CA2007062A1 - Process for reducing halogen impurities in oil products - Google Patents
Process for reducing halogen impurities in oil productsInfo
- Publication number
- CA2007062A1 CA2007062A1 CA002007062A CA2007062A CA2007062A1 CA 2007062 A1 CA2007062 A1 CA 2007062A1 CA 002007062 A CA002007062 A CA 002007062A CA 2007062 A CA2007062 A CA 2007062A CA 2007062 A1 CA2007062 A1 CA 2007062A1
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- Canada
- Prior art keywords
- ammonium
- acid
- method recited
- oil
- carried out
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/0016—Working-up used lubricants to recover useful products ; Cleaning with the use of chemical agents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Removal Of Specific Substances (AREA)
- Lubricants (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
ABSTRACT OF DISCLOSURE
The present invention provides a method for reprocessing, particularly the dehalogenation, of oil products which involves a) treating the oil product at temperatures up to about 150°C with an effective amount of an aqueous solution of at least one compound selected from the group consisting of a strong acid, a salt of a weak base and a strong acid and precursors thereof; b) treating the oil product of step (a) at increased temperatures with at least one halogen binding agent;
and c) separating water and/or the solids from the treated oil product of step (b).
The present invention provides a method for reprocessing, particularly the dehalogenation, of oil products which involves a) treating the oil product at temperatures up to about 150°C with an effective amount of an aqueous solution of at least one compound selected from the group consisting of a strong acid, a salt of a weak base and a strong acid and precursors thereof; b) treating the oil product of step (a) at increased temperatures with at least one halogen binding agent;
and c) separating water and/or the solids from the treated oil product of step (b).
Description
~ PROCESS FOR REDUCING HALOGEN IMPURITIES IN OIL PRODUCTS
1 Field of the Invention 200706Z
1 Field of the Invention 200706Z
2 The present invention relates to a method ~or 3 reducing the halogen content of oil products, particularly the 4 dehalogenation of waste oil such as used lubricating oil.
Background of the Invention 6 Efficient reconditioning of waste oils for reuse, so 7 called recycling, is advantageous from both economic and 8 ¦ ecological points of view. Use of reconditioned or recycled 9 oils (hereafter reprocessed waste oil) as fuel or propellant is subject to govexnmental regulation in most countries because ~1 impurities therein may be released into the atmosphere creating 12 an environmental hazard. In some cases, e.g., fuel oil 13 applications, the impurity combustion products are most 14 hazardous. Similar problems exist in other reprocessed waste oil applications, e.g., if they are used as base oil for the 16 manufacture of lubricant oils.
17 ~ The reprocessed waste oil impurities most commonly 18 j regulated for environmental reasons include inorganic and 19 organic compounds of metals, of sulfur, of phosphorus, and the halogens, in particular of chlorine. Limiting the 21 concentration of these impurities is particularly important 22 when the reprocessed waste oil is to be used as base oil for 23 the manufacturing lubricant oils~
24 Halogen compound concentration in reprocessed waste oil partlcularly chlorine compounds is of special importance 26 beca~se:
27 ! 1. the halogen compounds present in the waste oils ~8 and their combustion products may be harm~ul to man and the ~9 environment;
2. the legal limit for the chlorine content of ` 1 ¦~ heatin ils are very low: and 2 3. the e~ficient removal o~ high boili ~ ~ 6 3 organic halogen compounds (e.g., chlorine) down to residual 4 contents of less than about 100 mg chlorine/kg oil ~rom waste oils has not been economically practical.
6 Conventional methods for the reprocessing of waste 7 oils may involve acid treatment of the waste oil followed by a 8 separation and neutralization of the resultant acid phase, and 9 a thermal treatment step in which volatile fractions are driven off by distillation. In certain applications the reprocessed ~1 waste oils themselves are subse~uently distilled.
12 Waste oil feedstocks such as used motor oil, 13 typically contain about 1,000 to lO,000 mg or more of halogen 14 per kg and are not adeguately freed of halogens by the above conventional methods unless they are subjected to further 16 treatment.
1~ There are known methods that ca~ remove haloyen 18 impurity from waste oils down to a concentration of about 100 19 mg/kg (expressed as chlorine C12). These methods include, e.g., an after-treatment with additives which bind chlorine, 21 such as alkali or alkaline earth metals, alkali or alkaline 2~ earth hydrodixes such as sodium or potassium hydroxide solution 23 or calcium or magnesium hydroxide or alkali hydroxides in 24 combination with selected solvents, and/or may involve hydrogenation processes.
26 These methods have one or more of the following 27 disadvantages: ¦
28 1. they do not lower the residual halogen content 29 to below about 100 mg/kg (expressed as chlorine);
2- they requirF high temperatures that may effect .
-~ 1 conside ble thermal breakdown o~ the treated waste oils;
2 3. the remaining halogen and reaction ~ ~ n 3 be present in a form dif~icult ko separate, e.g., a sludge 4 which is difficult to filter or to centri~uge;
4. they can give rise to hazardous residues which 6 create additional disposal problems;
7 5. added halogen binding agents can significantly 8 increase the ash content of ~he recycled waste oils; and 9 6. they require special safety devices and/or precautionary measures due to the chemicals used.
.~1 Hence the above described methods are not 12 economically and/or technically practical for reducing the13 halogen content of the waste oil on a large scale.
14 U.S. Patent No. 3,930,988 is directed to a method for lS the reduction of the ash and metals content in used lubricating 16 oils in which the used oil is contacted with an aqueous 17 solution o~ ammonium sulfate and/or ammonium bisulfate at about 18 93 to 260 C and about 750 psig to react with the metal 19 compounds present thus forming separable metal containing solids. The reaction mixture is separated into an aqueous 21 phase containing the solids and an oil phase having reduced 22 metals and ash contents.
23 U.S. Patent No. 3,879,282 is directed ~o a method for 24 decreasing the ash and lead content in used motor oils wherein the used oil is brought into contact with an aqueous solution 26 of ammonium phosphate which forms insoluble metal ~alts which 27 are allowed to settle as precipitate. Thereafter, an oil 28 product phase separated ~rom the aqueous phase and precipitate.
29 U.S. Patent No. 4,151,072 is directed to a method for reclaiml used lubricant oils regardless o~ contaminants or ~3~
.. ~ , . .
. , .
~~ 1 additive systPms (impurities) contained therein, wherein, e.g., 2 (a) used oil is contacted with an aqueous solution æ ~ ~ 0~ 2 3 ammonium salt treating agent such as a salt selected from the 4 group consisting of ammonium sulfate, ammonium bisulfate, ammonium phosphate, diammonium hydrogen phosphate, ammonium 6 dihydrogen phosphate and mixtures thereof in appropriate 7 quantities at a temperature of 60 to 120C (b) removing a 8 major portion of the water and light hydrocarbons from the 9 ~ mixture of step (a~ at a temperature of 110 to 140C; (c) separating the resulting oil phase by filtration ; (d) heating ~1 the filtered oil phase to a temperature of 200 to 480C and 12 contacting it with an adsorption agent. For some applications 13 the resulting oil may be hydrogenated with hydrogen and a 14 catalyst and then stripped at a temperature of 280 to 395c.
DE-AS 25 08 713 is directed to a method for 16 reprocessing used mineral oil involving pre-purification by 17 means of coagulation, adsorption, filkration, distillation and 18 a hydrogenation after-treatment. After the prepurification the 19 oil is dehalogenated, fractionatsd, distilled, and hydrogenated. Dehalogenation is ef~ected by treatment o~ the 21 waste oil with an alkali metal, in particular Na or K, an 22 alkaline earth metal, in particular Mg or Ca, an alkali, 23 alkaline earth or aluminum alcoholake, and alkali hydride or 24 alkali amide, an organic base, in particular pyridine or piperidine or with metallic aluminum or anhydrous aluminum 26 chloride under conditions that exclude air and moisture, at a 27 reaction temperature of 15 to 300C.
2~ DE-OS 36 37 255 is directed to a method for the 29 reprocessing of waste oil wherein the waste oil is mixed at a pressure of 50 to 250 bar with a hydrogenous gas; at a _4_ reactio temperature of 350- to 500~C; and solids are removed 2 as sludge. ~n evaporated, oil-containing phase is ~ ~ ~ z 3 from the sludge and catalytically hydrogenated at temperatures 4 of 3000 to 4000C, the hydrogenated product is mixed with ammonia and degassed, and an ammonium chloxide-containing 6 aqueous phase is separated from the degassed product.
7 DE-OS 36 31 175 is directed to a method for the 8 dehalogenation of hydrocarbon oils in which the hydrocarbon 9 ~ oils in a homogenous phase are treated at 120 to 400C with alkali or alkaline earth alcoholate having alkyl groups which ~l contain 6 to 25~ C atoms and the resultant alkali or alkaline l~
12 earth halogenides are separated following the reaction.
13 DE-PS 36 00 024 is directed to a method for producing 14 high-quality lubricant oils from waste oils through the catalytic hydrogenation of puri~ied oil mixtures. The purified 16 oil mixtures are freed of solids, as well as other dissolved 17 and/or emulsified admixtures. The hydrogenating treatment is 18 carried out in the presenae of a commercially available l9 hydrocracking catalyst at temperatures of 3500 ~o 4800C and pressures of 20 to 400 bar.
21 United Kingdom Patent No. 856,764 is directed to a 22 method ~or decreasing the acidity o~ used lubricant oil wherein 23 the oil is treated with ammonia.
24 The above-cited methods are either costly or `otherwise lead to inefficient reprocessing of waste oils.
26 Ob~ects and Summary of the Invention 27 An objective of the present invention is to provide 28 an economic and technically simple method for removing 29 impurities, in particular halogens from various oil petroleum products such as hydrocarbon oils including waste oils, e.g., ' used motOr oils.
2 It is another object of the present inven ~ ~ 62 3 ! provide a process for reprocessing o~ waste oils which employs 4 1 small quantities of environmentally acceptable chemical~ at ¦ relatively low temperatures an~ without the use of pressure.
Background of the Invention 6 Efficient reconditioning of waste oils for reuse, so 7 called recycling, is advantageous from both economic and 8 ¦ ecological points of view. Use of reconditioned or recycled 9 oils (hereafter reprocessed waste oil) as fuel or propellant is subject to govexnmental regulation in most countries because ~1 impurities therein may be released into the atmosphere creating 12 an environmental hazard. In some cases, e.g., fuel oil 13 applications, the impurity combustion products are most 14 hazardous. Similar problems exist in other reprocessed waste oil applications, e.g., if they are used as base oil for the 16 manufacture of lubricant oils.
17 ~ The reprocessed waste oil impurities most commonly 18 j regulated for environmental reasons include inorganic and 19 organic compounds of metals, of sulfur, of phosphorus, and the halogens, in particular of chlorine. Limiting the 21 concentration of these impurities is particularly important 22 when the reprocessed waste oil is to be used as base oil for 23 the manufacturing lubricant oils~
24 Halogen compound concentration in reprocessed waste oil partlcularly chlorine compounds is of special importance 26 beca~se:
27 ! 1. the halogen compounds present in the waste oils ~8 and their combustion products may be harm~ul to man and the ~9 environment;
2. the legal limit for the chlorine content of ` 1 ¦~ heatin ils are very low: and 2 3. the e~ficient removal o~ high boili ~ ~ 6 3 organic halogen compounds (e.g., chlorine) down to residual 4 contents of less than about 100 mg chlorine/kg oil ~rom waste oils has not been economically practical.
6 Conventional methods for the reprocessing of waste 7 oils may involve acid treatment of the waste oil followed by a 8 separation and neutralization of the resultant acid phase, and 9 a thermal treatment step in which volatile fractions are driven off by distillation. In certain applications the reprocessed ~1 waste oils themselves are subse~uently distilled.
12 Waste oil feedstocks such as used motor oil, 13 typically contain about 1,000 to lO,000 mg or more of halogen 14 per kg and are not adeguately freed of halogens by the above conventional methods unless they are subjected to further 16 treatment.
1~ There are known methods that ca~ remove haloyen 18 impurity from waste oils down to a concentration of about 100 19 mg/kg (expressed as chlorine C12). These methods include, e.g., an after-treatment with additives which bind chlorine, 21 such as alkali or alkaline earth metals, alkali or alkaline 2~ earth hydrodixes such as sodium or potassium hydroxide solution 23 or calcium or magnesium hydroxide or alkali hydroxides in 24 combination with selected solvents, and/or may involve hydrogenation processes.
26 These methods have one or more of the following 27 disadvantages: ¦
28 1. they do not lower the residual halogen content 29 to below about 100 mg/kg (expressed as chlorine);
2- they requirF high temperatures that may effect .
-~ 1 conside ble thermal breakdown o~ the treated waste oils;
2 3. the remaining halogen and reaction ~ ~ n 3 be present in a form dif~icult ko separate, e.g., a sludge 4 which is difficult to filter or to centri~uge;
4. they can give rise to hazardous residues which 6 create additional disposal problems;
7 5. added halogen binding agents can significantly 8 increase the ash content of ~he recycled waste oils; and 9 6. they require special safety devices and/or precautionary measures due to the chemicals used.
.~1 Hence the above described methods are not 12 economically and/or technically practical for reducing the13 halogen content of the waste oil on a large scale.
14 U.S. Patent No. 3,930,988 is directed to a method for lS the reduction of the ash and metals content in used lubricating 16 oils in which the used oil is contacted with an aqueous 17 solution o~ ammonium sulfate and/or ammonium bisulfate at about 18 93 to 260 C and about 750 psig to react with the metal 19 compounds present thus forming separable metal containing solids. The reaction mixture is separated into an aqueous 21 phase containing the solids and an oil phase having reduced 22 metals and ash contents.
23 U.S. Patent No. 3,879,282 is directed ~o a method for 24 decreasing the ash and lead content in used motor oils wherein the used oil is brought into contact with an aqueous solution 26 of ammonium phosphate which forms insoluble metal ~alts which 27 are allowed to settle as precipitate. Thereafter, an oil 28 product phase separated ~rom the aqueous phase and precipitate.
29 U.S. Patent No. 4,151,072 is directed to a method for reclaiml used lubricant oils regardless o~ contaminants or ~3~
.. ~ , . .
. , .
~~ 1 additive systPms (impurities) contained therein, wherein, e.g., 2 (a) used oil is contacted with an aqueous solution æ ~ ~ 0~ 2 3 ammonium salt treating agent such as a salt selected from the 4 group consisting of ammonium sulfate, ammonium bisulfate, ammonium phosphate, diammonium hydrogen phosphate, ammonium 6 dihydrogen phosphate and mixtures thereof in appropriate 7 quantities at a temperature of 60 to 120C (b) removing a 8 major portion of the water and light hydrocarbons from the 9 ~ mixture of step (a~ at a temperature of 110 to 140C; (c) separating the resulting oil phase by filtration ; (d) heating ~1 the filtered oil phase to a temperature of 200 to 480C and 12 contacting it with an adsorption agent. For some applications 13 the resulting oil may be hydrogenated with hydrogen and a 14 catalyst and then stripped at a temperature of 280 to 395c.
DE-AS 25 08 713 is directed to a method for 16 reprocessing used mineral oil involving pre-purification by 17 means of coagulation, adsorption, filkration, distillation and 18 a hydrogenation after-treatment. After the prepurification the 19 oil is dehalogenated, fractionatsd, distilled, and hydrogenated. Dehalogenation is ef~ected by treatment o~ the 21 waste oil with an alkali metal, in particular Na or K, an 22 alkaline earth metal, in particular Mg or Ca, an alkali, 23 alkaline earth or aluminum alcoholake, and alkali hydride or 24 alkali amide, an organic base, in particular pyridine or piperidine or with metallic aluminum or anhydrous aluminum 26 chloride under conditions that exclude air and moisture, at a 27 reaction temperature of 15 to 300C.
2~ DE-OS 36 37 255 is directed to a method for the 29 reprocessing of waste oil wherein the waste oil is mixed at a pressure of 50 to 250 bar with a hydrogenous gas; at a _4_ reactio temperature of 350- to 500~C; and solids are removed 2 as sludge. ~n evaporated, oil-containing phase is ~ ~ ~ z 3 from the sludge and catalytically hydrogenated at temperatures 4 of 3000 to 4000C, the hydrogenated product is mixed with ammonia and degassed, and an ammonium chloxide-containing 6 aqueous phase is separated from the degassed product.
7 DE-OS 36 31 175 is directed to a method for the 8 dehalogenation of hydrocarbon oils in which the hydrocarbon 9 ~ oils in a homogenous phase are treated at 120 to 400C with alkali or alkaline earth alcoholate having alkyl groups which ~l contain 6 to 25~ C atoms and the resultant alkali or alkaline l~
12 earth halogenides are separated following the reaction.
13 DE-PS 36 00 024 is directed to a method for producing 14 high-quality lubricant oils from waste oils through the catalytic hydrogenation of puri~ied oil mixtures. The purified 16 oil mixtures are freed of solids, as well as other dissolved 17 and/or emulsified admixtures. The hydrogenating treatment is 18 carried out in the presenae of a commercially available l9 hydrocracking catalyst at temperatures of 3500 ~o 4800C and pressures of 20 to 400 bar.
21 United Kingdom Patent No. 856,764 is directed to a 22 method ~or decreasing the acidity o~ used lubricant oil wherein 23 the oil is treated with ammonia.
24 The above-cited methods are either costly or `otherwise lead to inefficient reprocessing of waste oils.
26 Ob~ects and Summary of the Invention 27 An objective of the present invention is to provide 28 an economic and technically simple method for removing 29 impurities, in particular halogens from various oil petroleum products such as hydrocarbon oils including waste oils, e.g., ' used motOr oils.
2 It is another object of the present inven ~ ~ 62 3 ! provide a process for reprocessing o~ waste oils which employs 4 1 small quantities of environmentally acceptable chemical~ at ¦ relatively low temperatures an~ without the use of pressure.
6 ¦ ¦ It is another object of the present invention to 7 ! I provide a process for dehalogenation of waste oil that also 8 1 produces a substantial decrease in the ash, phosphorus and 9 ¦ metal contents of the reprocessed waste oil.
It is yet another object of the present invention to ~1 provide a process that produces minimal amounts of waste and 12 i I minimal losses of reprocessed waste oil and the oils 13 i! reprocessed in accordance with the method are particularly 14 l; useful as a pre-stage feedstock in re~ining processes.
lS , The present invention provides a process for reducing , 16 ¦ impurities in oil products comprising the steps of: ¦
17 a) treating the oil product at temperatures up to 18 about 150C with an effective amount of an aqueou~ solution of 19 at least one compound selected from the group consisting of a ¦ strong acid, a salt of a weak base and a strong acid and 21 ' precursors thereof;
22 1 b) treating the oil product of step (a) at 23 l increased temperatures with at least one halogen binding ag~nt: ¦
24 and l c) separating water and/or the solids from the 26 l treated oil product of step (b).
27 1 The method of the invention is described in greater 28 detail below.
29 .
1.
l ~ Detailed Descr~ption of the Invent~on 2 In general step (a~ of the invention is c 3 at temperatures o~ up to about 150~c, pre~erably about 20 to 4 150C, and more pre~erably are about 80 to 120C, in a ¦ conventional stripping apparatus. The duration of step (a) is 6 1 ¦ preferably about 1 to 2 hours~
7 ¦¦ In step (a) the waste oil product is treated with an 8 !1 effective amount of an aqueous solution of at least one strong g l, acid and/or of at least one salt of a weak base and a stxong l acid or of a precursor thereof. The quantities of agueous ~ solution used depend on the particular impurities present in 12 ll the oil product and are generally in an amount less than or 13 i about equal to the equivalent weight of the impurities, 14 1 particularly halogen compounds, to be removed from the waste ¦ oil. For reasons of economy, as small a quantity of aqueous 16 ¦ solution as possible is preferred. Thus, in general quantities 17 ,l of aqueous solution below about 5 percent by weight of the 18 1¦ waste oil, are preferred. Particularly preferred are 9 !I quantities o~ agueous solution below about 0.2 percent by 2~ ¦ weight of the oil product.
21 ¦ The strong acid used in step (a~ can be any acid 22 l having a PKa greater than about 4 that is compatible with 23 , the desired product. Preferred strong acids include sulfuric 24 ` acid, sulfurous acid, amido sul~uric acid, sul~onic acid, ~ phosphoria acid, phosphorous acid, hypophosphorous acid, 26 phosphonic acid, hydrochloric acid, hydrofluoric acid and 27 mixtures thereof. Particularly preferred are sulfurous acid, 28 phosphoric acid, phosphorous acid and phosphonic acid. The 29 ¦ phosphoric acid may be an ortho- or meta-isomer or 1 polyphosphoric acid.
1 l 7 1 The salt of a weak base and a st~ong acid is 2 I preferably an a~nonium salt of a stxong acid and t ~ ~ i ~ e 3 has a PKb Of about 4 . Pre~erred ammonium salts include 4 'I ammonium sulfate, ammonium bisulfate, ammonium sulfite, j ammonium disulfite, ammonium amidosulfate, ammonium 6 ~ thiosulfate, ammonium sulfonate, ammonium phosphate, diammonium 7 hydrogen phosphate, ammonium dihydrogen phosphate, ammonium 8 amido phosphate, ammonium phosphite, ammonium phosphonic acid, f g i ammonium chloride, ammonium fluoride and mixtures thereof.
o i! Particularly preferred are ammonium sulfate, ammonium ~1 , bisulfate, ammonium sulfite, diammonium hydrogen phosphate, 12 'I ammonium dihydrogen phosphate, ammonium phosphite, and ammonium 13 , phosphonic acid. The ammonium phosphite may be mono-, di-, 14 and/or triammonium phosphite. I
lS Other compounds useful in step ~a) include salts of 16 guanidine or amides, such as carbamide or hydrazine; and alkyl 17 ,! or aryl compounds of the above listed acids such as 'I
18 l~ dimethylphosphite, diethylphosphite or triethylphosphite.
19 I Step (b) of the method according to the invention is li preferably a coagulation step wherein dissolved and undissolved I
21 !1 organic halogen compounds ln the product of step (a) break down !
22 1l into hydrogen halides which are neutralized by the added 23 '¦ halogen binding agents. The coagulation temperature is 24 il preferably about 250 to 300C and the duration of treatment i i about 0.5 to 24 hours, particularly preferred is a duration o~
26 ¦¦ about 3 to 24 hours. The preferred halogen binding agents are 27 ¦¦ ammonia and/or an organic base. Preferred organic bases 2~ 1! include urea, guanidine, hydrazine, hydrazine hydrate, 29 ¦¦ carbazides, semicarbazides, piperazine, phenylene diamine, 1! morpholine, diethanolamlne, triethanolamine and salts of these Il -8-mpounds .
~ ¦I Preferably the coagulation is carried ou~
3 ,1 exchangers so that the oil is heated in three stages and the 4 i oil from each staye is passed through a cascade tower. The j addition o~ halogen binding agent (ammonia and/or an organic 6 1I base) in this s~age ~b) causes ~he halogens (mainly chlorine) 7 , to be blown off and the corresponding ammonium compounds to be 8 ' fo~nd with small quantities of water and oil in the g l- condensate which is disposed. Alternatively, the ammonium ~ compounds may be deposited as inert/oil-insoluble halogen ~1 salts. A portion of the metal impurities in the treated oil 12 ii may be simultaneously precipitated.
13 I In step (c) of the method according to the invention 14 ¦ the product of step (b) is separated from the water and/or solids. Since the product can be sedimented readily , it can, 16 I for example, be decanted whereby approximately 95% o~ the water 17 ~ and/or solids are removed. Thereafter, depending on its 18 , viscosity the oil can be heated to a temperature o~ about 60 19 I to 150C, and subsequently filtered, e.g., in a ~ilter press to , remove remaining solids.
21 `¦ Optionally, the product of step ~a) can be cured 22 be~ore coagulation, e.g , by addition of an additive for 23 ! enhancing separation of the oil in step (c), preferably at a 24 1¦ temperature o~ about 140~ to 200C and for a duration of about ,~l 1 to 2 hours. Preferred additives for enhancing separation 26 '¦ include sodium, potassium or calcium hydroxide; sodium, 27 ,I potassium or calcium alcholate; a sodium, potassium or calcium 28 !I salts of an organic acid such as sodium ethylate or sodium 29 I stearate, urea, hydrazine, guanidine, a carbazide or a salt o~
~; these compounds. I~ such a curiny step is employed the ' ! _9_ ' 1 ¦~ trea~ment times in the subsequent coagulation step can be 2 ¦ shortened. 2007062 3 1l Optionally, after the coagulation step, an after-4 ¦ treatment of the product of step (b) can be employed be~ore the ~l separation step (~). In after treatment the product of step 6 i~ (b) is treated with an effective amount of the aqueous solution 7 1l used in step (a), preferably at a temperature of less than 8 1~ about 100C. This a~ter-treatment step can be continued for g ~ about l to 24 hours. The after-treatment step is particularly 1 useful suitable where a minimal ~uantity of the aqueous ~l solution is used in step (a), e.g., less than a~out 0.2 percent 12 ! by weight aqueous solution with respect to the waste oil.
13 ll Be~ore the treatment o~ the waste oil in accordance 14 ! with the method of the invention any conventional pre-treatment ¦ can be employed. Thus when a waste oil inoludes more than 5 16 wt. impurities a preliminary removal of water such as by 17 1¦ centrifugation, decanting or distillation may be employed.
18 I Reprocessed waste oil preparad by the method of the l9 l¦ invention is particularly use~ul as a heating oil or as a base oil for the renewed manufacture of lubricating oils.
21 ¦ The following exampIes are intended to further 22 ¦ illustrate without limiting the invention.
23 j Example l 24 A 250g sample of a waste oil containing 22% water, 1¦ 15,000 ppm total chlorine, and 1.70% wt. ash was mixed at room 26 1¦ temperature while being stirred with 2.5% wt. sulfuric acid 27 1 (40~) and heated to 80C. l,000 ppm of demulsi~ier was added, 28 ¦ and the mixture allowed to stand at thi.s temperature for 8 29 ¦ hours. The supernatant oil was then slowly heated to 150~C
producing a 4% wto condensate phase having a chlorine conte~t .
~ ' -10- 1 .
l I f 80,000 ppm and a 96% wt. residual oil phase having a 2 1l chlorine content of 9,350 ppm~ The oil phase was s ~ ~ ~ ~d 3 ~I to 280C and subsequently a total of 1.5g ammonia bubbled 4 " therethrough. After 12 hours at this temperature and e~posure to the ammonia the oil phase was cooled to 150~C and vacuum 6 i filtered. The filtrate~in the form of golden brown clear oil 7 ¦¦ contained 240 ppm of chlorine and had an ash content of 0.01%.
8 il The filtered solids (2 . 7% wto ) contained 12,400 ppm of g Ill chlorine.
Example 2 ~l il A 300g sample of a waste oil mixture of primarily 12 used motor and hydraulic oils having a water content of 3.5%
13 ,i wt., 3,600 ppm total chlorine, 850 ppm phosphorous, and 0.88%
14 , ash was mixed at 80~C with 2.5~ wt. of a 40% wt. aqueous solution of equal parts diammonium sulfite and ammonium 16 , sulfamide while being stirred and then slowly heated to 150~C
17 ! without stirring, i.e., 1 hour at 80 to 120C and 1 hour at 18 ' 120 to 150-C. The residual oil (organochlorine content 2,200 l9 i¦ ppm) was further heated rapidly to 280C, and beginning at 2~ 1 200C a 90C hot 75% wt. aqueous solution o~ equal parts of 21 ¦ carbamide and diethanolamine (total 4.0 g) was added dropwise.
22 l¦ After 4 hours the mixture was cooled and vacuum filtered at 23 l 150C with 1% wt. silicic acid. The ~iltrate still contained 24 il 140 ppm of chlorine, 8 ppm o~ phosphorous, and had an ash I content of 0.01% wt.
26 i¦ Example 3 27 ~ A 1 kg sample of a waste oil mixture of primarily 28 machine oil containing l.0~ wt. water, 13,770 ppm total ,~
~9 chlorine of which lZ mg were PCBs (polychlorinated hiphenyl) ll was mixed at 90'C with 20 ml of a 10% wt. solution of equal 1 parts ~mmonium monohydrogen p~osphate, ammon~um dihydrogen phosphate, and diammonium phosphite and within 1 ho ~ ~o 3 l¦ 150C while stirring. The residual oil containing 13,500 ppm 4 1l of chlorine was carefully mixed with 2sg of sooc hot, a~ueous 5 ¦ ¦ 75~ wt. mixture of guanidine, carbamide and diethanol amine and 6 1¦ within one-hal~ hour ~urther heated to 250C, and subsequently 7 '' a total of 1.2g ammonia was bubbled through the mixture which 8 I was heated to 330 for a total of 6 hours. The oil was cooled g ~l and treated at 100C with 15 ml o~ the same 10% solution used ,¦ initially and after 5 minutes mixed with 1,000 ppm of a .ll 1I demulsifier, and then allowed to,stand for 12 hours at 90c.
12 ' The supernatant oil was decanted and filtered through a vacuum 13 li filter. The filtered oil still contained 60 ppm of chlorine of 14 i, which 10 mg were PCB.
15 ll Example 4 16 " In this example the same starting oil was analyzed in 17 l, each instance, i.e., unfiltered waste oil, with a chlorine 18 1¦ content of 1,870 mg/kg and an ash content of 0.37%. The method 19 j~ with respect to the added agents varied, while the other ! conditions, namely temperature and treatment time were kept 21 constant in the method steps (a) and (b).
22 1 Step (a) was carried out by treatment of the waste 23 l~i oil at 70OC before stripping up to 140C. Step (b) took place 24 '! over five hours at 280C.
11 Table 1 lists the compounds added in steps (a) and 26 ¦l (b) as well as the chlorine and ash content as determined in 27 ,,, the filtered oil after completion of these steps. The 28 ¦¦ filterability of the oil after coagulation for five hours at 29 l¦ 280C is also described.
~¦ From the data summerized in Table 1 the following Il .
Il ~12- 1 .
1 ¦I conclus~ons can be drawn:
2 ~~ If neither an aqueous solution in accorda 3 1! step (a) nor a binding agent o~ step ~b) of the invention are 4 l¦ added to the waste oil tExperiment 1), some dehalogenation of ll the waste oil takes place, but the ash content remains high not 6 ' showing any significant change.
7 ~¦ Treatment of the waste oil according to step (b) of 8 ,, the mèthod of the invention without the addition o~ an aqueous g ~i solution of a strong acid and/or a salt of a weak base and a , strong acid in step (a) (Experiment 2), leads to the same results as obtained in Experiment 1. The chlorine content of 12 1 I the waste oil is decreased to some extent while the ash content 13 ~ is not reduced. This experiment shows that solely carrying out 14 Ij step (b) of the method according to the invention does not lead 15 l¦ to the desired dehalogenation of the waste oil.
16 In Experiment 3 the waste oil was treated according 17 to step (a) of the method according to the invention while in 18 ¦ I step (b) no halogen binding agent was added. Although a 19 sufficient decrease of the ash content was achieved the 1~ chlorine content was only minimally reduced.
21 , In Experiment 4, the method of the invention, a 22 ¦ I destabilization of the organochlorine compounds takes place in 23 1! step (a) and the chlorine i6 then nearly completely removed in 24 1l stage (b) and simultaneously the ash content is markedly ', reduced.
2~ ll In conclusion it can be stated that for satisfactory 27 1~ dehalogenation and ash removal or demetalization of waste oil 28 ,I both steps (a) and (b) according to the invention are necessary i 2g !! wherein each step in~luences the other leading to improved ,I halogen removal. The chemical treatment in step (a~
., Il -13- ,~
1 l~ destabilizes the chlorine compounds in the waste oil and also 2 i effects demetalization. The demetalization is not ~ ~ ~ in 3 1l step (a) only after the heat treatment in step (b) is maximum 4 1 l demetalization is achieved. Step (b) is also necessary for 5 ! good filterability of the waste oil product. Furthermore, the 6 I dehalogenation after step (a) is achieved only to the degree to 7 ~¦ which chlorides present in the waste oil are precipitated or 8 I converted to halogenated so~vents having a low boiling point g i¦ that can be distilled o~f in a vapor phase. Residual halogen i content in the oil after steps (a) and (b) is derived from ~1 l organic and other dissolved compounds which remain stable 12 throughout treatment in step (a), customarily up to cracking 13 ; temperatures of about 350C.
14 j The treatment in step (a) at temperatures below 150C
lS l effects destabilization of these halogen compounds so that they 16 ! split off hydrogen halides at temperatures o~ approximately 17 250C. If the hydrogen halide is not removed from the oil 18 ,¦ mixture, the reaction is partially reversible and effective 19 I dehalogenation is only partially effective.
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It is yet another object of the present invention to ~1 provide a process that produces minimal amounts of waste and 12 i I minimal losses of reprocessed waste oil and the oils 13 i! reprocessed in accordance with the method are particularly 14 l; useful as a pre-stage feedstock in re~ining processes.
lS , The present invention provides a process for reducing , 16 ¦ impurities in oil products comprising the steps of: ¦
17 a) treating the oil product at temperatures up to 18 about 150C with an effective amount of an aqueou~ solution of 19 at least one compound selected from the group consisting of a ¦ strong acid, a salt of a weak base and a strong acid and 21 ' precursors thereof;
22 1 b) treating the oil product of step (a) at 23 l increased temperatures with at least one halogen binding ag~nt: ¦
24 and l c) separating water and/or the solids from the 26 l treated oil product of step (b).
27 1 The method of the invention is described in greater 28 detail below.
29 .
1.
l ~ Detailed Descr~ption of the Invent~on 2 In general step (a~ of the invention is c 3 at temperatures o~ up to about 150~c, pre~erably about 20 to 4 150C, and more pre~erably are about 80 to 120C, in a ¦ conventional stripping apparatus. The duration of step (a) is 6 1 ¦ preferably about 1 to 2 hours~
7 ¦¦ In step (a) the waste oil product is treated with an 8 !1 effective amount of an aqueous solution of at least one strong g l, acid and/or of at least one salt of a weak base and a stxong l acid or of a precursor thereof. The quantities of agueous ~ solution used depend on the particular impurities present in 12 ll the oil product and are generally in an amount less than or 13 i about equal to the equivalent weight of the impurities, 14 1 particularly halogen compounds, to be removed from the waste ¦ oil. For reasons of economy, as small a quantity of aqueous 16 ¦ solution as possible is preferred. Thus, in general quantities 17 ,l of aqueous solution below about 5 percent by weight of the 18 1¦ waste oil, are preferred. Particularly preferred are 9 !I quantities o~ agueous solution below about 0.2 percent by 2~ ¦ weight of the oil product.
21 ¦ The strong acid used in step (a~ can be any acid 22 l having a PKa greater than about 4 that is compatible with 23 , the desired product. Preferred strong acids include sulfuric 24 ` acid, sulfurous acid, amido sul~uric acid, sul~onic acid, ~ phosphoria acid, phosphorous acid, hypophosphorous acid, 26 phosphonic acid, hydrochloric acid, hydrofluoric acid and 27 mixtures thereof. Particularly preferred are sulfurous acid, 28 phosphoric acid, phosphorous acid and phosphonic acid. The 29 ¦ phosphoric acid may be an ortho- or meta-isomer or 1 polyphosphoric acid.
1 l 7 1 The salt of a weak base and a st~ong acid is 2 I preferably an a~nonium salt of a stxong acid and t ~ ~ i ~ e 3 has a PKb Of about 4 . Pre~erred ammonium salts include 4 'I ammonium sulfate, ammonium bisulfate, ammonium sulfite, j ammonium disulfite, ammonium amidosulfate, ammonium 6 ~ thiosulfate, ammonium sulfonate, ammonium phosphate, diammonium 7 hydrogen phosphate, ammonium dihydrogen phosphate, ammonium 8 amido phosphate, ammonium phosphite, ammonium phosphonic acid, f g i ammonium chloride, ammonium fluoride and mixtures thereof.
o i! Particularly preferred are ammonium sulfate, ammonium ~1 , bisulfate, ammonium sulfite, diammonium hydrogen phosphate, 12 'I ammonium dihydrogen phosphate, ammonium phosphite, and ammonium 13 , phosphonic acid. The ammonium phosphite may be mono-, di-, 14 and/or triammonium phosphite. I
lS Other compounds useful in step ~a) include salts of 16 guanidine or amides, such as carbamide or hydrazine; and alkyl 17 ,! or aryl compounds of the above listed acids such as 'I
18 l~ dimethylphosphite, diethylphosphite or triethylphosphite.
19 I Step (b) of the method according to the invention is li preferably a coagulation step wherein dissolved and undissolved I
21 !1 organic halogen compounds ln the product of step (a) break down !
22 1l into hydrogen halides which are neutralized by the added 23 '¦ halogen binding agents. The coagulation temperature is 24 il preferably about 250 to 300C and the duration of treatment i i about 0.5 to 24 hours, particularly preferred is a duration o~
26 ¦¦ about 3 to 24 hours. The preferred halogen binding agents are 27 ¦¦ ammonia and/or an organic base. Preferred organic bases 2~ 1! include urea, guanidine, hydrazine, hydrazine hydrate, 29 ¦¦ carbazides, semicarbazides, piperazine, phenylene diamine, 1! morpholine, diethanolamlne, triethanolamine and salts of these Il -8-mpounds .
~ ¦I Preferably the coagulation is carried ou~
3 ,1 exchangers so that the oil is heated in three stages and the 4 i oil from each staye is passed through a cascade tower. The j addition o~ halogen binding agent (ammonia and/or an organic 6 1I base) in this s~age ~b) causes ~he halogens (mainly chlorine) 7 , to be blown off and the corresponding ammonium compounds to be 8 ' fo~nd with small quantities of water and oil in the g l- condensate which is disposed. Alternatively, the ammonium ~ compounds may be deposited as inert/oil-insoluble halogen ~1 salts. A portion of the metal impurities in the treated oil 12 ii may be simultaneously precipitated.
13 I In step (c) of the method according to the invention 14 ¦ the product of step (b) is separated from the water and/or solids. Since the product can be sedimented readily , it can, 16 I for example, be decanted whereby approximately 95% o~ the water 17 ~ and/or solids are removed. Thereafter, depending on its 18 , viscosity the oil can be heated to a temperature o~ about 60 19 I to 150C, and subsequently filtered, e.g., in a ~ilter press to , remove remaining solids.
21 `¦ Optionally, the product of step ~a) can be cured 22 be~ore coagulation, e.g , by addition of an additive for 23 ! enhancing separation of the oil in step (c), preferably at a 24 1¦ temperature o~ about 140~ to 200C and for a duration of about ,~l 1 to 2 hours. Preferred additives for enhancing separation 26 '¦ include sodium, potassium or calcium hydroxide; sodium, 27 ,I potassium or calcium alcholate; a sodium, potassium or calcium 28 !I salts of an organic acid such as sodium ethylate or sodium 29 I stearate, urea, hydrazine, guanidine, a carbazide or a salt o~
~; these compounds. I~ such a curiny step is employed the ' ! _9_ ' 1 ¦~ trea~ment times in the subsequent coagulation step can be 2 ¦ shortened. 2007062 3 1l Optionally, after the coagulation step, an after-4 ¦ treatment of the product of step (b) can be employed be~ore the ~l separation step (~). In after treatment the product of step 6 i~ (b) is treated with an effective amount of the aqueous solution 7 1l used in step (a), preferably at a temperature of less than 8 1~ about 100C. This a~ter-treatment step can be continued for g ~ about l to 24 hours. The after-treatment step is particularly 1 useful suitable where a minimal ~uantity of the aqueous ~l solution is used in step (a), e.g., less than a~out 0.2 percent 12 ! by weight aqueous solution with respect to the waste oil.
13 ll Be~ore the treatment o~ the waste oil in accordance 14 ! with the method of the invention any conventional pre-treatment ¦ can be employed. Thus when a waste oil inoludes more than 5 16 wt. impurities a preliminary removal of water such as by 17 1¦ centrifugation, decanting or distillation may be employed.
18 I Reprocessed waste oil preparad by the method of the l9 l¦ invention is particularly use~ul as a heating oil or as a base oil for the renewed manufacture of lubricating oils.
21 ¦ The following exampIes are intended to further 22 ¦ illustrate without limiting the invention.
23 j Example l 24 A 250g sample of a waste oil containing 22% water, 1¦ 15,000 ppm total chlorine, and 1.70% wt. ash was mixed at room 26 1¦ temperature while being stirred with 2.5% wt. sulfuric acid 27 1 (40~) and heated to 80C. l,000 ppm of demulsi~ier was added, 28 ¦ and the mixture allowed to stand at thi.s temperature for 8 29 ¦ hours. The supernatant oil was then slowly heated to 150~C
producing a 4% wto condensate phase having a chlorine conte~t .
~ ' -10- 1 .
l I f 80,000 ppm and a 96% wt. residual oil phase having a 2 1l chlorine content of 9,350 ppm~ The oil phase was s ~ ~ ~ ~d 3 ~I to 280C and subsequently a total of 1.5g ammonia bubbled 4 " therethrough. After 12 hours at this temperature and e~posure to the ammonia the oil phase was cooled to 150~C and vacuum 6 i filtered. The filtrate~in the form of golden brown clear oil 7 ¦¦ contained 240 ppm of chlorine and had an ash content of 0.01%.
8 il The filtered solids (2 . 7% wto ) contained 12,400 ppm of g Ill chlorine.
Example 2 ~l il A 300g sample of a waste oil mixture of primarily 12 used motor and hydraulic oils having a water content of 3.5%
13 ,i wt., 3,600 ppm total chlorine, 850 ppm phosphorous, and 0.88%
14 , ash was mixed at 80~C with 2.5~ wt. of a 40% wt. aqueous solution of equal parts diammonium sulfite and ammonium 16 , sulfamide while being stirred and then slowly heated to 150~C
17 ! without stirring, i.e., 1 hour at 80 to 120C and 1 hour at 18 ' 120 to 150-C. The residual oil (organochlorine content 2,200 l9 i¦ ppm) was further heated rapidly to 280C, and beginning at 2~ 1 200C a 90C hot 75% wt. aqueous solution o~ equal parts of 21 ¦ carbamide and diethanolamine (total 4.0 g) was added dropwise.
22 l¦ After 4 hours the mixture was cooled and vacuum filtered at 23 l 150C with 1% wt. silicic acid. The ~iltrate still contained 24 il 140 ppm of chlorine, 8 ppm o~ phosphorous, and had an ash I content of 0.01% wt.
26 i¦ Example 3 27 ~ A 1 kg sample of a waste oil mixture of primarily 28 machine oil containing l.0~ wt. water, 13,770 ppm total ,~
~9 chlorine of which lZ mg were PCBs (polychlorinated hiphenyl) ll was mixed at 90'C with 20 ml of a 10% wt. solution of equal 1 parts ~mmonium monohydrogen p~osphate, ammon~um dihydrogen phosphate, and diammonium phosphite and within 1 ho ~ ~o 3 l¦ 150C while stirring. The residual oil containing 13,500 ppm 4 1l of chlorine was carefully mixed with 2sg of sooc hot, a~ueous 5 ¦ ¦ 75~ wt. mixture of guanidine, carbamide and diethanol amine and 6 1¦ within one-hal~ hour ~urther heated to 250C, and subsequently 7 '' a total of 1.2g ammonia was bubbled through the mixture which 8 I was heated to 330 for a total of 6 hours. The oil was cooled g ~l and treated at 100C with 15 ml o~ the same 10% solution used ,¦ initially and after 5 minutes mixed with 1,000 ppm of a .ll 1I demulsifier, and then allowed to,stand for 12 hours at 90c.
12 ' The supernatant oil was decanted and filtered through a vacuum 13 li filter. The filtered oil still contained 60 ppm of chlorine of 14 i, which 10 mg were PCB.
15 ll Example 4 16 " In this example the same starting oil was analyzed in 17 l, each instance, i.e., unfiltered waste oil, with a chlorine 18 1¦ content of 1,870 mg/kg and an ash content of 0.37%. The method 19 j~ with respect to the added agents varied, while the other ! conditions, namely temperature and treatment time were kept 21 constant in the method steps (a) and (b).
22 1 Step (a) was carried out by treatment of the waste 23 l~i oil at 70OC before stripping up to 140C. Step (b) took place 24 '! over five hours at 280C.
11 Table 1 lists the compounds added in steps (a) and 26 ¦l (b) as well as the chlorine and ash content as determined in 27 ,,, the filtered oil after completion of these steps. The 28 ¦¦ filterability of the oil after coagulation for five hours at 29 l¦ 280C is also described.
~¦ From the data summerized in Table 1 the following Il .
Il ~12- 1 .
1 ¦I conclus~ons can be drawn:
2 ~~ If neither an aqueous solution in accorda 3 1! step (a) nor a binding agent o~ step ~b) of the invention are 4 l¦ added to the waste oil tExperiment 1), some dehalogenation of ll the waste oil takes place, but the ash content remains high not 6 ' showing any significant change.
7 ~¦ Treatment of the waste oil according to step (b) of 8 ,, the mèthod of the invention without the addition o~ an aqueous g ~i solution of a strong acid and/or a salt of a weak base and a , strong acid in step (a) (Experiment 2), leads to the same results as obtained in Experiment 1. The chlorine content of 12 1 I the waste oil is decreased to some extent while the ash content 13 ~ is not reduced. This experiment shows that solely carrying out 14 Ij step (b) of the method according to the invention does not lead 15 l¦ to the desired dehalogenation of the waste oil.
16 In Experiment 3 the waste oil was treated according 17 to step (a) of the method according to the invention while in 18 ¦ I step (b) no halogen binding agent was added. Although a 19 sufficient decrease of the ash content was achieved the 1~ chlorine content was only minimally reduced.
21 , In Experiment 4, the method of the invention, a 22 ¦ I destabilization of the organochlorine compounds takes place in 23 1! step (a) and the chlorine i6 then nearly completely removed in 24 1l stage (b) and simultaneously the ash content is markedly ', reduced.
2~ ll In conclusion it can be stated that for satisfactory 27 1~ dehalogenation and ash removal or demetalization of waste oil 28 ,I both steps (a) and (b) according to the invention are necessary i 2g !! wherein each step in~luences the other leading to improved ,I halogen removal. The chemical treatment in step (a~
., Il -13- ,~
1 l~ destabilizes the chlorine compounds in the waste oil and also 2 i effects demetalization. The demetalization is not ~ ~ ~ in 3 1l step (a) only after the heat treatment in step (b) is maximum 4 1 l demetalization is achieved. Step (b) is also necessary for 5 ! good filterability of the waste oil product. Furthermore, the 6 I dehalogenation after step (a) is achieved only to the degree to 7 ~¦ which chlorides present in the waste oil are precipitated or 8 I converted to halogenated so~vents having a low boiling point g i¦ that can be distilled o~f in a vapor phase. Residual halogen i content in the oil after steps (a) and (b) is derived from ~1 l organic and other dissolved compounds which remain stable 12 throughout treatment in step (a), customarily up to cracking 13 ; temperatures of about 350C.
14 j The treatment in step (a) at temperatures below 150C
lS l effects destabilization of these halogen compounds so that they 16 ! split off hydrogen halides at temperatures o~ approximately 17 250C. If the hydrogen halide is not removed from the oil 18 ,¦ mixture, the reaction is partially reversible and effective 19 I dehalogenation is only partially effective.
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Claims (22)
1. A method for reducing impurities in of products comprising the steps of:
(a) treating the oil product at temperatures up to about 150°C with an effective amount of an aqueous solution of at least one compound selected from the group consisting of a strong acid, a salt of a weak base and a strong acid and precursors thereof;
(b) treating the oil product of step (a) at increased temperatures with at least one halogen binding agent;
and (c) separating dehalogenated oil from the product of step (b).
(a) treating the oil product at temperatures up to about 150°C with an effective amount of an aqueous solution of at least one compound selected from the group consisting of a strong acid, a salt of a weak base and a strong acid and precursors thereof;
(b) treating the oil product of step (a) at increased temperatures with at least one halogen binding agent;
and (c) separating dehalogenated oil from the product of step (b).
2. The method of claim 1 wherein the strong acid is selected from the group consisting of:
sulfuric acid, sulfurous acid, amido sulfuric acid, sulfonic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid, hydrochloric acid, hydrofluoric acid and mixtures thereof:
the salt of a strong acid and a weak base is selected from the group consisting of:
ammonium sulfate, ammonium bisulfate, ammonium sulfite, ammonium disulfite, ammonium amidosulfate, ammonium thiosulfate, ammonium sulfonate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium amido phosphate, ammonium phosphite, ammonium phosphonic acid, ammonium chloride, ammonium fluoride, carbamide, hydrazine, diethylphosphite and triethylphosphite; and the halogen binding agent of step (b) is selected from the group consisting of ammonia urea, guanidine, hydrazine, hydrazine hydrate, carbazides, semicarbazides, piperazine, phenylene diamine, morpholine, diethanolamine, triethanolamine and salts thereof.
sulfuric acid, sulfurous acid, amido sulfuric acid, sulfonic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid, hydrochloric acid, hydrofluoric acid and mixtures thereof:
the salt of a strong acid and a weak base is selected from the group consisting of:
ammonium sulfate, ammonium bisulfate, ammonium sulfite, ammonium disulfite, ammonium amidosulfate, ammonium thiosulfate, ammonium sulfonate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium amido phosphate, ammonium phosphite, ammonium phosphonic acid, ammonium chloride, ammonium fluoride, carbamide, hydrazine, diethylphosphite and triethylphosphite; and the halogen binding agent of step (b) is selected from the group consisting of ammonia urea, guanidine, hydrazine, hydrazine hydrate, carbazides, semicarbazides, piperazine, phenylene diamine, morpholine, diethanolamine, triethanolamine and salts thereof.
3. A method for reducing the halogen content of waste oil, comprising the steps of:
(a) treating the waste oil at temperatures up to about 150°C with an effective amount of an aqueous solution of at least one compound selected from the group consisting of a strong acid, a salt of a weak base and a strong acid and precursors thereof;
(b) treating the product of step (a) at increased temperatures with at least one halogen binding agent, and (c) separating the dehalogenated oil from the product of step (b).
(a) treating the waste oil at temperatures up to about 150°C with an effective amount of an aqueous solution of at least one compound selected from the group consisting of a strong acid, a salt of a weak base and a strong acid and precursors thereof;
(b) treating the product of step (a) at increased temperatures with at least one halogen binding agent, and (c) separating the dehalogenated oil from the product of step (b).
4. The method recited in claim 3, wherein step (a) is carried out in stripping apparatus.
5. The method recited in claim 3, wherein step (a) is carried out at a temperature of about 20° to 150°C.
6. The method recited in claim 5, wherein step (a) is carried out over about 1 to 2 hours.
7. The method recited in claim 5, wherein step (a) is carried out with about 5 percent by weight of the aqueous solution with respect to the waste oil.
8. The method as recited in claim 7, wherein step (a) is carried out with an aqueous solution including an acid selected from the group consisting of sulfuric acid, sulfurous acid, amidosulfuric acid, sulfonic acid, phosphoric acid, phosphorous acid, hypophosphorous acid, phosphonic acid, hydrochloric acid, hydrofluoric acid and mixtures thereof.
9. The method recited in claim 7, wherein step (a) is carried out with an aqueous solution including a ?
selected from the group consisting of an ammonium salt of a strong acid and a precursor thereof.
selected from the group consisting of an ammonium salt of a strong acid and a precursor thereof.
10. The method recited in claim 9, wherein the ammonium salt is selected from the group consisting of ammonium sulfate, ammonium bisulfate, ammonium sulfite, ammonium disulfite, ammonium amidosulfate, ammonium thiosulfate, ammonium sulfonate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium amidophosphate, ammonium phosphite, ammonium phosphonic acid, ammonium chloride and ammonium fluoride.
11. The method recited in claim 7 wherein step (a) is carried out with an aqueous solution including a compound selected from the group consisting of a guanidinium salt, an amide, alkyl and aryl compounds of a strong acid and precursors thereof.
12. The method recited in claim 8, 9 or 10, wherein step (b) is carried out at a temperature of about 200° to 350°C.
13. The method recited in claim 8, 9, or 10, wherein step (b) is carried out over about 0.5 to 24 hours.
14. The method recited in claim 8, 9 or 10, wherein the halogen binding agent in step (b) is selected from the group consisting of ammonia and an organic base.
15. The method recited in claim 14, wherein the organic base is selected from the group consisting of urea, guanidine, hydrazine, hydrazine hydrate, a carbazide, a semicarbazide, piperazine, phenylenediamine, morpholine, diethanolamine, triethanolamine and salts thereof.
16. The method recited in claim 8, 9 or 10, wherein step (c) is carried out at a temperature of about
17. The method recited in claim 8, 9 or 10, wherein between steps (a) and (b) a curing step is carried out.
18. The method recited in claim 17, wherein the curing step is carried out by treating the product of step (a) with at least one additive for the improvement of the separability of the dehalogenated oil in step (c).
19. The method recited in claim 18, wherein the additive is selected from the group consisting of sodium, potassium and calcium hydroxide, sodium, potassium and calcium alcoholate, sodium, potassium and calcium salts of organic acids, urea, hydrazine, guanidine, and a carbazide.
20. The method recited in claim 8, 9 or 10, wherein between steps (b) and (c) an after-treatment step is carried out.
21. The method recited in claim 20, wherein the after-treatment step is carried out by treating the product of step (b) with an effective amount of the aqueous solution used in step (a).
22. The method recited in claim 21, wherein the after-treatment step is carried out at a temperature of less than about 100°C for a duration of about 1 to 24 hours.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3900159 | 1989-01-04 | ||
| DE3900159A DE3900159A1 (en) | 1989-01-04 | 1989-01-04 | METHOD FOR REFURBISHING ALTOEL |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2007062A1 true CA2007062A1 (en) | 1990-07-04 |
Family
ID=6371593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002007062A Abandoned CA2007062A1 (en) | 1989-01-04 | 1990-01-03 | Process for reducing halogen impurities in oil products |
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| Country | Link |
|---|---|
| US (1) | US5057207A (en) |
| EP (1) | EP0452409A1 (en) |
| JP (1) | JPH04504432A (en) |
| KR (1) | KR910700325A (en) |
| CN (1) | CN1043954A (en) |
| AU (1) | AU4949590A (en) |
| BR (1) | BR9006991A (en) |
| CA (1) | CA2007062A1 (en) |
| DE (1) | DE3900159A1 (en) |
| HU (1) | HUT61584A (en) |
| MY (1) | MY104878A (en) |
| PT (1) | PT92778A (en) |
| WO (1) | WO1990007566A1 (en) |
| YU (1) | YU46735B (en) |
| ZA (1) | ZA899547B (en) |
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|---|---|---|---|---|
| DE3903105A1 (en) * | 1989-02-02 | 1990-08-09 | Huels Chemische Werke Ag | LIQUID ENTHALOGEN |
| DE3920869A1 (en) * | 1989-06-26 | 1991-01-03 | Geut Ag | METHOD FOR TREATING ALTOEL |
| US5951852A (en) * | 1993-12-23 | 1999-09-14 | Commonwealth Scientific And Industrial Research Organisation Et Al. | Destruction of halide containing organics and solvent purification |
| US5458765A (en) * | 1994-08-05 | 1995-10-17 | Nalco Chemical Company | Process of drying and removing solids from waste oil |
| US5489390A (en) * | 1995-03-14 | 1996-02-06 | The Lubrizol Corporation | Treatment of organic compounds to reduce chlorine level |
| US5672266A (en) * | 1995-10-13 | 1997-09-30 | The Lubrizol Corporation | Treatment of organic compounds to reduce chlorine level |
| US5674819A (en) * | 1995-11-09 | 1997-10-07 | The Lubrizol Corporation | Carboxylic compositions, derivatives,lubricants, fuels and concentrates |
| FR2801808B1 (en) * | 1999-12-07 | 2002-05-17 | Atofina | PROCESS FOR REDUCING ELEMENTARY HALOGEN IN AN EFFLUENT AND INSTALLATION FOR IMPLEMENTING IT |
| DE10155281A1 (en) * | 2001-11-08 | 2003-06-05 | Solvent Innovation Gmbh | Process for removing polarizable impurities from hydrocarbons and hydrocarbon mixtures by extraction with ionic liquids |
| WO2013026014A1 (en) * | 2011-08-17 | 2013-02-21 | Nbip, Llc | Compositions and methods for remediation of chlorinated polyaromatic compounds |
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| CN106281481A (en) * | 2016-08-23 | 2017-01-04 | 陈晓锋 | A kind of biodiesel composite emulsifier and its preparation method and application |
| CN109468163B (en) * | 2018-04-13 | 2021-04-16 | 湖北爱国石化有限公司 | Refining process for waste mineral raw oil |
| CN108998194B (en) * | 2018-09-14 | 2021-07-27 | 闽江学院 | Waste lubricating oil decoloring method |
| FI128237B (en) * | 2018-12-21 | 2020-01-15 | Neste Oyj | Method for upgrading waste oil |
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| US2320629A (en) * | 1941-05-26 | 1943-06-01 | Phillips Petroleum Co | Treatment of predominantly saturated hydrocarbon materials |
| US2678954A (en) * | 1950-07-24 | 1954-05-18 | Phillips Petroleum Co | Removal of fluorine from hydrocarbon oils by treatment with boric oxide or boric acid |
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| US2822320A (en) * | 1956-09-28 | 1958-02-04 | Phillips Petroleum Co | Reclaiming used lubricating oil |
| US3528909A (en) * | 1967-09-25 | 1970-09-15 | Chevron Res | Conversion of metals-containing hydrocarbon oils |
| US3547806A (en) * | 1967-11-30 | 1970-12-15 | Phillips Petroleum Co | Prevention of corrosion and fouling in a hydrocarbon conversion process |
| US3879282A (en) * | 1974-02-26 | 1975-04-22 | Phillips Petroleum Co | Reclaiming used motor oil by chemical treatment with ammonium phosphate |
| US3930988A (en) * | 1975-02-24 | 1976-01-06 | Phillips Petroleum Company | Reclaiming used motor oil |
| DE2508713C3 (en) * | 1975-02-28 | 1979-04-12 | Adolf Schmids Erben Ag, Bern | Process for processing used mineral oil |
| US4029569A (en) * | 1975-09-16 | 1977-06-14 | Lubrication Company Of America | Process for reclaiming spent motor oil |
| US4151072A (en) * | 1977-05-16 | 1979-04-24 | Phillips Petroleum Company | Reclaiming used lubricating oils |
| GB2064578B (en) * | 1979-11-01 | 1983-08-24 | Phillips Petroleum Co | De-ashing lubricating oils |
| US4561969A (en) * | 1984-09-28 | 1985-12-31 | The United States Of America As Represented By The United States Department Of Energy | Method for removing chlorine compounds from hydrocarbon mixtures |
| LU86286A1 (en) * | 1986-01-31 | 1987-09-03 | Labofina Sa | PROCESS FOR DECOMPOSING POLYHALOGUE AROMATIC COMPOUNDS |
| FR2598089B1 (en) * | 1986-04-30 | 1989-07-21 | Labofina Sa | PROCESS FOR DECOMPOSING HALOGENATED ORGANIC COMPOUNDS APPLICABLE IN PARTICULAR TO MINERAL OILS |
| DE3621175A1 (en) * | 1986-06-25 | 1988-01-07 | Huels Chemische Werke Ag | METHOD FOR ENTHALOGENATING HYDROCARBON OILS |
-
1989
- 1989-01-04 DE DE3900159A patent/DE3900159A1/en not_active Withdrawn
- 1989-11-03 US US07/431,946 patent/US5057207A/en not_active Expired - Fee Related
- 1989-12-14 ZA ZA899547A patent/ZA899547B/en unknown
- 1989-12-21 MY MYPI89001831A patent/MY104878A/en unknown
-
1990
- 1990-01-03 AU AU49495/90A patent/AU4949590A/en not_active Abandoned
- 1990-01-03 BR BR909006991A patent/BR9006991A/en not_active Application Discontinuation
- 1990-01-03 YU YU190A patent/YU46735B/en unknown
- 1990-01-03 PT PT92778A patent/PT92778A/en not_active Application Discontinuation
- 1990-01-03 EP EP90902193A patent/EP0452409A1/en not_active Ceased
- 1990-01-03 CA CA002007062A patent/CA2007062A1/en not_active Abandoned
- 1990-01-03 JP JP2502320A patent/JPH04504432A/en active Pending
- 1990-01-03 WO PCT/EP1990/000004 patent/WO1990007566A1/en not_active Application Discontinuation
- 1990-01-03 HU HU901670A patent/HUT61584A/en unknown
- 1990-01-03 KR KR1019900701969A patent/KR910700325A/en not_active Application Discontinuation
- 1990-01-04 CN CN90100011A patent/CN1043954A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| MY104878A (en) | 1994-06-30 |
| DE3900159A1 (en) | 1990-07-05 |
| PT92778A (en) | 1990-07-31 |
| ZA899547B (en) | 1990-09-26 |
| EP0452409A1 (en) | 1991-10-23 |
| JPH04504432A (en) | 1992-08-06 |
| HUT61584A (en) | 1993-01-28 |
| YU190A (en) | 1991-08-31 |
| WO1990007566A1 (en) | 1990-07-12 |
| KR910700325A (en) | 1991-03-14 |
| US5057207A (en) | 1991-10-15 |
| CN1043954A (en) | 1990-07-18 |
| BR9006991A (en) | 1991-11-12 |
| YU46735B (en) | 1994-04-05 |
| HU901670D0 (en) | 1991-10-28 |
| AU4949590A (en) | 1990-08-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |