CN103263948A - 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
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- Y02E50/10—Biofuels, e.g. bio-diesel
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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, film catalytic field, relate to a kind of acidic catalyst film based on the original position synthetic technology 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, production of biodiesel technology efficiently, the process integration technology begins to be applied to production of biodiesel technology, as: reactive distillation process, film reaction technology.Wherein film reaction technology is a kind of film catalysis and the membrane separation and integration technology of newly-developed, it separates catalytic esterification, ester exchange reaction to be coupling in the same flow process and carries out with film, utilize Selective Separation and the infiltration function of film, can realize separating of feedstock oil and biodiesel product and catalyst, thereby improve reaction efficiency and reach the effect of purification.And, design the deficiency that can overcome heterogeneous catalysis with the load capacity regulation and control of catalyst by membrane material.
Chinese patent CN 102513081A discloses a kind of acidic catalyst film and preparation method thereof, adopts common infusion process that the acidic catalyst activated centre is carried on ceramic membrane surface, and 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 at tubulose single channel or multichannel separation membrane surface load one deck heterogeneous catalysis, can obtain the higher biodiesel of purity under suitable condition.The carrying method of the catalytic membrane active component that relates in the above-mentioned patent all is cement-dipping method, though this method is simple, but the coating uniformity is not high, and catalyst is combined firm inadequately with carrier surface, and is difficult to the problem that the catalyst of slurrying, coating exists the dip-coating process to carry out for some.
Molecular sieve has very important use value in catalysis and separation science, also is used as catalyst and carrier extensive use in biodiesel manufacture.But molecular sieve is difficult to dip-coating in carrier surface, if use binding agent will increase the pore passage structure of diffusion problem and saboteur's sieve in the dip-coating process.When preparation carried molecular sieve (molecular sieve of carrier surface), can utilize and be very much effective original position synthetic technology.Chinese patent CN 101574664 A disclose a kind of method at the synthetic MCM-22 of cordierite, and the load molecular sieve that this method obtains is in conjunction with firm, and synthesis condition is easy to control.Chinese patent CN 102133537 A disclose a kind of honeycomb ceramic type monolithic catalyst and preparation method, adopt in-situ synthesis in the ceramic honey comb surface-coated one deck β-molecular sieve as complex carrier.
Summary of the invention
Technical problem:The invention provides and a kind ofly solve that dipping process prepares the active component skewness that catalytic membrane brings and problem such as easily come off, be applicable to that membrane reactor prepares the acidic catalyst film based on the original position synthetic technology of biodiesel, provides a kind of preparation method of above-mentioned catalytic membrane simultaneously.
Technical scheme:The present invention is based on the acidic catalyst film of original position synthetic technology, is complex carrier with the molecular sieve of ceramic membrane and area load thereof, with SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2, in the p-methyl benzenesulfonic acid, sulfuric acid, phosphoric acid, phosphotungstic acid, citric acid one or more are active presoma, active presoma adopts excessive infusion process to be carried on the complex carrier.Ceramic membrane is by α-Al
2O
3Ceramic supporting body and diffusion barrier are formed, and the aperture is 0.01～10 μ m; Molecular sieve is any among ZSM-5, SBA-15, the MCM-41.
The preparation method based on the acidic catalyst film of original position synthetic technology among the present invention, its preparation process is:
1) be to be immersed in the organosilicon source after the washing of 5% ~ 10% nitric acid the ceramic membrane mass percent concentration, slowly splash into deionized water, wherein water under the strong agitation: organosilicon source quality ratio is 1 ~ 15:1;
2) after deionized water drip to finish, generate one of as follows the milky gel:
A) with ammoniacal liquor mixture pH value is adjusted between 10 ~ 11, continues to stir 0.5 ~ 5 hour, obtain the milky gel;
B) with ammoniacal liquor mixture pH value is transferred between 7 ~ 9, by the organosilicon source: the organic formwork agent mass ratio is that 5 ~ 50:1 adds organic formwork agent, being stirred to organic formwork agent dissolves fully, with ammoniacal liquor mixture pH value is transferred between 10 ~ 11 again, continue to stir 0.5 ~ 5 hour, obtain the milky gel, organic formwork agent is a kind of in softex kw, n-butylamine, the polymer P 123;
3) ceramic membrane and milky gel are placed water heating kettle, 100 ~ 200 ℃ of following crystallization 6 ~ 72 hours, ceramic membrane is taken out in the cooling back, and to neutral, the oven dry back obtains the ceramic membrane that load has molecular sieve in 300 ~ 700 ℃ of calcinings 1 ~ 10 hour down with deionized water rinsing;
4) adopting infusion process that active presoma is carried on load has on the ceramic membrane of molecular sieve, namely obtains the acidic catalyst film based on the original position synthetic technology.
Among the present invention, the idiographic flow of step 4) is: the load for preparing is had the ceramic membrane of molecular sieve flooded in the precursor solution of 0.1 ~ 15mol/L 1 ~ 36 hour, take out the back in 80 ~ 150 ℃ of oven dry, in 200 ~ 700 ℃ of calcinings 0.5 ~ 5 hour, namely obtain the acidic catalyst film based on the original position synthetic technology then.Wherein precursor solution is one or more the aqueous solution of p-methyl benzenesulfonic acid, sulfuric acid, phosphoric acid, phosphotungstic acid, citric acid.
Among the present invention, the idiographic flow of step 4) can also for: have the ceramic membrane of molecular sieve to impregnated in the zirconium nitrate of 0.1 ~ 1mol/L or the aqueous solution of titanyle sulfate 1 ~ 36 hour the load for preparing, take out, 80 ~ 150 ℃ of dryings were calcined 0.5 ~ 5 hour for 300 ~ 700 ℃.After the cooling, impregnated in the H of 1 ~ 18.4mol/L again
2SO
4In the solution 1 ~ 36 hour, 80 ~ 150 ℃ of dry backs were in 300 ~ 700 ℃ of calcinings 0.5 ~ 5 hour.
Organosilicon source in the step 1) of the present invention is one or more in positive tetraethyl orthosilicate, positive isopropyl silicate, the butyl silicate, or one or more the alcoholic solution in the positive tetraethyl orthosilicate, positive isopropyl silicate, 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 catalyst film of the present invention is that the synthetic molecular sieve of catalytic active component, ceramic membrane and surface in situ thereof is complex carrier with the solid acid, 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 prepared acidic catalyst film based on the original position synthetic technology of the present invention is a kind of acidic catalyst film that need not coating, with the common infusion process of employing the preparation method that the acidic catalyst activated centre is carried on ceramic membrane surface is compared, though common infusion process is simple, but the coating uniformity is not high, catalyst is combined firm inadequately with carrier surface, and be difficult to slurrying for some, the problem that the catalyst that applies exists the dip-coating process to carry out, if be difficult to dip-coating and use binding agent will increase the problems such as pore passage structure of diffusion problem and saboteur's sieve in carrier surface and in the dip-coating process and not only solved molecular sieve based on the acidic catalyst film of original position synthetic technology preparation, acidic catalyst film as the complex carrier preparation also shows stability and catalytic activity well, has improved catalytic activity and catalyst life.And this catalytic membrane has catalysis and separation function simultaneously, has simplified the product postprocessing process, has improved the feature of environmental protection of catalytic efficiency and process.
The specific embodiment
First kind of preparation method of the acidic catalyst film based on the original position synthetic technology provided by the invention is: it is in 5% ~ 10% the nitric acid 1 ~ 10 hour that ceramic membrane is soaked in mass percent concentration, it is extremely neutral with deionized water rinsing to take out the back, calcines 1 ~ 3 hour in 300 ~ 600 ℃ after 60 ~ 100 ℃ of oven dry.Ceramic membrane after above-mentioned rare nitric acid washing is immersed in the organosilicon source, and slowly splash into deionized water, wherein water under the strong agitation: organosilicon source quality ratio is 1 ~ 15:1; After dripping end, with ammoniacal liquor mixture pH value is adjusted between 10 ~ 11, continues to stir 0.5 ~ 5 hour, generate the milky gel; Then ceramic membrane and milky gel are placed water heating kettle, 100 ~ 200 ℃ of following crystallization 6 ~ 72 hours, ceramic membrane is taken out in the cooling back, and to neutral, the oven dry back obtains the ceramic membrane that load has molecular sieve in 300 ~ 700 ℃ of calcinings 1 ~ 10 hour down with deionized water rinsing; Then the load for preparing there is the ceramic membrane of molecular sieve in the precursor solution of 0.1 ~ 15mol/L, to flood 1 ~ 36 hour, takes out, calcined 0.5 ~ 5 hour in 200 ~ 700 ℃ after 80 ~ 150 ℃ of oven dry.
Second kind of preparation method of the acidic catalyst film based on the original position synthetic technology provided by the invention is: it is in 5% ~ 10% the nitric acid 1 ~ 10 hour that ceramic membrane is soaked in mass percent concentration, it is extremely neutral with deionized water rinsing to take out the back, calcines 1 ~ 3 hour in 300 ~ 600 ℃ after 60 ~ 100 ℃ of oven dry.Ceramic membrane after above-mentioned rare nitric acid washing is immersed in the organosilicon source, and slowly splash into deionized water, wherein water under the strong agitation: organosilicon source quality ratio is 1 ~ 15:1; After dripping end, with ammoniacal liquor mixture pH value is adjusted between 10 ~ 11, continues to stir 0.5 ~ 5 hour, generate the milky gel; Then ceramic membrane and milky gel are placed water heating kettle, 100 ~ 200 ℃ of following crystallization 6 ~ 72 hours, ceramic membrane is taken out in the cooling back, and to neutral, the oven dry back obtains the ceramic membrane that load has molecular sieve in 300 ~ 700 ℃ of calcinings 1 ~ 10 hour down with deionized water rinsing; Then the load for preparing is had the ceramic membrane of molecular sieve to impregnated in 0.1 ~ 1mol/L zirconium nitrate or the aqueous solution of titanyle sulfate 1 ~ 36 hour, take out, 80 ~ 150 ℃ of dry backs were in 300 ~ 700 ℃ of calcinings 0.5 ~ 5 hour.After the cooling, impregnated in the H of 1 ~ 18.4mol/L again
2SO
4In the solution 1 ~ 36 hour, 80 ~ 150 ℃ of dry backs were in 300 ~ 700 ℃ of calcinings 0.5 ~ 5 hour.
The third preparation method of acidic catalyst film based on the original position synthetic technology provided by the invention is: it is in 5% ~ 10% the nitric acid 1 ~ 10 hour that ceramic membrane is soaked in mass percent concentration, it is extremely neutral with deionized water rinsing to take out the back, calcines 1 ~ 3 hour in 300 ~ 600 ℃ after 60 ~ 100 ℃ of oven dry.Ceramic membrane after above-mentioned rare nitric acid washing is immersed in the organosilicon source, and slowly splash into deionized water, wherein water under the strong agitation: organosilicon source quality ratio is 1 ~ 15:1; After drip finishing, with ammoniacal liquor mixture pH value is transferred to 7 ~ 9, by the organosilicon source: the organic formwork agent mass ratio is 5 ~ 50:1 adding organic formwork agent, being stirred to organic formwork agent dissolves fully, again mixture pH value is transferred between 10 ~ 11, continue to stir 0.5 ~ 5 hour, generate the milky gel; Then ceramic membrane and milky gel are placed water heating kettle, 100 ~ 200 ℃ of following crystallization 6 ~ 72 hours, ceramic membrane is taken out in the cooling back, and to neutral, the oven dry back obtains the ceramic membrane that load has molecular sieve in 300 ~ 700 ℃ of calcinings 1 ~ 10 hour down with deionized water rinsing; Then the load for preparing there is the ceramic membrane of molecular sieve in the precursor solution of 0.1 ~ 15mol/L, to flood 1 ~ 36 hour, takes out the back in 80 ~ 150 ℃ of oven dry, then in 200 ~ 700 ℃ of calcinings 0.5 ~ 5 hour.
The 4th kind of preparation method of the acidic catalyst film based on the original position synthetic technology provided by the invention is: it is in 5% ~ 10% the nitric acid 1 ~ 10 hour that ceramic membrane is soaked in mass percent concentration, it is extremely neutral with deionized water rinsing to take out the back, calcines 1 ~ 3 hour in 300 ~ 600 ℃ after 60 ~ 100 ℃ of oven dry.Ceramic membrane after above-mentioned rare nitric acid washing is immersed in the organosilicon source, and slowly splash into deionized water, wherein water under the strong agitation: organosilicon source quality ratio is 1 ~ 15:1; After drip finishing, with ammoniacal liquor mixture pH value is transferred to 7 ~ 9, by the organosilicon source: the organic formwork agent mass ratio is 5 ~ 50:1 adding organic formwork agent, being stirred to organic formwork agent dissolves fully, again mixture pH value is transferred between 10 ~ 11, continue to stir 0.5 ~ 5 hour, generate the milky gel; Then ceramic membrane and milky gel are placed water heating kettle, 100 ~ 200 ℃ of following crystallization 6 ~ 72 hours, ceramic membrane is taken out in the cooling back, and to neutral, the oven dry back obtains the ceramic membrane that load has molecular sieve in 300 ~ 700 ℃ of calcinings 1 ~ 10 hour down with deionized water rinsing; There is the ceramic membrane of molecular sieve to impregnated in the zirconium nitrate of 0.1 ~ 1mol/L or the aqueous solution of titanyle sulfate 1 ~ 36 hour the load for preparing, takes out, 80 ~ 150 ℃ of dryings, 300 ~ 700 ℃ of calcinings 0.5 ~ 5 hour.After the cooling, impregnated in the H of 1 ~ 18.4mol/L again
2SO
4In the solution 1 ~ 36 hour, 80 ~ 150 ℃ of dry backs were in 300 ~ 700 ℃ of calcinings 0.5 ~ 5 hour.
The invention will be further described below in conjunction with specific embodiment, and embodiment is not limited.Convenient for follow-up narration, the ceramic membrane carrier represents that with CM prepared acidic catalyst film is represented with active component/molecular sieve carrier/CM.
Embodiment 1:
It is 5% HNO that ceramic membrane is placed mass percent concentration
3Soaked 2 hours in the solution, taking-up, was calcined 3 hours in 500 ℃ after 70 ℃ of oven dry to neutral with distilled water flushing, and is standby.
Ceramic membrane after the washing is immersed in the positive tetraethyl orthosilicate of 20g, slowly splash into the 20g deionized water under the strong agitation, dropwising the back uses the pH value of ammoniacal liquor regulator solution between 10-11, continue to stir after 0.5 hour ceramic membrane and feed liquid are placed water heating kettle, in 200 ℃ of crystallization 6 hours, take out ceramic membrane after being cooled to room temperature, spend deionised water to neutral, calcined 6 hours down in 550 ℃ 70 ℃ of dry backs, obtains the ceramic membrane that load has MCM-41.
Having the ceramic membrane of molecular sieve to impregnated in concentration load is in 0.3mol/L p-methyl benzenesulfonic acid (PTSA) aqueous solution 24 hours, takes out the back in 110 ℃ of dryings 5 hours, namely obtains PTSA/MCM-41/CM acidic catalyst film in 1 hour 200 ℃ of calcinings then.
Embodiment 2:
It is 8% HNO that ceramic membrane is placed mass percent concentration
3Soaked 2 hours in the solution, taking-up, was calcined 3 hours in 500 ℃ after 70 ℃ of oven dry to neutral with distilled water flushing, and is standby.
Ceramic membrane after the washing is immersed in the positive isopropyl silicate of 10g, slowly splash into the 150g deionized water under the strong agitation, dropwising the back uses the pH value of ammoniacal liquor regulator solution between 10-11, continue to stir after 2 hours ceramic membrane and feed liquid are placed water heating kettle, in 100 ℃ of crystallization 72 hours, take out ceramic membrane after being cooled to room temperature, spend deionised water to neutral, calcined 1 hour down in 700 ℃ 70 ℃ of dry backs, obtains the ceramic membrane that load has MCM-41.
Have the ceramic membrane of molecular sieve to impregnated in the aqueous solution of titanyle sulfate that concentration is 0.1mol/L 36 hours load, take out, 80 ℃ of dry backs were in 300 ℃ of calcinings 2 hours; And then the gained carrier flooded 1 hour in the concentrated sulfuric acid solution of 18.4mol/L, take out the back in 80 ℃ of dryings, 300 ℃ of calcinings obtained SO after 3 hours
4 2-/ TiO
2/ MCM-41/CM acidic catalyst film.
Embodiment 3:
It is 10% HNO that ceramic membrane is placed mass percent concentration
3Soaked 2 hours in the solution, taking-up, was calcined 3 hours in 500 ℃ after 70 ℃ of oven dry to neutral with distilled water flushing, and is standby.
Ceramic membrane after the washing is immersed in the 20g butyl silicate, slowly splash into the 100g deionized water under the strong agitation, dropwising the back uses the pH value of ammoniacal liquor regulator solution between 10-11, continue to stir after 5 hours ceramic membrane and feed liquid are placed water heating kettle, in 180 ℃ of crystallization 36 hours, take out ceramic membrane after being cooled to room temperature, spend deionised water to neutral, calcined 10 hours down in 300 ℃ 70 ℃ of dry backs, obtains the ceramic membrane that load has MCM-41.
Have the ceramic membrane of molecular sieve to impregnated in the zirconium nitrate solution that concentration is 0.3mol/L 24 hours load, take out, 150 ℃ of dry backs were in 700 ℃ of calcinings 0.5 hour; And then the gained carrier flooded 24 hours in the concentrated sulfuric acid solution of 15mol/L, take out the back in 150 ℃ of dryings, 700 ℃ of calcinings obtained SO after 0.5 hour
4 2-/ ZrO
2/ MCM-41/CM acidic catalyst film.
Embodiment 4:
It is 5% HNO that ceramic membrane is placed mass percent concentration
3Soaked 2 hours in the solution, taking-up, was calcined 3 hours in 500 ℃ after 70 ℃ of oven dry to neutral with distilled water flushing, and is standby.
Pretreated ceramic membrane is immersed in the ethanolic solution of the positive tetraethyl orthosilicate of 50g60%, with ammoniacal liquor material liquid pH value is transferred to 7 ~ 9, add 4g polymer P 123 again, be stirred to dissolving fully, slowly be added dropwise to the 150g deionized water, continue to stir and with the pH value of ammoniacal liquor regulator solution between 10-11, continue to stir after 0.5 hour ceramic membrane and feed liquid are placed water heating kettle, sealing back was in 180 ℃ of crystallization 36 hours, take out carrier after being cooled to room temperature, spend deionised water to neutral, drying, calcine down in 550 ℃ at last and removed the template agent in 6 hours, obtain the ceramic membrane that load has SBA-15.
Having the ceramic membrane of molecular sieve to impregnated in concentration load is in the 0.1mol/L PTSA solution 36 hours, takes out the back in 80 ℃ of dryings 5 hours, namely obtains PTSA/SBA-15/CM acidic catalyst film in 0.5 hour 300 ℃ of calcinings then.
Embodiment 5:
It is 5% HNO that ceramic membrane is placed mass percent concentration
3Soaked 2 hours in the solution, taking-up, was calcined 3 hours in 500 ℃ after 70 ℃ of oven dry to neutral with distilled water flushing, and is standby.
Pretreated ceramic membrane is immersed in the propanol solution of 50g30% butyl silicate, with ammoniacal liquor material liquid pH value is transferred to 7 ~ 9, add the 2g softex kw again, be stirred to dissolving fully, slowly be added dropwise to the 50g deionized water, continue to stir and with the pH value of ammoniacal liquor regulator solution between 10-11, continue to stir after 2 hours ceramic membrane and feed liquid are placed water heating kettle, sealing back is cooled to room temperature in 180 ℃ of crystallization 72 hours, takes out carrier, washing is to neutral, drying is calcined down in 550 ℃ at last and was removed the template agent in 6 hours, obtains the ceramic membrane that load has MCM-41.
Have the ceramic membrane of molecular sieve to impregnated in the aqueous solution of titanyle sulfate that concentration is 1mol/L 1 hour load, take out, 110 ℃ of dry backs were in 500 ℃ of calcinings 5 hours; And then the gained carrier flooded 36 hours in the sulfuric acid solution of 1mol/L, take out the back in 130 ℃ of dryings, 550 ℃ of calcinings obtained SO after 5 hours
4 2-/ TiO
2/ MCM-41/CM acidic catalyst film.
Embodiment 6:
It is 5% HNO that ceramic membrane is placed mass percent concentration
3Soaked 2 hours in the solution, taking-up, was calcined 3 hours in 500 ℃ after 70 ℃ of oven dry to neutral with distilled water flushing, and is standby.
Pretreated ceramic membrane is immersed in the butanol solution of the positive isopropyl silicate of 50g60%, with ammoniacal liquor material liquid pH value is transferred to 7 ~ 9, add the 0.4g softex kw again, be stirred to dissolving fully, slowly be added dropwise to the 50g deionized water, continue to stir and with the pH value of ammoniacal liquor regulator solution between 10-11, continue to stir after 5 hours ceramic membrane and feed liquid are placed water heating kettle, sealing back is cooled to room temperature in 180 ℃ of crystallization 72 hours, takes out carrier, washing is to neutral, drying is calcined down in 550 ℃ at last and was removed the template agent in 6 hours, obtains the ceramic membrane that load has MCM-41.
Have the ceramic membrane of molecular sieve to impregnated in the zirconium nitrate solution that concentration is 0.5mol/L 24 hours load, take out, 100 ℃ of dry backs were in 500 ℃ of calcinings 3 hours; And then the gained carrier flooded 24 hours in the concentrated sulfuric acid solution of 18.4mol/L, take out the back in 110 ℃ of dryings, 550 ℃ of calcinings obtained SO after 3 hours
4 2-/ ZrO
2/ MCM-41/CM acidic catalyst film.
Embodiment 7:
It is 5% HNO that ceramic membrane is placed mass percent concentration
3Soaked 2 hours in the solution, taking-up, was calcined 3 hours in 500 ℃ after 70 ℃ of oven dry to neutral with distilled water flushing, and is standby.
Pretreated ceramic membrane is immersed in the ethanolic solution of the positive tetraethyl orthosilicate of 50g5%, with ammoniacal liquor material liquid pH value is transferred to 7 ~ 9, add the 5g n-butylamine again, be stirred to dissolving fully, slowly be added dropwise to the 100g deionized water, continue to stir and with the pH value of ammoniacal liquor regulator solution between 10-11, continue to stir after 2 hours ceramic membrane and feed liquid are placed water heating kettle, sealing back was in 180 ℃ of crystallization 36 hours, take out carrier after being cooled to room temperature, spend deionised water to neutral, drying, calcine down in 550 ℃ at last and removed the template agent in 6 hours, obtain the ceramic membrane that load has ZSM-5.
There is the ceramic membrane of molecular sieve to impregnated in sulfuric acid-phosphoric acid that concentration is 15mol/L-phosphotungstic acid-aqueous citric acid solution 1 hour load, take out the back in 150 ℃ of dryings 5 hours, namely obtained sulfuric acid-phosphoric acid-phosphotungstic acid-citric acid/ZSM-5/CM acidic catalyst film in 5 hours 700 ℃ of calcinings then.
Embodiment 8:
Palm oil and methyl alcohol are pressed molar ratio of methanol to oil 20:1, enter membrane reactor through blender, and the control reaction temperature is 65 ℃, and the palm oil time of staying is 20 minutes.Product and methyl alcohol come out through the catalytic membrane permeability and separation, and excessive methanol is removed in decompression distillation, namely obtain biodiesel; By analysis, the palm oil conversion ratio reaches more than 98%, and the yield of biodiesel is 96%.
Claims (5)
1. the acidic catalyst film based on the original position synthetic technology is characterized in that, this catalytic membrane is complex carrier with the molecular sieve of ceramic membrane and area load thereof, with SO
4 2-/ ZrO
2, SO
4 2-/ TiO
2, in the p-methyl benzenesulfonic acid, sulfuric acid, phosphoric acid, phosphotungstic acid, citric acid one or more are active presoma, described active presoma adopts excessive infusion process to be carried on the complex carrier; Described ceramic membrane is by α-Al
2O
3Ceramic supporting body and diffusion barrier are formed, and the aperture is 0.01～10 μ m; Described molecular sieve is any among ZSM-5, SBA-15, the MCM-41.
2. a method for preparing the described acidic catalyst film based on the original position synthetic technology of claim 1 is characterized in that, steps of the method are:
1) be to be immersed in the organosilicon source after the washing of 5% ~ 10% nitric acid the ceramic membrane mass percent concentration, slowly splash into deionized water, wherein water under the strong agitation: organosilicon source quality ratio is 1 ~ 15:1;
2) after deionized water drip to finish, generate one of as follows the milky gel:
A) with ammoniacal liquor mixture pH value is adjusted between 10 ~ 11, continues to stir 0.5 ~ 5 hour, obtain the milky gel;
B) with ammoniacal liquor mixture pH value is transferred between 7 ~ 9, by the organosilicon source: the organic formwork agent mass ratio is that 5 ~ 50:1 adds organic formwork agent, being stirred to organic formwork agent dissolves fully, with ammoniacal liquor mixture pH value is transferred between 10 ~ 11 again, continue to stir 0.5 ~ 5 hour, obtain the milky gel, described organic formwork agent is a kind of in softex kw, n-butylamine, the polymer P 123;
3) ceramic membrane and milky gel are placed water heating kettle, 100 ~ 200 ℃ of following crystallization 6 ~ 72 hours, ceramic membrane is taken out in the cooling back, and to neutral, the oven dry back obtains the ceramic membrane that load has molecular sieve in 300 ~ 700 ℃ of calcinings 1 ~ 10 hour down with deionized water rinsing;
4) adopting infusion process that active presoma is carried on load has on the ceramic membrane of molecular sieve, namely obtains the acidic catalyst film based on the original position synthetic technology.
3. according to the method for the described preparation of claim 2 based on the acidic catalyst film of original position synthetic technology, it is characterized in that, the idiographic flow of described step 4) is: the load for preparing is had the ceramic membrane of molecular sieve flooded in the precursor solution of 0.1 ~ 15mol/L 1 ~ 36 hour, take out the back in 80 ~ 150 ℃ of oven dry, then in 200 ~ 700 ℃ of calcinings 0.5 ~ 5 hour, namely obtain the acidic catalyst film based on the original position synthetic technology, described precursor solution is one or more the aqueous solution of p-methyl benzenesulfonic acid, sulfuric acid, phosphoric acid, phosphotungstic acid, citric acid.
4. according to the method for the described preparation of claim 2 based on the acidic catalyst film of original position synthetic technology, it is characterized in that, the idiographic flow of described step 4) is: have the ceramic membrane of molecular sieve to impregnated in 0.1 ~ 1mol/L zirconium nitrate or the aqueous solution of titanyle sulfate 1 ~ 36 hour the load for preparing, take out the back in 80 ~ 150 ℃ of oven dry, then in 300 ~ 700 ℃ of calcinings 0.5 ~ 5 hour, after the cooling, impregnated in 1 ~ 18.4mol/LH again
2SO
4In the solution 1 ~ 36 hour, 80 ~ 150 ℃ of dry backs namely obtained the acidic catalyst film based on the original position synthetic technology in 300 ~ 700 ℃ of calcinings 0.5 ~ 5 hour.
5. according to claim 2, the 3 or 4 described preparations preparation method based on the acidic catalyst film of original position synthetic technology, it is characterized in that, organosilicon source in the described step 1) is one or more in positive tetraethyl orthosilicate, positive isopropyl silicate, the butyl silicate, or one or more the alcoholic solution in the positive tetraethyl orthosilicate, positive 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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|---|---|---|---|---|
| CN104190346A (en) * | 2014-08-18 | 2014-12-10 | 华南理工大学 | Plasma electrolytic oxidation ceramic membrane catalytic transesterification stirring device |
| CN104525247A (en) * | 2015-01-26 | 2015-04-22 | 南开大学 | Preparation method used for preparing biological jet fuel hydrogenation deoxidization and hydrogenation isomerization catalysts by castor oil |
| CN109847092A (en) * | 2018-06-18 | 2019-06-07 | 浙江大学 | A kind of hemostasis compound and preparation method thereof |
| CN111686793A (en) * | 2020-05-28 | 2020-09-22 | 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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| 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190346A (en) * | 2014-08-18 | 2014-12-10 | 华南理工大学 | Plasma electrolytic oxidation ceramic membrane catalytic transesterification stirring device |
| CN104190346B (en) * | 2014-08-18 | 2016-03-02 | 华南理工大学 | A kind of research of plasma electrolytic oxidation ceramic coatings catalysis transesterification agitating device |
| CN104525247A (en) * | 2015-01-26 | 2015-04-22 | 南开大学 | Preparation method used for preparing biological jet fuel hydrogenation deoxidization and hydrogenation isomerization catalysts by castor oil |
| CN109847092A (en) * | 2018-06-18 | 2019-06-07 | 浙江大学 | A kind of hemostasis compound and preparation method thereof |
| CN111686793A (en) * | 2020-05-28 | 2020-09-22 | 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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