CN103263948B - Acidic catalytic film based on in situ synthesis technology and preparation method of acidic catalytic film - Google Patents
Acidic catalytic film based on in situ synthesis technology and preparation method of acidic catalytic film Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses an acidic catalytic film based on in situ synthesis technology and a preparation method of the acidic catalytic film. A ceramic film surface and one of the ZSM-5, SBA-15 and MCM-41 molecular sieve in situ synthesis on the surface are used as a composite carrier of the catalytic film, and one or more of the SO42/-ZrO2, SO42-TiO2, p-toluene sulfonic acid, sulfuric acid, phosphoric acid, phosphotungstic acid and citric acid is used as the active precursor. The second carrier of the acidic catalytic film prepared by the invention is tightly combined with the ceramic film, the distribution is uniform, and the influence on the ceramic film duct is small; the acidic catalytic film can be applied to preparing the biodiesel in a continuous catalytic film reactor, the integration of the esterification, transesterification of the oil and the methanol and the separation of the generated biodiesel and other components is realized, thereby environment-friendly, fast and efficiently preparing the biodiesel.
Description
Technical field
The invention belongs to solid acid catalysis, Membrane catalysis field, relate to a kind of acidic catalytic membrane based on situ synthesis techniques and preparation method thereof.
Background technology
In recent years, along with deepening continuously and the promotion of industrialization of Global biodiesel research, in order to develop energy-saving and environmental protection more, efficiently biodiesel production method, process integrated technology starts to be applied to biodiesel production method, as: reactive distillation process, film reaction technique.Wherein film reaction technique is a kind of Membrane catalysis and the membrane separation and integration technology of newly-developed, catalytic esterification, ester exchange reaction and UF membrane are coupling in same flow process by it to carry out, utilize Selective Separation and the infiltration function of film, being separated of feedstock oil and biodiesel oil product and catalyst can be realized, thus improve reaction efficiency and reach the effect of purification.Further, the deficiency that can overcome heterogeneous catalysis is regulated and controled by the load capacity of membrane material design and catalyst.
Chinese patent CN 102513081A discloses a kind of acidic catalytic membrane and preparation method thereof, and adopt conventional impregnation by acidic catalytic activity central loading in ceramic membrane surface, prepared catalytic membrane shows stability and catalytic activity well.US Patent No. 20110150713 discloses a kind of catalytic membrane for the production of biodiesel, by tubulose single channel or multichannel separation membrane surface load one deck heterogeneous catalysis, can obtain the higher biodiesel of purity under appropriate conditions.The carrying method of the catalytic membrane active component related in above-mentioned patent is all cement-dipping method, although this method is simple, but coating uniformity is not high, catalyst is combined not infirm with carrier surface, and slurrying is difficult to for some, there is the problem that dip coating process cannot carry out in the catalyst of coating.
Molecular sieve has very important using value in catalysis and separation science, also by as catalyst and carrier extensive use in biodiesel preparation.But molecular sieve is difficult to dip-coating in carrier surface, if use binding agent to increase diffusion problem in dip coating process and the pore passage structure of saboteur's sieve.Can utilize when preparing carried molecular sieve (molecular sieve of carrier surface) is very effective situ synthesis techniques.Chinese patent CN 101574664 A discloses a kind of method of synthesizing MCM-22 on cordierite, and the load molecular sieve that this method obtains combines firmly, and synthesis condition is easy to control.Chinese patent CN 102133537 A discloses a kind of honeycomb ceramic type monolithic catalyst and preparation method, adopts in-situ synthesis to be coated with one deck β-molecular sieve on ceramic honey comb surface as complex carrier.
Summary of the invention
Technical problem: the invention provides a kind of dipping process that solves and prepare the uneven and problem such as easily to come off of Active components distribution that catalytic membrane brings, be applicable to the acidic catalytic membrane based on situ synthesis techniques that membrane reactor prepares biodiesel, provide a kind of preparation method of above-mentioned catalytic membrane simultaneously.
Technical scheme: the acidic catalytic membrane that the present invention is based on situ synthesis techniques, with the molecular sieve of ceramic membrane and area load thereof for complex carrier, with SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2, p-methyl benzenesulfonic acid, sulfuric acid, phosphoric acid, phosphotungstic acid, one or more in citric acid are active presoma, active presoma adopts excessive infusion process to be carried on complex carrier.Ceramic membrane is by α-Al
2o
3ceramic supporting body and diffusion barrier composition, aperture is 0.01 ~ 10 μm; Molecular sieve is any one in ZSM-5, SBA-15, MCM-41.
The preparation method of the acidic catalytic membrane based on situ synthesis techniques in the present invention, its preparation process is:
1) by ceramic membrane mass percent concentration be 5% ~ 10% nitric acid washing after be immersed in organosilicon source, slowly instill deionized water under strong agitation, Qi Zhongshui: organosilicon source quality ratio is 1 ~ 15:1;
2), after deionized water drips and terminates, one of as follows milk white gel is generated:
A) with ammoniacal liquor, mixture ph is adjusted between 10 ~ 11, continues stirring 0.5 ~ 5 hour, obtain milk white gel;
B) with ammoniacal liquor, mixture ph is adjusted between 7 ~ 9, by organosilicon source: organic formwork agent mass ratio is that 5 ~ 50:1 adds organic formwork agent, be stirred to organic formwork agent to dissolve completely, with ammoniacal liquor, mixture ph is adjusted between 10 ~ 11 again, continue stirring 0.5 ~ 5 hour, obtain milk white gel, organic formwork agent is the one in softex kw, n-butylamine, polymer P 123;
3) ceramic membrane and milk white gel are placed in water heating kettle, at 100 ~ 200 DEG C, crystallization 6 ~ 72 hours, takes out ceramic membrane after cooling, with deionized water rinsing to neutral, calcine 1 ~ 10 hour at 300 ~ 700 DEG C after oven dry, obtain the ceramic membrane that load has molecular sieve;
4) adopting infusion process that active presoma is carried on load has on the ceramic membrane of molecular sieve, namely obtains the acidic catalytic membrane based on situ synthesis techniques.
In the present invention, step 4) idiographic flow be: the load prepared had the ceramic membrane of molecular sieve to flood 1 ~ 36 hour in the precursor solution of 0.1 ~ 15mol/L, in 80 ~ 150 DEG C of oven dry after taking-up, then in 200 ~ 700 DEG C of calcinings 0.5 ~ 5 hour, the acidic catalytic membrane based on situ synthesis techniques is namely obtained.Wherein precursor solution is the aqueous solution of one or more of p-methyl benzenesulfonic acid, sulfuric acid, phosphoric acid, phosphotungstic acid, citric acid.
In the present invention, step 4) idiographic flow can also be: the load prepared had the ceramic membrane of molecular sieve to impregnated in the zirconium nitrate of 0.1 ~ 1mol/L or aqueous solution of titanyle sulfate 1 ~ 36 hour, take out, 80 ~ 150 DEG C of dryings, calcine 0.5 ~ 5 hour for 300 ~ 700 DEG C.After cooling, then impregnated in the H of 1 ~ 18.4mol/L
2sO
4in solution 1 ~ 36 hour, in 300 ~ 700 DEG C of calcinings 0.5 ~ 5 hour after 80 ~ 150 DEG C of dryings.
Step 1 of the present invention) in organosilicon source be one or more in tetraethyl orthosilicate, positive isopropyl silicate, butyl silicate, or tetraethyl orthosilicate, positive isopropyl silicate, the alcoholic solution of one or more in butyl silicate.The solvent of alcoholic solution is one or more of ethanol, propyl alcohol or butanols, and the mass percent solubility of alcoholic solution is 5% ~ 60%.
Acidic catalytic membrane of the present invention take solid acid as the molecular sieve of catalytic active component, ceramic membrane and surface in situ thereof synthesis is complex carrier, can be applicable to membrane reactor preparation, separating bio diesel oil.
Beneficial effect: the present invention compared with prior art, has the following advantages:
The acidic catalytic membrane based on situ synthesis techniques obtained by the present invention is a kind of acidic catalytic membrane without the need to coating, with adopt conventional impregnation by acidic catalytic activity central loading in ceramic membrane surface preparation method compared with, although conventional impregnation is simple, but coating uniformity is not high, catalyst is combined firm not with carrier surface, and slurrying is difficult to for some, there is the problem that dip coating process cannot carry out in the catalyst applied, if and not only solve molecular sieve based on acidic catalytic membrane prepared by situ synthesis techniques and be difficult to dip-coating in carrier surface and use binding agent to increase diffusion problem in dip coating process and the problem such as pore passage structure of saboteur's sieve, the acidic catalytic membrane prepared as complex carrier also shows stability and catalytic activity well, improve catalytic activity and catalyst life.And this catalytic membrane has catalysis and separation function simultaneously, simplify product postprocessing process, improve the feature of environmental protection of catalytic efficiency and process.
Detailed description of the invention
The first preparation method of acidic catalytic membrane based on situ synthesis techniques provided by the invention is: ceramic membrane being soaked in mass percent concentration is in the nitric acid of 5% ~ 10% 1 ~ 10 hour, extremely neutral with deionized water rinsing after taking-up, in 300 ~ 600 DEG C of calcinings 1 ~ 3 hour after 60 ~ 100 DEG C of oven dry.Ceramic membrane after above-mentioned dust technology washing is immersed in organosilicon source, slowly instills deionized water under strong agitation, Qi Zhongshui: organosilicon source quality ratio is 1 ~ 15:1; After dropping terminates, with ammoniacal liquor, mixture ph is adjusted between 10 ~ 11, continues stirring 0.5 ~ 5 hour, generate milk white gel; Then ceramic membrane and milk white gel are placed in water heating kettle, at 100 ~ 200 DEG C, crystallization 6 ~ 72 hours, takes out ceramic membrane after cooling, with deionized water rinsing to neutral, calcine 1 ~ 10 hour at 300 ~ 700 DEG C after oven dry, obtain the ceramic membrane that load has molecular sieve; Then the load prepared there is the ceramic membrane of molecular sieve to flood 1 ~ 36 hour in the precursor solution of 0.1 ~ 15mol/L, take out, in 200 ~ 700 DEG C of calcinings 0.5 ~ 5 hour after 80 ~ 150 DEG C of oven dry.
The second preparation method of the acidic catalytic membrane based on situ synthesis techniques provided by the invention is: ceramic membrane being soaked in mass percent concentration is in the nitric acid of 5% ~ 10% 1 ~ 10 hour, extremely neutral with deionized water rinsing after taking-up, in 300 ~ 600 DEG C of calcinings 1 ~ 3 hour after 60 ~ 100 DEG C of oven dry.Ceramic membrane after above-mentioned dust technology washing is immersed in organosilicon source, slowly instills deionized water under strong agitation, Qi Zhongshui: organosilicon source quality ratio is 1 ~ 15:1; After dropping terminates, with ammoniacal liquor, mixture ph is adjusted between 10 ~ 11, continues stirring 0.5 ~ 5 hour, generate milk white gel; Then ceramic membrane and milk white gel are placed in water heating kettle, at 100 ~ 200 DEG C, crystallization 6 ~ 72 hours, takes out ceramic membrane after cooling, with deionized water rinsing to neutral, calcine 1 ~ 10 hour at 300 ~ 700 DEG C after oven dry, obtain the ceramic membrane that load has molecular sieve; Then the load prepared there is the ceramic membrane of molecular sieve to impregnated in 0.1 ~ 1mol/L zirconium nitrate or aqueous solution of titanyle sulfate 1 ~ 36 hour, take out, in 300 ~ 700 DEG C of calcinings 0.5 ~ 5 hour after 80 ~ 150 DEG C of dryings.After cooling, then impregnated in the H of 1 ~ 18.4mol/L
2sO
4in solution 1 ~ 36 hour, in 300 ~ 700 DEG C of calcinings 0.5 ~ 5 hour after 80 ~ 150 DEG C of dryings.
The third preparation method of acidic catalytic membrane based on situ synthesis techniques provided by the invention is: ceramic membrane being soaked in mass percent concentration is in the nitric acid of 5% ~ 10% 1 ~ 10 hour, extremely neutral with deionized water rinsing after taking-up, in 300 ~ 600 DEG C of calcinings 1 ~ 3 hour after 60 ~ 100 DEG C of oven dry.Ceramic membrane after above-mentioned dust technology washing is immersed in organosilicon source, slowly instills deionized water under strong agitation, Qi Zhongshui: organosilicon source quality ratio is 1 ~ 15:1; After dropping terminates, with ammoniacal liquor, mixture ph is adjusted to 7 ~ 9, by organosilicon source: organic formwork agent mass ratio is that 5 ~ 50:1 adds organic formwork agent, be stirred to organic formwork agent to dissolve completely, again mixture ph is adjusted between 10 ~ 11, continues stirring 0.5 ~ 5 hour, generate milk white gel; Then ceramic membrane and milk white gel are placed in water heating kettle, at 100 ~ 200 DEG C, crystallization 6 ~ 72 hours, takes out ceramic membrane after cooling, with deionized water rinsing to neutral, calcine 1 ~ 10 hour at 300 ~ 700 DEG C after oven dry, obtain the ceramic membrane that load has molecular sieve; Then the ceramic membrane of molecular sieve the load prepared is had to flood 1 ~ 36 hour in the precursor solution of 0.1 ~ 15mol/L, in 80 ~ 150 DEG C of oven dry after taking-up, then in 200 ~ 700 DEG C of calcinings 0.5 ~ 5 hour.
4th kind of preparation method of the acidic catalytic membrane based on situ synthesis techniques provided by the invention is: ceramic membrane being soaked in mass percent concentration is in the nitric acid of 5% ~ 10% 1 ~ 10 hour, extremely neutral with deionized water rinsing after taking-up, in 300 ~ 600 DEG C of calcinings 1 ~ 3 hour after 60 ~ 100 DEG C of oven dry.Ceramic membrane after above-mentioned dust technology washing is immersed in organosilicon source, slowly instills deionized water under strong agitation, Qi Zhongshui: organosilicon source quality ratio is 1 ~ 15:1; After dropping terminates, with ammoniacal liquor, mixture ph is adjusted to 7 ~ 9, by organosilicon source: organic formwork agent mass ratio is that 5 ~ 50:1 adds organic formwork agent, be stirred to organic formwork agent to dissolve completely, again mixture ph is adjusted between 10 ~ 11, continues stirring 0.5 ~ 5 hour, generate milk white gel; Then ceramic membrane and milk white gel are placed in water heating kettle, at 100 ~ 200 DEG C, crystallization 6 ~ 72 hours, takes out ceramic membrane after cooling, with deionized water rinsing to neutral, calcine 1 ~ 10 hour at 300 ~ 700 DEG C after oven dry, obtain the ceramic membrane that load has molecular sieve; The load prepared there is the ceramic membrane of molecular sieve to impregnated in the zirconium nitrate of 0.1 ~ 1mol/L or aqueous solution of titanyle sulfate 1 ~ 36 hour, take out, 80 ~ 150 DEG C of dryings, 300 ~ 700 DEG C of calcinings 0.5 ~ 5 hour.After cooling, then impregnated in the H of 1 ~ 18.4mol/L
2sO
4in solution 1 ~ 36 hour, in 300 ~ 700 DEG C of calcinings 0.5 ~ 5 hour after 80 ~ 150 DEG C of dryings.
Below in conjunction with specific embodiment, the invention will be further described, and embodiment is not limited.In order to follow-up describes conveniently, ceramic membrane carrier CM represents, prepared acidic catalytic membrane active component/molecular sieve carrier/CM represents.
Embodiment 1:
Ceramic membrane being placed in mass percent concentration is 5%HNO
3soak 2 hours in solution, taking-up, is calcined 3 hours after 70 DEG C of oven dry to neutral with distilled water flushing in 500 DEG C, for subsequent use.
Ceramic membrane after washing is immersed in 20g tetraethyl orthosilicate, slowly 20g deionized water is instilled under strong agitation, dropwising rear ammoniacal liquor regulates the pH value of solution between 10-11, continue stirring, after 0.5 hour, ceramic membrane and feed liquid are placed in water heating kettle, in 200 DEG C of crystallization 6 hours, after being cooled to room temperature, take out ceramic membrane, spend deionized water to neutral, calcine 6 hours at 550 DEG C after 70 DEG C of dryings, obtain the ceramic membrane that load has MCM-41.
Load being had the ceramic membrane of molecular sieve to impregnated in concentration is in 0.3mol/L p-methyl benzenesulfonic acid (PTSA) aqueous solution 24 hours, in 110 DEG C of dryings 5 hours after taking-up, then within 1 hour, namely obtains PTSA/MCM-41/CM acidic catalytic membrane 200 DEG C of calcinings.
Embodiment 2:
Ceramic membrane being placed in mass percent concentration is 8%HNO
3soak 2 hours in solution, taking-up, is calcined 3 hours after 70 DEG C of oven dry to neutral with distilled water flushing in 500 DEG C, for subsequent use.
Ceramic membrane after washing is immersed in the positive isopropyl silicate of 10g, slowly 150g deionized water is instilled under strong agitation, dropwising rear ammoniacal liquor regulates the pH value of solution between 10-11, continue stirring, after 2 hours, ceramic membrane and feed liquid are placed in water heating kettle, in 100 DEG C of crystallization 72 hours, after being cooled to room temperature, take out ceramic membrane, spend deionized water to neutral, calcine 1 hour at 700 DEG C after 70 DEG C of dryings, obtain the ceramic membrane that load has MCM-41.
Load being had the ceramic membrane of molecular sieve to impregnated in concentration is in the aqueous solution of titanyle sulfate of 0.1mol/L 36 hours, takes out, in 300 DEG C of calcinings 2 hours after 80 DEG C of dryings; And then gained carrier is flooded 1 hour in the concentrated sulfuric acid solution of 18.4mol/L, in 80 DEG C of dryings after taking-up, 300 DEG C of calcinings obtained SO after 3 hours
4 2-/ TiO
2/ MCM-41/CM acidic catalytic membrane.
Embodiment 3:
Ceramic membrane being placed in mass percent concentration is 10%HNO
3soak 2 hours in solution, taking-up, is calcined 3 hours after 70 DEG C of oven dry to neutral with distilled water flushing in 500 DEG C, for subsequent use.
Ceramic membrane after washing is immersed in 20g butyl silicate, slowly 100g deionized water is instilled under strong agitation, dropwising rear ammoniacal liquor regulates the pH value of solution between 10-11, continue stirring, after 5 hours, ceramic membrane and feed liquid are placed in water heating kettle, in 180 DEG C of crystallization 36 hours, after being cooled to room temperature, take out ceramic membrane, spend deionized water to neutral, calcine 10 hours at 300 DEG C after 70 DEG C of dryings, obtain the ceramic membrane that load has MCM-41.
Load being had the ceramic membrane of molecular sieve to impregnated in concentration is in the zirconium nitrate solution of 0.3mol/L 24 hours, takes out, in 700 DEG C of calcinings 0.5 hour after 150 DEG C of dryings; And then gained carrier is flooded 24 hours in the concentrated sulfuric acid solution of 15mol/L, in 150 DEG C of dryings after taking-up, 700 DEG C of calcinings obtained SO after 0.5 hour
4 2-/ ZrO
2/ MCM-41/CM acidic catalytic membrane.
Embodiment 4:
Ceramic membrane being placed in mass percent concentration is 5%HNO
3soak 2 hours in solution, taking-up, is calcined 3 hours after 70 DEG C of oven dry to neutral with distilled water flushing in 500 DEG C, for subsequent use.
Pretreated ceramic membrane is immersed in the ethanolic solution of 50g60% tetraethyl orthosilicate, with ammoniacal liquor, material liquid pH value is adjusted to 7 ~ 9, add 4g polymer P 123 again, be stirred to and dissolve completely, slowly be added dropwise to 150g deionized water, continue to stir and regulate the pH value of solution between 10-11 with ammoniacal liquor, continue stirring, after 0.5 hour, ceramic membrane and feed liquid are placed in water heating kettle, in 180 DEG C of crystallization 36 hours after sealing, carrier is taken out after being cooled to room temperature, spend deionized water to neutral, dry, last calcining at 550 DEG C removes template in 6 hours, obtain the ceramic membrane that load has SBA-15.
Load being had the ceramic membrane of molecular sieve to impregnated in concentration is in 0.1mol/L PTSA solution 36 hours, in 80 DEG C of dryings 5 hours after taking-up, then within 0.5 hour, namely obtains PTSA/SBA-15/CM acidic catalytic membrane 300 DEG C of calcinings.
Embodiment 5:
Ceramic membrane being placed in mass percent concentration is 5%HNO
3soak 2 hours in solution, taking-up, is calcined 3 hours after 70 DEG C of oven dry to neutral with distilled water flushing in 500 DEG C, for subsequent use.
Pretreated ceramic membrane is immersed in the propanol solution of 50g30% butyl silicate, with ammoniacal liquor, material liquid pH value is adjusted to 7 ~ 9, add 2g softex kw again, be stirred to and dissolve completely, slowly be added dropwise to 50g deionized water, continue to stir and regulate the pH value of solution between 10-11 with ammoniacal liquor, continue stirring, after 2 hours, ceramic membrane and feed liquid are placed in water heating kettle, in 180 DEG C of crystallization 72 hours after sealing, be cooled to room temperature, take out carrier, washing is to neutral, dry, last calcining at 550 DEG C removes template in 6 hours, obtain the ceramic membrane that load has MCM-41.
Load being had the ceramic membrane of molecular sieve to impregnated in concentration is in the aqueous solution of titanyle sulfate of 1mol/L 1 hour, takes out, in 500 DEG C of calcinings 5 hours after 110 DEG C of dryings; And then gained carrier is flooded 36 hours in the sulfuric acid solution of 1mol/L, in 130 DEG C of dryings after taking-up, 550 DEG C of calcinings obtained SO after 5 hours
4 2-/ TiO
2/ MCM-41/CM acidic catalytic membrane.
Embodiment 6:
Ceramic membrane being placed in mass percent concentration is 5%HNO
3soak 2 hours in solution, taking-up, is calcined 3 hours after 70 DEG C of oven dry to neutral with distilled water flushing in 500 DEG C, for subsequent use.
Pretreated ceramic membrane is immersed in the butanol solution of the positive isopropyl silicate of 50g60%, with ammoniacal liquor, material liquid pH value is adjusted to 7 ~ 9, add 0.4g softex kw again, be stirred to and dissolve completely, slowly be added dropwise to 50g deionized water, continue to stir and regulate the pH value of solution between 10-11 with ammoniacal liquor, continue stirring, after 5 hours, ceramic membrane and feed liquid are placed in water heating kettle, in 180 DEG C of crystallization 72 hours after sealing, be cooled to room temperature, take out carrier, washing is to neutral, dry, last calcining at 550 DEG C removes template in 6 hours, obtain the ceramic membrane that load has MCM-41.
Load being had the ceramic membrane of molecular sieve to impregnated in concentration is in the zirconium nitrate solution of 0.5mol/L 24 hours, takes out, in 500 DEG C of calcinings 3 hours after 100 DEG C of dryings; And then gained carrier is flooded 24 hours in the concentrated sulfuric acid solution of 18.4mol/L, in 110 DEG C of dryings after taking-up, 550 DEG C of calcinings obtained SO after 3 hours
4 2-/ ZrO
2/ MCM-41/CM acidic catalytic membrane.
Embodiment 7:
Ceramic membrane being placed in mass percent concentration is 5%HNO
3soak 2 hours in solution, taking-up, is calcined 3 hours after 70 DEG C of oven dry to neutral with distilled water flushing in 500 DEG C, for subsequent use.
Pretreated ceramic membrane is immersed in the ethanolic solution of 50g5% tetraethyl orthosilicate, with ammoniacal liquor, material liquid pH value is adjusted to 7 ~ 9, add 5g n-butylamine again, be stirred to and dissolve completely, slowly be added dropwise to 100g deionized water, continue to stir and regulate the pH value of solution between 10-11 with ammoniacal liquor, continue stirring, after 2 hours, ceramic membrane and feed liquid are placed in water heating kettle, in 180 DEG C of crystallization 36 hours after sealing, carrier is taken out after being cooled to room temperature, spend deionized water to neutral, dry, last calcining at 550 DEG C removes template in 6 hours, obtain the ceramic membrane that load has ZSM-5.
Load being had the ceramic membrane of molecular sieve to impregnated in concentration is in the sulfuric-phosphoric-phosphotungstic acid-aqueous citric acid solution of 15mol/L 1 hour, in 150 DEG C of dryings 5 hours after taking-up, then within 5 hours, namely obtain sulfuric-phosphoric-phosphotungstic acid-citric acid/ZSM-5/CM acidic catalytic membrane 700 DEG C of calcinings.
Embodiment 8:
Palm oil and methyl alcohol press molar ratio of methanol to oil 20:1, enter membrane reactor through blender, and controlling reaction temperature is 65 DEG C, and the palm oil time of staying is 20 minutes.Through catalytic membrane permeability and separation out, decompression distillation removing excessive methanol, namely obtains biodiesel for product and methyl alcohol; By analysis, palm oil conversion ratio reaches more than 98%, and the yield of biodiesel is 96%.
Claims (4)
1. prepare a method for the acidic catalytic membrane based on situ synthesis techniques, it is characterized in that, steps of the method are:
1) by ceramic membrane mass percent concentration be 5% ~ 10% nitric acid washing after be immersed in organosilicon source, slowly instill deionized water under strong agitation, Qi Zhongshui: organosilicon source quality ratio is 1 ~ 15:1;
2), after deionized water drips and terminates, one of as follows milk white gel is generated:
A) with ammoniacal liquor, mixture ph is adjusted between 10 ~ 11, continues stirring 0.5 ~ 5 hour, obtain milk white gel;
B) with ammoniacal liquor, mixture ph is adjusted between 7 ~ 9, by organosilicon source: organic formwork agent mass ratio is that 5 ~ 50:1 adds organic formwork agent, be stirred to organic formwork agent to dissolve completely, with ammoniacal liquor, mixture ph is adjusted between 10 ~ 11 again, continue stirring 0.5 ~ 5 hour, obtain milk white gel, described organic formwork agent is the one in softex kw, n-butylamine, polymer P 123;
3) ceramic membrane and milk white gel are placed in water heating kettle, at 100 ~ 200 DEG C, crystallization 6 ~ 72 hours, takes out ceramic membrane after cooling, with deionized water rinsing to neutral, calcine 1 ~ 10 hour at 300 ~ 700 DEG C after oven dry, obtain the ceramic membrane that load has molecular sieve;
4) adopting infusion process that active presoma is carried on load has on the ceramic membrane of molecular sieve, namely obtains the acidic catalytic membrane based on situ synthesis techniques.
2. prepare the method for the acidic catalytic membrane based on situ synthesis techniques according to claim 1, it is characterized in that, described step 4) idiographic flow be: the load prepared had the ceramic membrane of molecular sieve to flood 1 ~ 36 hour in the precursor solution of 0.1 ~ 15mol/L, in 80 ~ 150 DEG C of oven dry after taking-up, then in 200 ~ 700 DEG C of calcinings 0.5 ~ 5 hour, namely obtain the acidic catalytic membrane based on situ synthesis techniques, described precursor solution is the aqueous solution of one or more of p-methyl benzenesulfonic acid, sulfuric acid, phosphoric acid, phosphotungstic acid, citric acid.
3. prepare the method for the acidic catalytic membrane based on situ synthesis techniques according to claim 1, it is characterized in that, described step 4) idiographic flow be: the load prepared had the ceramic membrane of molecular sieve to impregnated in 0.1 ~ 1mol/L zirconium nitrate or aqueous solution of titanyle sulfate 1 ~ 36 hour, in 80 ~ 150 DEG C of oven dry after taking-up, then in 300 ~ 700 DEG C of calcinings 0.5 ~ 5 hour, after cooling, then impregnated in 1 ~ 18.4mol/LH
2sO
4in solution 1 ~ 36 hour, in 300 ~ 700 DEG C of calcinings 0.5 ~ 5 hour after 80 ~ 150 DEG C of dryings, namely obtain the acidic catalytic membrane based on situ synthesis techniques.
4. according to claim 1,2 or 3, prepare the preparation method of the acidic catalytic membrane based on situ synthesis techniques, it is characterized in that, described step 1) in organosilicon source be one or more in tetraethyl orthosilicate, positive isopropyl silicate, butyl silicate, or the alcoholic solution of one or more in tetraethyl orthosilicate, just isopropyl silicate, butyl silicate, the solvent of described alcoholic solution is one or more of ethanol, propyl alcohol or butanols, and the mass percent solubility of described alcoholic solution is 5% ~ 60%.
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| CN104525247B (en) * | 2015-01-26 | 2017-10-20 | 南开大学 | A kind of preparation method that biological kerosene hydrogenation deoxidation and hydroisomerisation catalysts are prepared for castor oil |
| CN109847092B (en) * | 2018-06-18 | 2020-03-31 | 浙江大学 | Hemostatic compound and preparation method thereof |
| CN111686793B (en) * | 2020-05-28 | 2023-04-18 | 宁夏大学 | Composite catalyst and preparation and application thereof |
| CN111804335A (en) * | 2020-07-09 | 2020-10-23 | 长春工业大学 | Phosphotungstic acid and propylsulfonic acid functionalized silicon oxide composite material in non-hydrochloric acid system and preparation method thereof |
| CN114100644A (en) * | 2021-10-29 | 2022-03-01 | 中国科学院金属研究所 | Solid acid catalytic separation integrated filler and preparation method and application thereof |
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| CN100999324A (en) * | 2006-12-27 | 2007-07-18 | 中国科学院成都有机化学有限公司 | Preparation method of titanium silicon molecular sieve membrane |
| CN101797518A (en) * | 2010-04-14 | 2010-08-11 | 太原理工大学 | Method for preparing monolithic catalyst for purification of diesel exhaust |
| CN102500400A (en) * | 2011-11-08 | 2012-06-20 | 东南大学 | Acidic catalytic membrane and preparation method thereof |
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2013
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100999324A (en) * | 2006-12-27 | 2007-07-18 | 中国科学院成都有机化学有限公司 | Preparation method of titanium silicon molecular sieve membrane |
| CN101797518A (en) * | 2010-04-14 | 2010-08-11 | 太原理工大学 | Method for preparing monolithic catalyst for purification of diesel exhaust |
| CN102500400A (en) * | 2011-11-08 | 2012-06-20 | 东南大学 | Acidic catalytic membrane and preparation method thereof |
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