CN103896302A - Silicon molecular sieve and preparation method thereof - Google Patents
Silicon molecular sieve and preparation method thereof Download PDFInfo
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- CN103896302A CN103896302A CN201210589933.XA CN201210589933A CN103896302A CN 103896302 A CN103896302 A CN 103896302A CN 201210589933 A CN201210589933 A CN 201210589933A CN 103896302 A CN103896302 A CN 103896302A
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Abstract
The invention provides a silicon molecular sieve. The silicon molecular sieve is characterized by having an MFI crystal structure; the pore volume of the silicon molecular sieve is 0.3cm<3>/g, the total specific surface area of the silicon molecular sieve is 200-400m<2>/g, the outer surface area of the silicon molecular sieve is 30-150m<2>/g, and the ratio of the outer surface area in the total specific surface area ranges from 10% to 55%; the molecular sieve has the advantages that a benzene adsorption amount measured under the conditions of 25 DEG C, P/P0=0.10 and the adsorption time of 1 hour is at least 75mg of each g of molecular sieve, and the micropore diameter of the molecular sieve is in the range of 0.9-1.5nm under a nitrogen static adsorption test.
Description
Technical field
The present invention relates to a kind of silicon zeolite molecular sieve and preparation method thereof, more specifically to a kind of method of utilizing the amidoxime catalyzer of inactivation to prepare silicon zeolite molecular sieve.
Background technology
Si molecular sieves, also referred to as total silicon zeolite, is the molecular sieve that skeleton is all made up of silica element.Wherein Silicalite-1(S-1) molecular sieve is to have ZSM-5(MFI) silica zeolite of the framework of molecular sieve of structure.Can, directly as the material of membrane sepn, also can form hetero-atom molecular-sieve by the part silicon that utilizes other heteroatoms to replace in skeleton, have a extensive future.
In US4061724, having disclosed si molecular sieves S-1 and synthetic method thereof, had MFI crystalline structure, there is no aluminium source in its raw materials, only had silicon source, alkali source, template and water, is direct synthetic si molecular sieves.In the existing technology of preparing si molecular sieves, as JP59164617 and Catal.Rev.-Sci.Eng., 1997,39(4): in 395～424, do silicon source with organosilicon acid esters, when early stage is synthetic, organosilicon acid esters need to be hydrolyzed and need heating except alcohol, makes that generated time is relatively long in earlier stage; Meanwhile, a little less than the brilliant ability of leading of Si itself, the crystallization time that makes to prepare si molecular sieves is also longer.In the last few years, although improve through certain, effect was not also very good.
CN1338427A discloses a kind of si molecular sieves of MFI crystalline structure, it is characterized in that grain surface is empty male and fomale(M&F), and BET specific surface area is 430～500m
2/ g and Extra specific surface area are 5～100m
2/ g, the absorption of its nitrogen absorption under low temperature is propped up with desorption and is propped up at P/P
0between=0.45～0.98, there is hysteresis loop.
TS-1 molecular sieve is that transition metal titanium is introduced and had a kind of novel titanosilicate with good catalytic selectivity oxidation susceptibility forming in the framework of molecular sieve of ZSM-5 structure.TS-1 not only has the catalysed oxidn of titanium, but also has the shape effect selected and the good stability of ZSM-5 molecular sieve, and this molecular sieve has successfully been realized industrial application in pimelinketone catalytic ammoxidation is prepared the technique of cyclohexanone-oxime.But, there is deactivation phenomenom in catalytic performance meeting variation after operation for some time conventionally.Inactivation is divided into again temporary inactivation and permanent inactivation.The catalysis of temporary inactivation can make it recuperation section or all active through regeneration, and permanent inactivation cannot be by regeneration activity recovery (if activity after regenerating is lower than 50% situation of initial activity).Amidoxime catalyzer TS-1 occurs, after permanent deactivation, cannot recycle at present, adopts the mode processing of piling up landfill.Like this, valuable land resources and stock space have been taken.
Summary of the invention
Contriver finds through a large amount of research, when the MFI of inactivation crystalline structure HTS after roasting with the acid solution combination treatment of volumetric molar concentration >0.1mol/L, reclaim the product obtaining, there is special physical chemical characteristics, and its relative crystallinity is higher, benzene adsorptive capacity is larger.Based on this, complete the present invention.
Therefore, one of object of the present invention is to provide a kind of si molecular sieves with special physical chemical characteristics, and two of object is to provide the preparation method of above-mentioned si molecular sieves.
Si molecular sieves provided by the invention, is characterized in that this molecular sieve has MFI crystalline structure, and its pore volume is greater than 0.3cm
3/ g, total specific surface area 200～400m
2/ g, outer surface area 30～150m
2/ g, and the ratio that outer surface area accounts for total specific surface area is 10%～55%; This molecular sieve is at 25 ℃, P/P
0=0.10, adsorption time be the benzene adsorptive capacity that records under the condition of 1 hour is 75mg/g molecular sieve at least, N
2under Static Adsorption test, there is the micropore size of 0.9～1.5nm scope.
The present invention also provides the preparation method of above-mentioned si molecular sieves, it is characterized in that the HTS of the MFI crystalline structure of inactivation after roasting, mix again making beating with the acid solution of volumetric molar concentration >0.1mol/L and at 10～200 ℃, process 0.5～36 hour, reclaim product and obtain si molecular sieves, wherein, with SiO
2the HTS of the MFI crystalline structure of meter with take the sour molar ratio of H+ as 100:(5～200).
Si molecular sieves provided by the invention, has special physical chemical characteristics.The raw materials of method provided by the invention using the MFI crystalline structure HTS of inactivation as si molecular sieves, turns waste into wealth, and the yield of gained zeolite product and benzene adsorptive capacity higher.
Embodiment
Si molecular sieves provided by the invention, is characterized in that this molecular sieve has MFI crystalline structure, and its pore volume is greater than 0.3cm
3/ g, total specific surface area 200～400m
2/ g, outer surface area 30～150m
2/ g, and the ratio that outer surface area accounts for total specific surface area is 10%～55%; This molecular sieve is at 25 ℃, P/P
0=0.10, adsorption time be the benzene adsorptive capacity that records under the condition of 1 hour is 75mg/g molecular sieve at least, N
2under Static Adsorption test, there is the micropore size of 0.9～1.5nm scope.
In the present invention, its total specific surface area of the si molecular sieves providing refers to BET specific surface area, and external surface area refers to the surface-area of the outside surface of si molecular sieves, also can, referred to as outer surface area, all can record according to ASTM D4222-98 standard method.
Si molecular sieves of the present invention, Si is with SiO
2the quality percentage composition >99% of meter, preferably >99.5%, further preferred >99.9%.Generally can contain a small amount of Ti, with TiO
2the quality percentage composition <1% of meter, preferably <0.5%, further preferred <0.1%.
Si molecular sieves of the present invention, has MFI crystalline structure, and its pore volume is greater than 0.3cm
3/ g, for example, pore volume is at 0.3～0.5cm
3/ g.Total specific surface area 200～400m
2/ g, outer surface area 30～150m
2/ g, and the ratio that outer surface area accounts for total specific surface area is 10%～55%, preferred, the ratio that outer surface area accounts for total specific surface area is 10%～35%.
Si molecular sieves of the present invention, at 25 ℃, P/P
0=0.10, adsorption time be the benzene adsorptive capacity that records under the condition of 1 hour is 75mg/g molecular sieve at least, preferably, is 100mg/g molecular sieve at least, for example, be 100～130mg/g molecular sieve.
Si molecular sieves of the present invention, its micropore size is except near 0.4～0.7nm(0.55nm) have the peculiar pore size distribution of typical MFI topological framework molecular sieve in scope, within the scope of 0.9～1.5nm, also there is distribution.Here it should be noted that, if micropore size distributes while accounting for the ratio <1% of total pore size distribution amount within the scope of 0.9～1.5nm, the pore distribution of this part is ignored, think and within the scope of 0.9～1.5nm, do not have micropore to distribute, this is that those skilled in the art are in common knowledge.So the present invention is said at N
2the micropore size under Static Adsorption test with 0.9～1.5nm scope refers to that micropore size distributes within the scope of 0.9～1.5nm and accounts for ratio>=1% of total pore size distribution amount; The present invention is preferred, and within the scope of 0.4～0.7nm, micropore size distributes and accounts for ratio≤95% of total pore size distribution amount, and within the scope of 0.9～1.5nm, micropore size distributes and accounts for ratio>=5% of total pore size distribution amount; Preferred, within the scope of 0.4～0.7nm, micropore size distributes and accounts for ratio≤90% of total pore size distribution amount, and within the scope of 0.9～1.5nm, micropore size distributes and accounts for ratio>=10% of total pore size distribution amount; Most preferred, within the scope of 0.4～0.7nm, micropore size distributes and accounts for ratio≤85% of total pore size distribution amount, and within the scope of 0.9～1.5nm, micropore size distributes and accounts for ratio>=15% of total pore size distribution amount, and for example 15～30%.The testing method of micropore size is well known to those skilled in the art, as adopted N
2the method tests such as Static Adsorption.
The present invention also provides the preparation method of above-mentioned si molecular sieves, it is characterized in that the HTS of the MFI crystalline structure of inactivation after roasting, mix again making beating with the acid solution of volumetric molar concentration >0.1mol/L and at 10～200 ℃, process 0.5～36 hour, reclaim product and obtain si molecular sieves, wherein, with SiO
2meter MFI crystalline structure HTS with H
+the sour molar ratio of meter is 100:(5～200).
Preparation method provided by the invention, is that preferably to adopt the HTS of inactivation be raw material, and the HTS that conventionally can not continue again to meet operation activity all belongs to available raw material.For example, the pimelinketone oximate catalyzer (particle diameter is at 100～500nm for titanium-silicon molecular sieve TS-1, powdery) of inactivation is as main raw material.The HTS of said inactivation, take pimelinketone oximate catalyzer as example, refer to and conventional regeneration methods such as adopting solvent wash or roasting cannot make it activation recovering (initial activity refers under reaction conditions, the average activity of catalyzer within 1h to the pimelinketone oximate catalyzer of the inactivation in the situation of initial activity 50%.As in actual rings hexanone oximation reaction, the initial activity of general catalyzer will reach more than 95%).The oximate catalyzer of inactivation can derive from industrial deactivator or in laboratory, carry out the decaying catalyst after Ammoximation reaction.Certainly,, from the angle of preparation effect, method of the present invention also can adopt fresh HTS as raw material, just can be unsuitable from the angle of cost control, method provided by the invention, the main HTS using inactivation is as raw material, turn waste into wealth, saved cost.The si molecular sieves that the inventive method obtains, owing to being preferably take the HTS of inactivation as raw material, therefore, generally can contain a small amount of Ti, conventionally with TiO in product si molecular sieves
2the quality percentage composition <1% of meter, preferably <0.5%, further preferred <0.1%.
In method provided by the invention, the roasting of the HTS of inactivation is preparation method's provided by the invention necessary preparation process, but the process of baking operation is ordinary method, by those skilled in the art is familiar with, at this and have no special requirements, said roasting can be 300～800 ℃ of temperature ranges, for example 550～600 ℃ of temperature ranges, under air atmosphere or under inert gas atmosphere, operate, for example, can be first under maturing temperature, in nitrogen atmosphere, carry out in air atmosphere, carrying out 3～12 hours after 0.5～6 hour.
In method provided by the invention, said acid is one or more in organic acid and mineral acid.Wherein mineral acid can be one or more in sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid etc., and organic acid can be one or more in formic acid, acetic acid, propionic acid, naphthenic acid and Peracetic Acid, Perpropionic Acid etc.The wherein mineral acid such as preferably sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, more preferably phosphoric acid.In method provided by the invention, the preferred pH<0 of said acid solution, acid solution volumetric molar concentration >0.1mol/L, in the preferred embodiment of the present invention, acid solution volumetric molar concentration preferably >=1mol/L, its pore volume of the si molecular sieves preparing like this, specific surface area, benzene adsorptive capacity and more obvious in the feature of the pore distribution of 0.9～1.5nm etc.
In method provided by the invention, with SiO
2the HTS of the MFI crystalline structure of meter with take the sour molar ratio of H+ as 100:(5～200), preferably 100:(20～50).
In method provided by the invention, said mixing making beating is preferably carried out at normal temperatures and pressures, and said mixing making beating is also processed 0.5～36 hour treating processes at 10～200 ℃, preferably at 100～180 ℃, processes 1～24 hour.At one more preferably in embodiment of the present invention, said HTS is mixed making beating processing process with the acid solution of volumetric molar concentration >0.1mol/L is to carry out under acid solution reflux conditions, and the si molecular sieves obtaining with this understanding has more obvious physical chemical characteristics.
In method provided by the invention, the process of said recovery product is ordinary method, by those skilled in the art is familiar with, at this and have no special requirements, generally refers to that product filters, washing, dry and roasting process.Wherein, said drying process can be carried out at the temperature between room temperature～200 ℃, and said roasting process can first carry out between 300～800 ℃ for after 0.5～6 hour 3～12 hours in air atmosphere in nitrogen atmosphere.
Below by embodiment, the invention will be further described, but therefore do not limit content of the present invention.
In comparative example and embodiment, agents useful for same is commercially available chemically pure reagent.
In embodiment, the amidoxime catalyzer of inactivation used derives from following process: get TS-1 molecular sieve (by the method preparation described in " Zeolites, 1992, Vol.12:943～950 ", TiO
2quality percentage composition be 2.1%) be placed in the continuously feeding of 100mL band and membrane separation unit slurry bed reactor, under whipped state, add the mixture (volume ratio of water and hydrogen peroxide is as 10:9) of the hydrogen peroxide of water and 30wt% take the speed of 5.7mL/h, add the mixture (volume ratio of pimelinketone and the trimethyl carbinol is as 1:2.5) of pimelinketone and the trimethyl carbinol take the speed of 10.5mL/h, add 36wt% ammoniacal liquor with the speed of 5.7mL/h, above-mentioned three bursts of streams are for add simultaneously, simultaneously with corresponding speed continuous discharge, temperature of reaction maintains 80 ℃, after stable reaction, every 1 hour, product sampling is analyzed by chromatogram.The pimelinketone transformation efficiency of measuring is for the first time its initial activity, and its value is 99.5%.Through approximately 168 hours after a while, after pimelinketone transformation efficiency drops to 50% by initial 99.5%, isolate after catalyzer with roasting regeneration mode regenerate (at 570 ℃ in air atmosphere roasting 4 hours), then continue on in cyclohexanone oxamidinating reaction, repeatedly carry out this step, until the activity after regeneration is lower than 50% of initial activity.At this moment the amidoxime catalyst sample of inactivation is designated as SH-1.Within 3 hours, obtain the amidoxime catalyst S H-B of the inactivation after roasting at 550 ℃ of roasting temperatures.
In each embodiment, X-ray diffraction (XRD) the crystalline phase figure of sample measures on Siemens D5005 type x-ray diffractometer, represent the degree of crystallinity of sample with respect to authentic specimen take sample and authentic specimen at the ratio of diffracted intensity (peak height) sum at 2 θ the five fingers diffractive features peak between 22.5 °～25.0 °, here take comparative example 1 sample as authentic specimen, its degree of crystallinity counts 100%, and the relative crystallinity data of each sample and the yield data of preparation process are in table 1.Benzene adsorptive capacity, pore volume, pore size distribution, total specific surface area and the external surface area of sample are measured on the static n2 absorption apparatus of the ASAP2405 of Micromeritics company, and concrete data are in table 1.
Comparative example 1
This comparative example illustrates that conventional hydrothermal crystallizing prepares the process of S-1 sieve sample.
Tetraethyl orthosilicate is mixed with TPAOH, and add appropriate distilled water to be uniformly mixed, among reaction system, mole consist of tetraethyl orthosilicate: TPAOH: water=100:10:200, wherein tetraethyl orthosilicate is with SiO
2meter; At normal pressure and 60 ℃, be hydrolyzed 1.0 hours, then stir 3 hours at 75 ℃, obtain clear colloid.This colloid is put into stainless steel sealed reactor, and at the temperature of 170 ℃, constant temperature is placed 3 days, obtains the mixture of crystallization product; This mixture is filtered, is washed with water, and in 110 ℃ dry 60 minutes, obtain the former powder of S-1.Former this S-1 powder, in 550 ℃ of roasting temperatures 3 hours, is obtained to S-1 molecular sieve, and its XRD crystalline phase is MFI structure.The relative crystallinity data of later embodiment and comparative example are all take it as 100% degree of crystallinity benchmark.
Embodiment 1
The present embodiment illustrates method provided by the invention and product.
At normal temperatures and pressures, first the inactivation pimelinketone oximate catalyst S H-B after roasting is mixed to making beating with the hydrochloric acid soln of 1mol/L, then by mixed serum mix and blend reflow treatment 2 hours at 120 ℃, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:20, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washed with water, and dry 120 minutes in 110 ℃, then 550 ℃ of roasting temperatures 3 hours, obtain molecular sieve.Figure is consistent with comparative example 1 for its XRD crystalline phase, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Embodiment 2
The present embodiment illustrates method provided by the invention and product.
At normal temperatures and pressures, first the inactivation pimelinketone oximate catalyst S H-B after roasting is mixed to making beating with the hydrochloric acid soln of 5mol/L, then by mixed serum mix and blend reflow treatment 1 hour at 160 ℃, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:10, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washed with water, and dry 120 minutes in 110 ℃, then 550 ℃ of roasting temperatures 3 hours, obtain molecular sieve.Figure is consistent with comparative example 1 for its XRD crystalline phase, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Embodiment 3
The present embodiment illustrates method provided by the invention and product.
Be at normal temperatures and pressures, first the inactivation pimelinketone oximate catalyst S H-B after roasting is mixed to making beating with the salpeter solution of 8mol/L, then by mixed serum mix and blend reflow treatment 2 hours at 100 ℃, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:5, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washed with water, and dry 120 minutes in 110 ℃, then 550 ℃ of roasting temperatures 3 hours, obtain molecular sieve.Figure is consistent with comparative example 1 for its XRD crystalline phase, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Embodiment 4
The present embodiment illustrates method provided by the invention and product.
At normal temperatures and pressures, first the inactivation pimelinketone oximate catalyst S H-B after roasting is mixed to making beating with the sulphuric acid soln of 5mol/L, then by mixed serum mix and blend reflow treatment 1 hour at 120 ℃, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:30, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washed with water, and dry 120 minutes in 110 ℃, then 550 ℃ of roasting temperatures 3 hours, obtain molecular sieve.Figure is consistent with comparative example 1 for its XRD crystalline phase, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Embodiment 5
The present embodiment illustrates method provided by the invention and product.
At normal temperatures and pressures, first the pimelinketone oximate catalyst S H-B of the inactivation after roasting is mixed to making beating with the sulphuric acid soln of 2mol/L, then by mixed serum mix and blend reflow treatment 5 hours at 170 ℃, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:2, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washed with water, and dry 120 minutes in 110 ℃, then 550 ℃ of roasting temperatures 3 hours, obtain molecular sieve.Figure is consistent with comparative example 1 for its XRD crystalline phase, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Embodiment 6
The present embodiment illustrates method provided by the invention and product.
At normal temperatures and pressures, first the pimelinketone oximate catalyst S H-B of the inactivation after roasting is mixed to making beating with the acetic acid solution of 12mol/L, then by mixed serum mix and blend reflow treatment 6 hours at 160 ℃, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:10, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washed with water, and dry 120 minutes in 110 ℃, then 550 ℃ of roasting temperatures 3 hours, obtain molecular sieve.Figure is consistent with comparative example 1 for its XRD crystalline phase, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Embodiment 7
The present embodiment illustrates method provided by the invention and product.
At normal temperatures and pressures, first the pimelinketone oximate catalyst S H-B of the inactivation after roasting is mixed to making beating with the sulphuric acid soln of 0.5mol/L, then by mixed serum mix and blend reflow treatment 4 hours at 130 ℃, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:45, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washed with water, and dry 120 minutes in 110 ℃, then 550 ℃ of roasting temperatures 3 hours, obtain molecular sieve.Figure is consistent with comparative example 1 for its XRD crystalline phase, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Embodiment 8
The present embodiment illustrates method provided by the invention and product.
At normal temperatures and pressures, first the pimelinketone oximate catalyst S H-B of the inactivation after roasting is mixed to making beating with the phosphoric acid solution of 15mol/L, then by mixed serum mix and blend reflow treatment 3 hours at 180 ℃, wherein material mole consists of the pimelinketone oximate catalyzer of inactivation: acid=100:20, and the pimelinketone oximate catalyzer of inactivation is with SiO
2meter, acid is with H
+meter.Products therefrom is filtered, washed with water, and dry 120 minutes in 110 ℃, then 550 ℃ of roasting temperatures 3 hours, obtain molecular sieve.Figure is consistent with comparative example 1 for its XRD crystalline phase, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Embodiment 9
The present embodiment illustrates method provided by the invention and product.
Method according to embodiment 8 is prepared molecular sieve, and that different is the pimelinketone oximate catalyzer that material mole consists of inactivation: acid=100:5.The XRD crystalline phase figure of gained sample is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Embodiment 10
The present embodiment illustrates method provided by the invention and product.
Method according to embodiment 8 is prepared molecular sieve, and that different is the pimelinketone oximate catalyzer that material mole consists of inactivation: acid=100:100.The XRD crystalline phase figure of gained sample is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Embodiment 11
The present embodiment illustrates method provided by the invention and product.
Method according to embodiment 8 is prepared molecular sieve, and the concentration of different is raw material phosphoric acid is 0.2mol/L.The XRD crystalline phase figure of gained sample is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Embodiment 12
The present embodiment illustrates method provided by the invention and product.
Method according to embodiment 8 is prepared molecular sieve, and different is that raw material is the TS-1 molecular sieve after roasting.The XRD crystalline phase figure of gained sample is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Embodiment 13
The present embodiment illustrates method provided by the invention and product.
Method according to embodiment 8 is prepared molecular sieve, the airtight static processing 3 hours at 180 ℃ of different is mixed serum.The XRD crystalline phase figure of gained sample is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Embodiment 14
The present embodiment illustrates method provided by the invention and product.
Method according to embodiment 2 is prepared molecular sieve, and different is to use phosphoric acid Instead of Hydrochloric.The XRD crystalline phase figure of gained sample is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Comparative example 2
The situation when explanation of this comparative example is raw material without the pimelinketone oximate catalyzer of the inactivation of roasting.
Method according to embodiment 8 is prepared molecular sieve, and different is that raw material is the pimelinketone oximate catalyst S H-1 of inactivation.The XRD crystalline phase figure of gained sample is consistent with comparative example 1, illustrates that what obtain is the S-1 molecular sieve with MFI structure.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Comparative example 3
The explanation of this comparative example is prepared S-1 sieve sample according to the method for embodiment in CN1338427A 1.
The data such as the relative crystallinity of sample, pore volume, total specific surface area, external surface area, 0.9～1.5nm pore size distribution, benzene adsorptive capacity, molecular sieve yield are in table 1.
Table 1
As can be seen from Table 1: its relative crystallinity of si molecular sieves prepared by the preferred process of the present invention and yield are all better than comparative example.In addition, its pore volume of si molecular sieves that prepared by the preferred process of the present invention is greater than 0.3cm
3/ g, total specific surface area 200～400m
2/ g, wherein, outer surface area 30～150m
2/ g, and the ratio that outer surface area accounts for total specific surface area is between 10%～55%.
Claims (12)
1. a si molecular sieves, is characterized in that this molecular sieve has MFI crystalline structure, and its pore volume is greater than 0.3cm
3/ g, total specific surface area 200～400m
2/ g, outer surface area 30～150m
2/ g, and the ratio that outer surface area accounts for total specific surface area is 10%～55%; This molecular sieve is at 25 ℃, P/P
0=0.10, adsorption time be the benzene adsorptive capacity that records under the condition of 1 hour is 75mg/g molecular sieve at least, N
2under Static Adsorption test, there is the micropore size of 0.9～1.5nm scope.
2. according to the si molecular sieves of claim 1, wherein, said pore volume is at 0.3～0.5cm
3/ g, the ratio that said outer surface area accounts for total specific surface area is 10%～35%.
3. according to the si molecular sieves of claim 1, wherein, said at 25 ℃, P/P
0=0.10, adsorption time be the benzene adsorptive capacity that records under the condition of 1 hour is 100mg/g molecular sieve at least.
4. according to the si molecular sieves of claim 1, wherein, the said micropore size with 0.9～1.5nm scope accounts for ratio >=5% of total pore size distribution amount.
5. according to the si molecular sieves of claim 1, wherein, the said micropore size with 0.9～1.5nm scope accounts for ratio >=10% of total pore size distribution amount.
6. according to the si molecular sieves of claim 1, wherein, the said micropore size with 0.9～1.5nm scope accounts for ratio >=15% of total pore size distribution amount.
7. according to the si molecular sieves of claim 1, wherein, the ratio that the said micropore size with 0.9～1.5nm scope accounts for total pore size distribution amount is 15～30%.
8. the preparation method of the si molecular sieves of one of claim 1～7, it is characterized in that the HTS of the MFI crystalline structure of inactivation after roasting, mix again making beating with the acid solution of volumetric molar concentration >0.1mol/L and at 10～200 ℃, process 0.5～36 hour, reclaim product and obtain si molecular sieves, wherein, with SiO
2the HTS of the MFI crystalline structure of the inactivation of meter with take the sour molar ratio of H+ as 100:(5～200).
9. according to the method for claim 8, the pimelinketone oximate catalyzer that wherein HTS of the MFI crystalline structure of said inactivation is inactivation.
10. according to the method for claim 9, the wherein pimelinketone oximate catalyzer of said inactivation, its activity is down to below 50% of initial activity.
11. according to the method for claim 8, wherein volumetric molar concentration >=the 1mol/L of acid in said acid solution.
12. according to the method for claim 8, and wherein said processing is at 100～180 ℃, to reflux 1～24 hour.
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