dried pulp, also referred to as bone dry pulp and abbreviated as ODP, is I 5 tormed under moisture-free condition. It is usually forrned by drying a known sample to a constant ~eight in a completely dry atmosphere at a t~lllpeldlule of 100~C to 105~C.
T~-o units/g oven dried pulp of xylanse and 0.1% (based on ODP) of sodium glucoheptonate would be added to a solution as described in Example 10 at pH 4.0 and let to react for 30 min in the presence and absence of metal tlcA~ nt and washed.
- Subsequently, the pH of the pulp would be adjusted to 1 1.1 and the pulp would be bleached with 1.5% peroxide on ODP for one hour. The-pulp would be washed and 5 brightn~ measured.
Changes can be made in the composition, operation and arrangement of the method of the present invention described herein without departing from the concept and scope of the invention as defined in the following claims:
Claims (52)
1. A method for ameliorating oxygen-based treatments of cellulosic materials in aqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based treatment stabilizing amount of a compound selected from the group consisting of tris(hydroxymethyl)aminomethane, N-alkyl dimethyl benzyl ammonium chloride, N-dialkyl methyl benzyl ammonium chloride and combinations thereof.
2. The method of Claim 1 wherein the oxygen-based treatment is selected from the group consisting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide bleaching and pressurized peroxide bleaching.
3. The method of Claim 2 wherein the aqueous system is a pulp and paper system.
4. The method of Claim 3 wherein from about 0.0001 to about 2.0 percent by weight of compound is added based on the dry weight of the cellulosic material.
5. The method of Claim 3 wherein from about 0.01 to about 1.0 percent by weight of compound is added based on the dry weight of the cellulosic material.
6. The method of Claim 3 wherein from about 0.1 to about 0.8 percent by weight of compound is added based on the dry weight of the cellulosic material.
7. A method for ameliorating oxygen-based treatments of cellulosic materials in aqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based treatment stabilizing amount of a combination of:
a) diethylenetriaminepentaacetic acid and b) a second compound selected from the group consisting of citric acid, sodium gluconate, sodium glucoheptonate, ethylenediaminetetraacetic acid, tris (hydroxymethyl)aminomethane, and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride.
a) diethylenetriaminepentaacetic acid and b) a second compound selected from the group consisting of citric acid, sodium gluconate, sodium glucoheptonate, ethylenediaminetetraacetic acid, tris (hydroxymethyl)aminomethane, and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride.
8. The method of Claim 7 wherein the oxygen-based treatment is selected from the group consisting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide bleaching and pressurized peroxide bleaching.
9. The method of Claim 8 wherein the aqueous system is a pulp and paper system.
10. The method of Claim 7 wherein the mole ratio of diethylenetriaminepentaacetic acid to the second compound is from 0.001: 99.999 to 99.999:0.001.
11. A method for ameliorating oxygen-based treatments of cellulosic materials in aqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based treatment stabilizing amount of a combination of:
a) citric acid and b) a second compound selected from the group consisting of sodium gluconate, sodium glucoheptonate, ethylenediaminetetraacetic acid, tris (hydroxymethyl) aminomethane, and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride.
a) citric acid and b) a second compound selected from the group consisting of sodium gluconate, sodium glucoheptonate, ethylenediaminetetraacetic acid, tris (hydroxymethyl) aminomethane, and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride.
12. The method of Claim 11 wherein the oxygen-based treatment is selected from the group consisting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide bleaching and pressurized peroxide bleaching.
13. The method Claim 12 wherein the aqueous system is a pulp and paper system.
14. The method of Claim 12 wherein the mole ratio of citric acid to the second compound is from 0.001:99.999 to 99.999:0.001.
15. A method for ameliorating oxygen-based treatments of cellulosic materials in aqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based treatment stabilizing amount of a combination of:
a) sodium gluconate and b) a second compound selected from the group consisting of sodium glucoheptonate, ethylenediaminetetraacetic acid, tris(hydroxymethyl)aminomethane, and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride.
a) sodium gluconate and b) a second compound selected from the group consisting of sodium glucoheptonate, ethylenediaminetetraacetic acid, tris(hydroxymethyl)aminomethane, and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride.
16. The method of Claim 15 wherein the oxygen-based treatment is selected from the group consisting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide bleaching and pressurized peroxide bleaching.
17. The method of Claim 16 wherein the aqueous system is a pulp and paper system.
18. The method of Claim 16 wherein the mole ratio of sodium gluconate to the second compound is from 0.001: 99.999 to 99.999: 0.001.
19. A method for ameliorating oxygen-based treatments of cellulosic materials in aqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based treatment stabilizing amount of a combination of:
a) ethylenediaminetetraacetic acid, and b) tris(hydroxymethyl)aminomethane, and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl ammonium chloride.
a) ethylenediaminetetraacetic acid, and b) tris(hydroxymethyl)aminomethane, and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl ammonium chloride.
20. The method of Claim 19 wherein the oxygen-based treatment is selected from the group consisting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide bleaching and pressurizedperoxide bleaching.
21. The method of Claim 20 wherein the aqueous system is a pulp and paper system.
22. The method of Claim 20 wherein the mole ratio of ethylenediaminetetraacetic acid to the second compound is from 0.001: 99.999 to 99.999:0.001.
23. A method for stabilizing peroxide treatments in aqueous paper production streams containing kraft pulp, peroxide, manganese and iron comprising the step of adding to the aqueous paper production stream containing kraft pulp, peroxide, manganese and iron, wherein an equal or greater amount of iron is present than manganese, an effective peroxide-stabilizing amount of a combination selected from the group consisting of:
poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/diethylenetriaminepentaacetic acid, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/citric acid, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid/and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, diethylenetriaminepentaacetic acid/ethylene diaminetetraacetic acid, citric acid/and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, citric acid/sodium glucoheptonate, citric acid/ ethylenediaminetetraacetic acid, sodium gluconate/sodium glucoheptonate, sodium gluconate/ethylenediaminetetraacetic acid and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride/sodium glucoheptonate.
poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/diethylenetriaminepentaacetic acid, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/citric acid, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid/and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, diethylenetriaminepentaacetic acid/ethylene diaminetetraacetic acid, citric acid/and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, citric acid/sodium glucoheptonate, citric acid/ ethylenediaminetetraacetic acid, sodium gluconate/sodium glucoheptonate, sodium gluconate/ethylenediaminetetraacetic acid and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride/sodium glucoheptonate.
24. A method for stabilizing peroxide treatments in aqueous paper production streams containing peroxide, kraft pulp, manganese and iron comprising the step of adding to the aqueous paper production stream containing peroxide, kraft pulp, manganese and iron, wherein an equal or lower amount of iron is present than manganese, an effective peroxide-stabilizing amount of a combination selected from the group consisting of:
poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/
diethylenetriaminepentaacetic acid, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, poly(aspartic acid)/citric acid, poly(aspartic acid)/sodium glucoheptonate, poly(aspartic acid)/ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid/citric acid and diethylenetriaminepentaacetic acid/sodium gluconate.
poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/
diethylenetriaminepentaacetic acid, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, poly(aspartic acid)/citric acid, poly(aspartic acid)/sodium glucoheptonate, poly(aspartic acid)/ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid/citric acid and diethylenetriaminepentaacetic acid/sodium gluconate.
25. A method for stabilizing peroxide treatments in aqueous paper production streams containing peroxide, mechanical pulp, manganese and iron comprising the step of adding to the aqueous paper production streams containing peroxide, mechanical pulp, manganese and iron, wherein an equal or greater amount of iron is present than manganese, an effective peroxide-stabilizing amount of a combination selected from the group consisting of: poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/sodium gluconate, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/sodium glucoheptonate, diethylenetriaminepentaacetic acid/sodium gluconate, diethylenetriaminepentaacetic acid /and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, diethylenetriaminepentaacetic acid/sodium glucoheptonate, citric acid/and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, citric acid/sodium glucoheptonate, sodium gluconate/sodium glucoheptonate, sodium gluconate/ethylenediaminetetraacetic acid, and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride/ethylenediaminetetraacetic acid.
26. A method for stabilizing peroxide treatments in aqueous paper production streams containing peroxide, mechanical pulp, manganese and iron comprising the step of adding to the aqueous paper production stream containing peroxide, mechanical pulp, manganese and iron, wherein an equal or lower amount of iron is present than manganese, an effective peroxide-stabilizing amount of a combination selected from the group consisting of: poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/sodium gluconate, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/
and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/ ethylenediaminetetraacetic acid, poly(aspartic acid)/ ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid/citric acid, diethylenetriaminepentaacetic acid/sodium gluconate, diethylenetriaminepentaacetic acid/and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, diethylenetriaminepentaacetic acid/sodium glucoheptonate, citric acid/ethylenediaminetetraacetic acid and sodium gluconate/and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride.
and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide)/ ethylenediaminetetraacetic acid, poly(aspartic acid)/ ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid/citric acid, diethylenetriaminepentaacetic acid/sodium gluconate, diethylenetriaminepentaacetic acid/and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride, diethylenetriaminepentaacetic acid/sodium glucoheptonate, citric acid/ethylenediaminetetraacetic acid and sodium gluconate/and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride.
27. A method for ameliorating oxygen-based treatments of cellulosic materials in aqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based treatment stabilizing amount of a water-soluble polymer selected from the group consisting of poly(aspartic acid), poly(dithiocarbamate), poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate), poly(sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), poly(sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate) and poly(acrylamide/sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate).
28. The method of Claim 27 wherein the oxygen-based treatment is selected from the group consisting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide bleaching and pressurized peroxide bleaching.
29. The method of Claim 28 wherein from about 0.001 to about 2 percent by weight of water-soluble polymer is added based on the dry weight of the cellulosic material.
30. The method of Claim 28 wherein the aqueous system is a pulp and paper system.
31. The method of Claim 28 wherein the water-soluble polymer is poly(acrylamide/
sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), and the mole ratio of acrylamide to sodium acrylate to N-(trishydroxymethyl)methyl acrylamide is from 0:1:99 to 10:60:30 and the molecular weight is from 1,000 to 10,000,000.
sodium acrylate/N-(trishydroxymethyl)methyl acrylamide), and the mole ratio of acrylamide to sodium acrylate to N-(trishydroxymethyl)methyl acrylamide is from 0:1:99 to 10:60:30 and the molecular weight is from 1,000 to 10,000,000.
32. The method of Claim 28 wherein the water-soluble polymer is poly(acrylamide/
sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate) and the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(2-hydroxyphenyl) methane sulfonate is from 0:10:90 to 10:60:30 and the molecular weight is from 1,000 to 10.000.000.
sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate) and the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(2-hydroxyphenyl) methane sulfonate is from 0:10:90 to 10:60:30 and the molecular weight is from 1,000 to 10.000.000.
33. The method of Claim 28 wherein the water-soluble polymer is poly(acrylamide/
sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate) and the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate is from 0:10:90 to 10.60:30 and the molecular weight is from 1,000 to 10,000,000.
sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate) and the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate is from 0:10:90 to 10.60:30 and the molecular weight is from 1,000 to 10,000,000.
34. A method for ameliorating oxygen-based treatments of cellulosic materials inaqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based treatment stabilizing amount of:
a) a compound selected from the group consisting of diethylenetriaminepentaacetic acid, citric acid, sodium gluconate, sodium glucoheptonate, ethylenediaminetetraacetic acid, tris(hydroxymethyl)aminomethane, and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride and b) a water-soluble polymer selected from the group consisting of poly(aspartic acid), poly(dithiocarbamate), poly(acrylamide/sodium acrylate/N-(tris-hydroxymethyl)methyl acrylamide), poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate), poly(sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), poly(sodium acrylate/N-(trishydroxymethyl)methyl acrylamide) and poly(acrylamide/sodium acrylate/sodiumacrylamido(2-hydroxyphenyl) methane sulfonate).
a) a compound selected from the group consisting of diethylenetriaminepentaacetic acid, citric acid, sodium gluconate, sodium glucoheptonate, ethylenediaminetetraacetic acid, tris(hydroxymethyl)aminomethane, and a combination of N-alkyl dimethyl benzyl ammonium chloride and N-dialkyl methyl benzyl ammonium chloride and b) a water-soluble polymer selected from the group consisting of poly(aspartic acid), poly(dithiocarbamate), poly(acrylamide/sodium acrylate/N-(tris-hydroxymethyl)methyl acrylamide), poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate), poly(sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate), poly(sodium acrylate/N-(trishydroxymethyl)methyl acrylamide) and poly(acrylamide/sodium acrylate/sodiumacrylamido(2-hydroxyphenyl) methane sulfonate).
35. The method of Claim 34 wherein the oxygen-based treatment is selected from the group consisting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide bleaching and pressurized peroxide bleaching.
36. The method of Claim 35 wherein the aqueous system is a pulp and paper system.
37. The method of Claim 35 wherein the mole ratio of the compound to the water-soluble polymer is from about 0.00001: 99.99999 to about 99.99999: 0.00001.
38. The method of Claim 35 wherein wherein the water-soluble polymer is poly(acrylamide/sodium acrylate/N-(trishydroxymethyl)methyl acrylamide) and the mole ratio of acrylamide to sodium acrylate to N-(trishydroxymethyl)methyl acrylamide is from 0:1:99 to 10:60:30 and the molecular weight is from 1,000 to 10,000,000.
39. The method of Claim 35 wherein the water-soluble polymer is poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate) and the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate is from 0:1:99 to 10:30:60 and the molecular weight is from 1,000 to 10.000.000.
40. The method of Claim 35 wherein the water-soluble polymer is poly(acrylamide/sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate) and the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(2-hydroxyphenyl) methane sulfonate is from 0:1:99 to 10:30:60 and the molecular weight is from 1,000 to 10,000,000.
41. A water-soluble polymer of the formula poly(acrylamide/sodium acrylate/sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate).
42. The polymer of Claim 41 wherein the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate) is from 0:1:99 to 10:30:60 and the molecular weight is from 1,000 to 10,000,000.
43. A water-soluble polymer of the formula poly(acrylamide/sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate).
44. The polymer of Claim 43 wherein the mole ratio of acrylamide to sodium acrylate to sodium acrylamido(2-hydroxyphenyl) methane sulfonate is from 0:1:99 to 10:30:60 and the molecular weight is from 1,000 to 10,000,000.
45. A water-soluble polymer of the formula poly(sodium acrylate/sodium acrylamido(2-hydroxyphenyl) methane sulfonate).
46. The polymer of Claim 45 wherein the mole ratio of sodium acrylate to sodium acrylamido(2-hydroxyphenyl) methane sulfonate is from 99:1 to 60:40 and the molecular weight is from 1,000 to 10,000,000.
47. A water-soluble polymer of the formula poly(sodium acrylate/N-(trishydroxymethyl)methyl acrylamide).
48. The polymer of Claim 47 wherein the mole ratio of sodium acrylate to N-(trishydroxymethyl)methyl acrylamide is from 99:1 to 60:40 and the molecular weight is from 1,000 to 10,000,000.
49. A water-soluble polymer of the formula poly(sodium acrylate/sodium acrylamido(3.4-dihydroxyphenyl) methane sulfonate).
50. The polymer of Claim 49 wherein the mole ratio of sodium acrylate to sodium acrylamido(3,4-dihydroxyphenyl) methane sulfonate is from 99:1 to 60:40 and the molecular weight is from 1,000 to 10,000,000.
51. A method for ameliorating oxygen-based treatments of cellulosic materials in aqueous systems comprising adding to an aqueous system containing cellulosic materials an effective oxygen-based treatment stabilizing amount of a combination of sodium glucoheptonate and xylanase enzyme.
52. The method of Claim 51 wherein the oxygen-based treatment is selected from the group consisting of oxygen delignification, oxygen-aided extraction, peroxide-aided extraction, peroxide/oxygen-aided extraction, peroxide bleaching and pressurized peroxide bleaching.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US71950796A | 1996-09-23 | 1996-09-23 | |
| US08/719,507 | 1996-09-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2216084A1 true CA2216084A1 (en) | 1998-03-23 |
Family
ID=24890341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002216084A Abandoned CA2216084A1 (en) | 1996-09-23 | 1997-09-22 | Stabilizers for use in oxygen-based treatments of cellulosic materials |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0831169A2 (en) |
| AU (1) | AU3918397A (en) |
| BR (1) | BR9704791A (en) |
| CA (1) | CA2216084A1 (en) |
| ID (1) | ID18322A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112533864A (en) * | 2018-08-02 | 2021-03-19 | 赢创有限公司 | Method for producing stabilized aqueous hydrogen peroxide solution |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6702921B2 (en) * | 2001-05-01 | 2004-03-09 | Ondeo Nalco Company | Methods to enhance pulp bleaching and delignification using an organic sulfide chelating agent |
| CA2576424C (en) | 2004-08-19 | 2013-05-07 | Tyco Healthcare Group Lp | Water-swellable copolymers and articles and coatings made therefrom |
| US20210307332A1 (en) * | 2018-08-02 | 2021-10-07 | Evonik Corporation | Polymer-stabilized aqueous hydrogen peroxide solutions and associated methods |
-
1997
- 1997-09-22 CA CA002216084A patent/CA2216084A1/en not_active Abandoned
- 1997-09-22 EP EP97116469A patent/EP0831169A2/en not_active Withdrawn
- 1997-09-23 AU AU39183/97A patent/AU3918397A/en not_active Abandoned
- 1997-09-23 ID IDP973262A patent/ID18322A/en unknown
- 1997-09-23 BR BR9704791A patent/BR9704791A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112533864A (en) * | 2018-08-02 | 2021-03-19 | 赢创有限公司 | Method for producing stabilized aqueous hydrogen peroxide solution |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0831169A2 (en) | 1998-03-25 |
| AU3918397A (en) | 1998-03-26 |
| BR9704791A (en) | 1999-01-19 |
| ID18322A (en) | 1998-03-26 |
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