CN101032693A - Catalyst for producing pyridine alkali and its preparation method - Google Patents
Catalyst for producing pyridine alkali and its preparation method Download PDFInfo
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- CN101032693A CN101032693A CN 200710021347 CN200710021347A CN101032693A CN 101032693 A CN101032693 A CN 101032693A CN 200710021347 CN200710021347 CN 200710021347 CN 200710021347 A CN200710021347 A CN 200710021347A CN 101032693 A CN101032693 A CN 101032693A
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- catalyst
- molecular sieve
- pyridine
- zsm
- bismuth
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 140
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000003513 alkali Substances 0.000 title 1
- 239000002808 molecular sieve Substances 0.000 claims abstract description 43
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910001868 water Inorganic materials 0.000 claims description 6
- 150000001621 bismuth Chemical class 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001802 infusion Methods 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims description 2
- 238000009835 boiling Methods 0.000 abstract description 21
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 description 29
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 16
- 229910021529 ammonia Inorganic materials 0.000 description 15
- 239000006227 byproduct Substances 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 150000001299 aldehydes Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000011049 filling Methods 0.000 description 6
- 150000002576 ketones Chemical class 0.000 description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical class [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical class CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- -1 alkyl pyridines Chemical class 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 239000000110 cooling liquid Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- AOKYJAAYDKAMJZ-UHFFFAOYSA-N 2-methylpyridine;pyridine Chemical compound C1=CC=NC=C1.CC1=CC=CC=N1 AOKYJAAYDKAMJZ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000005653 Chichibabin synthesis reaction Methods 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
The present invention discloses one kind of catalyst for producing pyridine base and its preparation process. The catalyst includes ZSM-5 molecular sieve carrier in 90-99.9 wt% and Bi supported on the carrier in 0.1-10 wt%. The catalyst of the present invention has increased pyridine selectivity, capacity of reducing high boiling point product, total pyridine and methyl pyridine yield raised to 88 %, and simple and feasible preparation process.
Description
Technical field
The present invention relates to chemical field, be specifically related to a kind of metal-modified Catalysts and its preparation method that is used to produce pyridine base.
Background technology
Pyridine and derivative thereof are widely used in fields such as medicine, agricultural chemicals.In addition, they also are widely used in rubber industry, surfactant, dye industry etc.
The production of early stage pyridine mainly is to extract from the coal coking byproduct, and this kind method productive rate is low, the products therefrom purity difference.Along with the continuous increase of demand, this method is the incompatibility mass industrialized production, and present 95% above pyridine is by synthetic method production, and its output concentrates on the U.S., the nations of China and India.
The pyridine synthetic method is more, as aldehyde (ketone)-ammonia process, and the unsaturated hydrocarbons method, side chain alkylation method, cyanamide process etc., wherein aldehyde (ketone)-ammonia process process route is simple, and technical maturity is the heat subject of research always.
Aldehyde (ketone)-ammonia process, general designation Chichibabin reaction by ammonia, aldehydes or ketones gas phase cyclizative condensation, generates pyridine compounds and their.Fan Ying exploration started from for 19th century hereto, and its detailed research is finished 1924 by Chichibabin, and nineteen fifty is for the beginning industrial production.This method adopts gas and solid phase catalytic to produce pyridine and derivative thereof, only need just can produce various pyridine derivates in same device by changing raw material.
Aldehyde (ketone)-ammonia process pyridine synthesis uses amorphous silicon aluminate (SiO in early days
2-Al
2O
3) make catalyst.Adopt the amorphous silicon aluminate to make catalyst, initial reaction stage, the productive rate of pyridine base is satisfactory, but use limited all after dates, productive rate descends rapidly, and catalyst is using several all after dates, heat endurance descends, activity of such catalysts is difficult to recover by regeneration, and selection of catalysts is relatively poor simultaneously, and incoagulable gas, light component and high boiling component proportion are higher.
There is the researcher to attempt improving the course of reaction of aldehyde (ketone)-ammonia process pyridine synthesis from technology and project angle.The steam that adds larger proportion in raw material improves pyridine and generates ratio; In raw material, add hydrogen, can improve the pyridine productive rate, also can prolong the life cycle of catalyst; In raw material, add oxygen, improve the selectivity of pyridine; Change fixed bed reactors into fluidized-bed reactor or the like.These measures are little to the selectivity and the yield raising spoke degree of pyridine.Therefore, the improvement catalyst remains an important directions in the pyridine production research.
Along with the discovery of the 1970's shape-selective molecular sieve MFI, the synthetic crystalline form sieve peg-raking catalyst that gradually adopts of pyridine.The catalyst that pyridine production is at present used mostly is the crystalline form alumino-silicate of restricted index between 1～12, especially uses the ZSM-5 zeolite with three dimensional intersection straight channel structure, and the productive rate of pyridine base and the selectivity of pyridine are had a greater degree of improvement.
For synthesizing of pyridine base, though adopting shape-selective molecular sieve to make catalyst makes moderate progress, but, except generating primary product pyridine and picoline, might generate incoagulable gas such as hydrogen, methane, carbon monoxide, carbon dioxide because the High Temperature Gas solid phase reaction is very complicated; Low-boiling-point substances such as monomethyl amine, dimethylamine, trimethylamine, hydrogen cyanide, dimethyl ether, enamine, benzene, toluene; Higher boiling products such as many alkyl pyridines, quinoline, alkyl quinoline.The existence of these accessory substances reduces reaction efficiency, has also increased the recovery difficult of principal product simultaneously.
It is catalyst that U.S. Pat 4220783 has disclosed with the HZSM-5 molecular sieve, formaldehyde, acetaldehyde, methyl alcohol and ammonia are the pyridine base-synthesized method of raw material, pyridine and picoline accounted for 69.8～71% of gross weight during its product was formed, low-boiling products accounts for 4.1～4.5%, and the higher boiling product accounts for 22.9～25.7%.
The ZSM-5 molecular sieve that Chinese patent CN1506353A has disclosed with the silicon modification is a catalyst, and formaldehyde, acetaldehyde and ammonia are the pyridine base-synthesized method of raw material, and the molar yield of its pyridine and picoline is 65.7%, higher boiling product 32.3%.
It is catalyst that Chinese patent CN1506354A has disclosed the ZSM-5 molecular sieve of handling with highly basic, and formaldehyde, acetaldehyde and ammonia are the pyridine base-synthesized method of raw material, and the molar yield of its pyridine and picoline is 74.7%, higher boiling product 23.3%.
This shows that the method yield of above-mentioned catalyst pyridine synthesis and 3-picoline is not high, have high boiling point by-products produced in a large number, thereby give the refining of product and reclaim and brought very big difficulty, and then improved production cost.
Summary of the invention
The objective of the invention is to overcome the problem that existing catalyst yield is not high, accessory substance is many, provide a kind of and can improve pyridine and picoline yield, reduce the catalyst that high boiling point by-products produced metal-modified production pyridine base is used.
Another object of the present invention is to provide a kind of above-mentioned Preparation of catalysts method.
Purpose of the present invention can reach by following measure:
A kind of catalyst that is used to produce pyridine base, this catalyst is for to load on bismuth on the ZSM-5 molecular sieve carrier; Its composition comprises that mass percent is 90～99.9% ZSM-5 molecular sieve carrier and load 10～0.1% a bismuth thereon.
It is 94～99% ZSM-5 molecular sieve carrier and load 6～1% bismuth thereon that the composition of this catalyst preferably includes mass percent.
Described ZSM-5 molecular sieve carrier is made up of mass percent 20～80%ZSM-5 molecular sieve and 80～20% binding agents.
The silica alumina ratio of described ZSM-5 molecular sieve is 30～350, is preferably silica alumina ratio and is 80～120 HZSM-5 molecular sieve.
Described binding agent is aluminium oxide, silica or its mixture.
A kind of preparation is used to produce the method for the catalyst of pyridine base, it is characterized in that adopting following steps:
1) bismuth salt is mixed with the solution (preferred 0.01～0.3mol/L) of bismuth-containing;
2) with infusion process the ZSM-5 molecular sieve carrier is immersed in the solution that step 1) prepares, regulating temperature is 80～100 ℃, stirs 10～24 hours;
3) cool to room temperature filters, water wash to the pH value be 6～7, the modified catalyst that obtains wetting;
4) the step 3) gained is wet modified catalyst is under 100～200 ℃ of temperature, and dry 6～12 hours, then 500～600 ℃ of roastings 4～6 hours, cool to room temperature obtained being used to produce the catalyst of pyridine base.
Purpose of the present invention specifically can reach by following measure:
Producing the pyridine catalyst, is the modified catalyst that is carried on the ZSM-5 molecular sieve carrier with bismuth.Modified catalyst comprises following component by weight percentage:
A.ZSM-5 molecular sieve carrier 90～99.9%; With load thereon
B. bismuth 10～0.1%;
Wherein, the ZSM-5 molecular sieve carrier comprises following component by weight percentage:
A) silica alumina ratio is 30～350 HZSM-5 molecular sieve (Hydrogen ZSM-5 molecular sieve) 20～80%;
B) aluminium oxide, silica or its mixture are binding agent, and consumption is 80～20%.
Being used for the used ZSM-5 molecular sieve carrier of the present invention can make required shape by tablet press machine, banded extruder or comminutor, as sheet shape, bar shaped, powdery etc.After ZSM-5 molecular sieve and adhesive such as silica, aluminium oxide, water etc. are mixed aftershaping, obtain the ZSM-5 molecular sieve carrier, after the bismuth modification, can be used for fixed bed reactors.Obtain slurries after perhaps for example aluminium oxide, silica or its mixture mix with adhesive with the ZSM-5 molecular sieve, spray-driedly then obtain a kind of microballoon, can be used for fluidized-bed reactor.The ZSM-5 molecular sieve carrier that obtains can be 300 to 800 ℃ of roastings 1～20 hour in air, improving its intensity, and remove the volatile components in the binding agent.
Employed bismuth can be the bismuth simple substance of any form or the bismuth in the bismuth salt, halide, nitrate or the sulfate of the bismuth of preferred 3 valencys of bismuth salt, most preferably bismuth nitrate.
Be used for the synthetic of pyridine base compound with the catalyst that uses in the inventive method, can in fixed bed reactors, carry out, also can in fluidized-bed reactor or moving-burden bed reactor, carry out.
An example of the inventive method of using fixed bed reactors is described below:
It is 16 millimeters that catalyst is loaded in internal diameter, and length is in 500 millimeters the stainless steel reactor.Adopt electrical heating, temperature is controlled automatically.Reactor bottom filling 20～40 purpose inert materials are as supporter, a certain amount of catalyst of filling in the reactor, and filling 20～40 purpose inert materials in catalyst top are made for the usefulness of raw material preheating and vaporization.Raw material formaldehyde, acetaldehyde and ammonia mix, from top to bottom by beds, and gas phase air speed 300～1000 hours
-1, the vapour phase condensation reaction takes place in 350～500 ℃ of temperature (430～470 ℃ of preferable reaction temperatures), generates purpose product pyridine and picoline, and low boiling and high boiling point by-products produced.
After reacting as mentioned above,, carry out quantitatively with gas-chromatography from the pyridine base process cooling liquid that contains reacting gas that reactor outlet flows out.The product molar yield adopts following formula to calculate:
Molal quantity * 100% of acetaldehyde in the molal quantity of pyridine * 2/ reactant in pyridine molar yield (%)=product
Molal quantity * 100% of acetaldehyde in the molal quantity of picoline * 2/ reactant in picoline pyridine molar yield (%)=product
Molal quantity * 100% of acetaldehyde in molal quantity * 2/ reactant of hypothesis lutidines in high boiling point by-products produced molar yield (%)=product
Because high boiling point by-products produced composition is complicated, supposing it for convenience of calculation is lutidines.
The present invention carries out modification to HZSM-5, the introducing of bismuth element by load bismuth element on the ZSM-5 molecular sieve, cause the redistribution of catalyst surface acid site, guaranteed that suitable acid site exposes and aldehyde reaction, helped reaction, improved the selectivity of pyridine and the yield of pyridine base.The existence of bismuth element makes catalyst have suitable redox active simultaneously, and it is high boiling point by-products produced that appropriateness has suppressed, and also increased the selectivity of pyridine and picoline.
Catalyst of the present invention has increased the selectivity of pyridine, has reduced high boiling point by-products producedly, and the total recovery that improves pyridine and picoline is up to 88%, and method for preparing catalyst is simple.
The specific embodiment
Embodiment 1:
12 grams, five water bismuth nitrates are joined wiring solution-forming in rare nitric acid of 500ml 0.1mol/L, with 100 gram ZSM-5 molecular sieve carriers (mass percent HZSM-5 molecular sieve 40% wherein, binding agent aluminium oxide 60%; The silica alumina ratio of HZSM-5 molecular sieve is 115) be immersed in the solution, regulating temperature is 90～100 ℃, stirs 24h, cool to room temperature filters then, is 6～7 with deionized water rinsing to pH value.Then under 115 ℃, dry 12 hours, 550 ℃ of roastings 5 hours placed air to naturally cool to room temperature, obtain catalyst.Bismuth-containing 2.5% in the catalyst.
The catalyst of preparation is applied to the synthetic reaction of pyridine base, continuous fixed bed reaction or continuous 6 hours.
It is 16 millimeters that catalyst is loaded in internal diameter, and length is in 500 millimeters the stainless steel reactor.Adopt electrical heating, temperature is controlled automatically.Reactor bottom filling 20～40 purpose inert materials are as supporter, a certain amount of catalyst of filling in the reactor, and filling 20～40 purpose inert materials in catalyst top are made for the usefulness of raw material preheating and vaporization.Raw material formaldehyde, acetaldehyde and ammonia mix, and from top to bottom by beds, under certain gas phase air speed and temperature, the vapour phase condensation reaction take place, and generate purpose product pyridine and picoline, and low boiling and high boiling point by-products produced.
After the above reacts,, carry out quantitatively with gas-chromatography from the pyridine base process cooling liquid that contains reacting gas that reactor outlet flows out.
Reaction condition and result are as shown in table 1:
Table 1 example 1 gained catalyst is used for the synthetic reaction condition and the result of pyridine base
| Reaction temperature (℃) | Reaction gas air speed (h -1) | Formaldehyde: acetaldehyde: ammonia mol ratio | The pyridine molar yield | The total molar yield of pyridine and picoline | High boiling point by-products produced molar yield |
| 450 | 800 | 1∶1∶3 | 64 | 88 | 10 |
Embodiment 2:
Replace 12 grams, five water bismuth nitrates with 8.5g anhydrous slufuric acid bismuth, mass percent HZSM-5 molecular sieve 60% in the ZSM-5 molecular sieve carrier, binding agent silica 40%, the silica alumina ratio of HZSM-5 molecular sieve are 90, preparation process is identical with embodiment 1 with method, and this catalyst contains bismuth 1.1%.The catalyst of preparation is applied to the pyridine base synthetic reaction.Reaction condition is with embodiment 1, and reaction condition and reaction result are as shown in table 2:
Table 2 example 2 gained catalyst are used for the synthetic reaction condition and the result of pyridine base
| Reaction temperature (℃) | Reaction gas air speed (h -1) | Formaldehyde: acetaldehyde: ammonia mol ratio | The pyridine molar yield | The total molar yield of pyridine and picoline | High boiling point by-products produced molar yield |
| 450 | 800 | 1∶1∶3 | 62 | 86 | 12 |
Embodiment 3:
Preparation process is identical with embodiment 1 with method, five water bismuth nitrates, 35 grams during obtain solution, and this catalyst contains bismuth 6.0%.The catalyst of preparation is applied to the pyridine base synthetic reaction.Reaction condition is with embodiment 1, and reaction condition and reaction result are as shown in table 3:
Table 3 example 3 gained catalyst are used for the synthetic reaction condition and the result of pyridine base
| Reaction temperature (℃) | Reaction gas air speed (h -1) | Formaldehyde: acetaldehyde: ammonia mol ratio | The pyridine molar yield | The total molar yield of pyridine and picoline | High boiling point by-products produced molar yield |
| 450 | 800 | 1∶1∶3 | 59 | 87 | 11 |
Comparative example 1:
ZSM-5 molecular sieve carrier (HZSM-5 molecular sieve 40%, binding agent 60% without the bismuth modification; The silica alumina ratio of HZSM-5 molecular sieve is 115), directly apply to the pyridine base synthetic reaction.Reaction condition is with embodiment 1, and reaction condition and reaction result are as shown in table 4:
Table 4 comparative example 1 gained catalyst is used for the synthetic reaction condition and the result of pyridine base
| Reaction temperature (℃) | Reaction gas air speed (h -1) | Formaldehyde: acetaldehyde: ammonia mol ratio | The pyridine molar yield | The total molar yield of pyridine and picoline | High boiling point by-products produced molar yield |
| 450 | 800 | 1∶1∶3 | 51 | 76 | 22 |
Claims (7)
1, a kind of catalyst that is used to produce pyridine base is characterized in that this catalyst is for to load on bismuth on the ZSM-5 molecular sieve carrier; Its composition comprises that mass percent is 90～99.9% ZSM-5 molecular sieve carrier and load 10～0.1% a bismuth thereon.
2, catalyst according to claim 1, the composition that it is characterized in that this catalyst comprise that mass percent is 94～99% ZSM-5 molecular sieve carrier and load 6～1% a bismuth thereon.
3, catalyst according to claim 1 and 2 is characterized in that described ZSM-5 molecular sieve carrier is made up of mass percent 20～80%ZSM-5 molecular sieve and 80～20% binding agents.
4, catalyst according to claim 3, the silica alumina ratio that it is characterized in that described ZSM-5 molecular sieve is 30～350.
5, catalyst according to claim 4 is characterized in that described ZSM-5 molecular sieve is that silica alumina ratio is 80～120 HZSM-5 molecular sieve.
6, catalyst according to claim 3 is characterized in that described binding agent is aluminium oxide, silica or its mixture.
7, a kind of described method that is used to produce the catalyst of pyridine base of claim 1 for preparing is characterized in that adopting following steps:
1) bismuth salt is mixed with the solution of bismuth-containing;
2) with infusion process the ZSM-5 molecular sieve carrier is immersed in the solution that step 1) prepares, regulating temperature is 80～100 ℃, stirs 10～24 hours;
3) cool to room temperature filters, water wash to the pH value be 6～7, the modified catalyst that obtains wetting;
4) the step 3) gained is wet modified catalyst is under 100～200 ℃ of temperature, and dry 6～12 hours, then 500～600 ℃ of roastings 4～6 hours, cool to room temperature obtained being used to produce the catalyst of pyridine base.
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| CNB2007100213474A CN100540140C (en) | 2007-04-09 | 2007-04-09 | Be used to produce the Catalysts and its preparation method of pyridine base |
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| CNB2007100213474A CN100540140C (en) | 2007-04-09 | 2007-04-09 | Be used to produce the Catalysts and its preparation method of pyridine base |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100577286C (en) * | 2009-02-18 | 2010-01-06 | 中国科学院大连化学物理研究所 | Titanium-based catalyst for synthesizing pyridine base with formaldehyde, acetaldehyde and ammonia, as well as preparation method thereof |
| CN108816275A (en) * | 2018-04-19 | 2018-11-16 | 南京红太阳生物化学有限责任公司 | A kind of catalyst and preparation method and application for synthesis gas pyridine base |
| CN109174168A (en) * | 2018-10-26 | 2019-01-11 | 南京红太阳生物化学有限责任公司 | A kind of catalyst and preparation method and application preparing 2- picoline for pyridine alkylation |
| CN111468178A (en) * | 2020-05-18 | 2020-07-31 | 山东师范大学 | Metal modified ZSM-5 molecular sieve catalyst and preparation method and application thereof |
| CN111468177A (en) * | 2020-05-15 | 2020-07-31 | 山东师范大学 | Molecular sieve catalyst for preparing pyridine base and preparation method and application thereof |
| CN113385220A (en) * | 2021-07-21 | 2021-09-14 | 西南化工研究设计院有限公司 | Preparation method of catalyst for preparing pyridine and picoline by methanol and ammonia water in one step |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE758201A (en) * | 1969-11-08 | 1971-04-29 | Koei Chemical Cy Ltd | PYRIDIC BASES PREPARATION PROCESS |
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2007
- 2007-04-09 CN CNB2007100213474A patent/CN100540140C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100577286C (en) * | 2009-02-18 | 2010-01-06 | 中国科学院大连化学物理研究所 | Titanium-based catalyst for synthesizing pyridine base with formaldehyde, acetaldehyde and ammonia, as well as preparation method thereof |
| CN108816275A (en) * | 2018-04-19 | 2018-11-16 | 南京红太阳生物化学有限责任公司 | A kind of catalyst and preparation method and application for synthesis gas pyridine base |
| CN108816275B (en) * | 2018-04-19 | 2021-02-05 | 南京红太阳生物化学有限责任公司 | Catalyst for preparing pyridine base from synthesis gas, preparation method and application |
| CN109174168A (en) * | 2018-10-26 | 2019-01-11 | 南京红太阳生物化学有限责任公司 | A kind of catalyst and preparation method and application preparing 2- picoline for pyridine alkylation |
| CN109174168B (en) * | 2018-10-26 | 2021-06-29 | 南京红太阳生物化学有限责任公司 | Catalyst for preparing 2-methylpyridine by pyridine alkylation, preparation method and application |
| CN111468177A (en) * | 2020-05-15 | 2020-07-31 | 山东师范大学 | Molecular sieve catalyst for preparing pyridine base and preparation method and application thereof |
| CN111468177B (en) * | 2020-05-15 | 2022-04-15 | 山东师范大学 | Molecular sieve catalyst for preparing pyridine base and preparation method and application thereof |
| CN111468178A (en) * | 2020-05-18 | 2020-07-31 | 山东师范大学 | Metal modified ZSM-5 molecular sieve catalyst and preparation method and application thereof |
| CN111468178B (en) * | 2020-05-18 | 2022-07-12 | 山东师范大学 | Metal modified ZSM-5 molecular sieve catalyst and preparation method and application thereof |
| CN113385220A (en) * | 2021-07-21 | 2021-09-14 | 西南化工研究设计院有限公司 | Preparation method of catalyst for preparing pyridine and picoline by methanol and ammonia water in one step |
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| CN100540140C (en) | 2009-09-16 |
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