CN106748975A - A kind of method with the molecular sieves of CoSAPO 34 as catalyst preparation pyridine - Google Patents
A kind of method with the molecular sieves of CoSAPO 34 as catalyst preparation pyridine Download PDFInfo
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- CN106748975A CN106748975A CN201710005417.0A CN201710005417A CN106748975A CN 106748975 A CN106748975 A CN 106748975A CN 201710005417 A CN201710005417 A CN 201710005417A CN 106748975 A CN106748975 A CN 106748975A
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- cosapo
- molecular sieves
- pyridine
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- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 112
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 81
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005342 ion exchange Methods 0.000 claims abstract description 25
- 238000002425 crystallisation Methods 0.000 claims abstract description 17
- 230000008025 crystallization Effects 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 23
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 10
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 10
- 239000005909 Kieselgur Substances 0.000 claims description 9
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 239000004816 latex Substances 0.000 claims description 7
- 229920000126 latex Polymers 0.000 claims description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- 229910001593 boehmite Inorganic materials 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract description 4
- 230000002779 inactivation Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 8
- MMWRGWQTAMNAFC-UHFFFAOYSA-N 1,2-dihydropyridine Chemical class C1NC=CC=C1 MMWRGWQTAMNAFC-UHFFFAOYSA-N 0.000 description 6
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000004445 quantitative analysis Methods 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- -1 alkyl Pyridine Chemical compound 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical class CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical class CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical class CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 1
- 150000000644 6-membered heterocyclic compounds Chemical class 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229940001007 aluminium phosphate Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/08—Preparation by ring-closure
- C07D213/09—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles
- C07D213/10—Preparation by ring-closure involving the use of ammonia, amines, amine salts, or nitriles from acetaldehyde or cyclic polymers thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a kind of method with the molecular sieves of CoSAPO 34 as catalyst preparation pyridine, including the 1) preparation of the molecular sieve catalysts of CoSAPO 34：Diatomite pretreatment, gel preparation, crystallization, ion exchange；2) pyridine is catalyzed and synthesized：Activate, catalyze and synthesize.The obtained molecular sieve catalysts of CoSAPO 34 of the invention have stability higher, carbon distribution is difficult to inactivate and environment-friendly, it is used as preparing the catalyst of pyridine, aldehyde and ammonia convert pyridine base processed in the presence of a catalyst, efficiently solve influence of the carbon distribution inactivation to reacting on molecular sieve catalyst, pyridine base yield is increased substantially, pyridine yield is more than 75.0%, pyridine base yield is 85.0% or so, and it is relatively low to prepare reaction pressure, product is easily separated with catalyst, simple to operate, is easy to large-scale production.
Description
Technical field
The present invention relates to system with molecular sieve for preparing is standby and its applied technical field, and in particular to one kind is with CoSAPO-34 molecular sieves
The method of catalyst preparation pyridine.
Background technology
Pyridine is the 6-membered heterocyclic compound that a carbon atom is formed after being replaced by nitrogen-atoms on phenyl ring.Pyridine and alkyl
Pyridine is commonly referred to as pyridine base, mainly including pyridine, 2- picolines, 3- picolines, 4- picolines etc..Pyridine series raw material
The important Organic Ingredients for producing high added value fine chemical product as chemical industrial product, be widely used in medicine, agricultural chemicals,
The fields such as dyestuff, spices, feed addictive, food additives, rubber chemicals and synthetic material.
Nineteen twenty-four Chichbabin is proposed with aldehyde and ammonia as raw material, produces the commercial run of pyridine base in enormous quantities, is passed through
Catalyst is updated, yield oneself bring up to 80% or so by the 40%-50% of the fifties.At present, in the world 95%
Pyridine base is, using aldehyde and ammonia as raw material, to be obtained through catalyzing and synthesizing.The catalyst of current pyridine synthesis is mainly ZSM-5 molecular sieve
And various modified ZSM-5 molecular sieves, but because the skeleton of ZSM-5 is made up of the channel system of two kinds of intersections, in duct easily
Block, while ZSM-5 molecular sieve surface acid center intensity is high, easy carbon distribution is inactivated during the course of the reaction, and this molecular sieve analog is catalyzed
Agent, pyridine and pyridine base yield are all relatively low, thus it is pyridine synthesis technique to find the catalyst of a kind of high activity and anti-carbon
It is crucial.Compared with ZSM-5 molecular sieve, the one-dimensional oval duct that SAPO-41 molecular sieves are made up of ten-ring, and acid strength ratio
It is relatively low, duct can be prevented effectively from and blocked or area carbon inactivation.Different metal Me (such as Si, Fe, Co, Mn, Mg) is taken
Skeleton is introduced for the Al in aluminium phosphate molecular sieve skeleton, its acidity is greatly improved on the premise of skeleton structure is not changed and is urged
Change performance, the CoSAPOs molecular sieves of wherein Co substitutions have special acidity and redox property, are always Zeolite synthesis
One study hotspot of aspect.So far, it is not used to prepare the report of pyridine on CoSAPO-41 molecular sieves.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of green high-efficient, economic security with CoSAPO-34 molecules
It is the method for catalyst preparation pyridine to sieve.
To realize object above, the present invention is achieved by the following technical programs：
A kind of method with CoSAPO-34 molecular sieves as catalyst preparation pyridine, it is characterised in that step is as follows：
1) preparation of CoSAPO-34 molecular sieve catalysts：
A. diatomite pretreatment：Natural diatomaceous earth is calcined at 500-800 DEG C；
B. prepared by gel：The phosphoric acid solution of 45-50% is prepared, 3-8 addition boehmite is divided thereto, add the time
In 1-5h, then add water stirring 2-3h, obtains slurry for control；By tetraethyl ammonium hydroxide, morpholine, pretreated diatomite
With water mixing, 1-1.5h is stirred, obtain mixed liquor；Slurry is added drop-wise in mixed liquor, add water stirring 6-8h, obtains gel, and gained coagulates
Glue pH is in 6.7-7.5；
C. crystallization：Gel is added in polytetrafluoro liner reactor, crystallization is then centrifuged for, filters, washs, dries, roasted
Burn to obtain SAPO-34 molecular sieves；
D. ion exchange：SAPO-34 molecular sieves and soluble cobalt solution are carried out into ion exchange, ion exchange temperature is controlled
It is 60 DEG C -120 DEG C to spend, and obtains CoSAPO-34 molecular sieves；
2) pyridine is catalyzed and synthesized：
E., CoSAPO-34 molecular sieves are loaded the flat-temperature zone of the reaction tube of fixed-bed micro-reactor, heat up activation, then
Reaction temperature is cooled to, and the CoSAPO-34 molecular sieves after activation are placed in the beds of fixed-bed micro-reactor；
F. the beds of formaldehyde, acetaldehyde and ammonia injection fixed-bed micro-reactor are reacted, reaction temperature
For 400-430 DEG C, pressure be 0.01-0.15MPa, nitrogen flow rate be 10-40ml/min.
Preferably, the step 1) in sintering temperature be 650-750 DEG C.
Preferably, the step 1) in boehmite add time control in 1.5-2.5h.
Preferably, the soluble cobalt solution is cobalt nitrate or cobalt acetate, and mass concentration is 3%-8%.
Preferably, the step 1) in obtained CoSAPO-34 molecular sieves cobalt content in 0.1%-0.5%.
Preferably, the step 2) in formaldehyde, acetaldehyde and ammonia mol ratio be 0.95-1.2：1：1.9-2.2.
Preferably, the step 2) in CoSAPO-34 molecular sieve catalysts consumption be formaldehyde and acetaldehyde gross mass
0.5%-3%.
Preferably, the step 2) in CoSAPO-34 molecular sieve catalysts particle size be 5-40 mesh.
Beneficial effect of the present invention：Using natural diatomaceous earth as silicon source, it contains various metals cation to the present invention, is dividing
A greater variety of acidic sites can be introduced during sub- sieve series is standby；The ratio for changing silicon and cobalt by ion exchange realizes two kinds
The modulation of acidic site, can introduce the more acidic sites of generation, and obtained CoSAPO-34 molecular sieve catalysts have stabilization higher
Property, it is difficult carbon distribution and inactivates and environment-friendly.By CoSAPO-34 molecular sieve catalysts first as the catalyst for preparing pyridine, aldehyde
Convert pyridine base processed in the presence of a catalyst with ammonia, efficiently solve shadow of the carbon distribution inactivation to reaction on molecular sieve catalyst
Ring, pyridine base yield is increased substantially, more than 75.0%, pyridine base yield is prepared anti-pyridine yield 85.0% or so
Answer pressure relatively low, product is easily separated with catalyst, it is simple to operate, it is easy to large-scale production.
Specific embodiment
To make the purpose, technical scheme and advantage of the embodiment of the present invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, belongs to the scope of protection of the invention.
Embodiment 1：
A kind of method with CoSAPO-34 molecular sieves as catalyst preparation pyridine, step is as follows：
1) preparation of CoSAPO-34 molecular sieve catalysts：
A. diatomite pretreatment：Natural diatomaceous earth is calcined at 650 DEG C；
B. prepared by gel：By the phosphoric acid solution of 23.6g phosphoric acid preparation 46.6% soluble in water, by 13.8g boehmites
Divide in 5 addition phosphoric acid solutions, add time control in 1.5h, then add water stirring 3h, obtains slurry；By tetraethyl hydroxide
The mixing of ammonium, morpholine, pretreated diatomite and water, stirs 1.5h, obtains mixed liquor；Slurry is added drop-wise in mixed liquor, plus
Water stirs 6h, obtains gel, and gained pH of latex gel is 6.7；
C. crystallization：Gel is added in polytetrafluoro liner reactor, crystallization is then centrifuged for, filters, washs, dries, roasted
Burn to obtain SAPO-34 molecular sieves；
D. ion exchange：The cobalt nitrate solution of 5g SAPO-34 molecular sieves and 100g 6.2% is carried out into ion exchange, is controlled
Ion-exchange temperature processed is 90 DEG C, obtains CoSAPO-34 molecular sieves；
2) pyridine is catalyzed and synthesized：
The CoSAPO-34 molecular sieves of 2g 10-20 mesh are loaded the flat-temperature zone of the reaction tube of fixed-bed micro-reactor, 550
DEG C activation, be then down to 420 DEG C, pressure is 0.01MPa, and nitrogen flow rate is 20mL/min, question response system components temperature liter
Start charging during to design temperature, 85.7g formaldehyde, 114.3g acetaldehyde, 92.5g ammonias drip the time meter of product from outflow first
It is the t=0 moment, and a product is gathered every 1h, quantitative analysis is carried out with gas-chromatography, the yield for reacting 6h pyridines is
75.0%, pyridine base yield is 85.2%.
Embodiment 2：
A kind of method with CoSAPO-34 molecular sieves as catalyst preparation pyridine, step is as follows：
1) preparation of CoSAPO-34 molecular sieve catalysts：
A. diatomite pretreatment：Natural diatomaceous earth is calcined at 650 DEG C；
B. prepared by gel：By the phosphoric acid solution of 23.6g phosphoric acid preparation 46.6% soluble in water, by 13.8g boehmites
Divide in 5 addition phosphoric acid solutions, add time control in 1.5h, then add water stirring 3h, obtains slurry；By tetraethyl hydroxide
The mixing of ammonium, morpholine, pretreated diatomite and water, stirs 1.5h, obtains mixed liquor；Slurry is added drop-wise in mixed liquor, plus
Water stirs 6h, obtains gel, and gained pH of latex gel is 6.7；
C. crystallization：Gel is added in polytetrafluoro liner reactor, crystallization is then centrifuged for, filters, washs, dries, roasted
Burn to obtain SAPO-34 molecular sieves；
D. ion exchange：5gSAPO-34 molecular sieves and the cobalt nitrate solutions of 100g 6.2% are carried out into ion exchange, control from
Sub- exchange temperature is 90 DEG C, obtains CoSAPO-34 molecular sieves；
2) pyridine is catalyzed and synthesized：
2g 10-20 mesh CoSAPO-34 molecular sieves are loaded the constant temperature of the stainless steel reaction pipe of fixed-bed micro-reactor
Area, 550 DEG C of activation, is then down to 430 DEG C, and pressure is 0.03MPa, and nitrogen flow rate is 20mL/min, question response system components
Temperature starts charging 85.7g formaldehyde, 114.3g acetaldehyde, 92.5g ammonias when being raised to design temperature, from outflow first drip product when
Between be calculated as the t=0 moment, and gather a product every 1h, quantitative analysis is carried out with gas-chromatography, the yield for reacting 6h pyridines is
75.2%, pyridine base yield is 85.4%.
Embodiment 3：
A kind of method with CoSAPO-34 molecular sieves as catalyst preparation pyridine, step is as follows：
1) preparation of CoSAPO-34 molecular sieve catalysts：
A. diatomite pretreatment：Natural diatomaceous earth is calcined at 750 DEG C；
B. prepared by gel：By the phosphoric acid solution of 23.6g phosphoric acid preparation 45% soluble in water, by 13.8g boehmites point 8
In secondary addition phosphoric acid solution, time control is added in 1.5h, then add water stirring 3h, obtains slurry；By tetraethyl ammonium hydroxide,
The mixing of coffee quinoline, pretreated diatomite and water, stirs 1.5h, obtains mixed liquor；Slurry is added drop-wise in mixed liquor, add water stirring
8h, obtains gel, and gained pH of latex gel is 6.8；
C. crystallization：Gel is added in polytetrafluoro liner reactor, crystallization is then centrifuged for, filters, washs, dries, roasted
Burn to obtain SAPO-34 molecular sieves；
D. ion exchange：The cobalt nitrate solution of 5g SAPO-34 molecular sieves and 100g 6.2% is carried out into ion exchange, is controlled
Ion-exchange temperature processed is 110 DEG C, obtains CoSAPO-34 molecular sieves；
2) pyridine is catalyzed and synthesized：
3g 10-20 mesh CoSAPO-34 molecular sieves are loaded the constant temperature of the stainless steel reaction pipe of fixed-bed micro-reactor
Area, 550 DEG C of activation, is then down to 410 DEG C, and pressure is 0.15MPa, and nitrogen flow rate is 10mL/min, question response system components
Temperature starts charging 39.3g formaldehyde, 60.7g acetaldehyde, 44.7g ammonias when being raised to design temperature, from outflow first drip product when
Between be calculated as the t=0 moment, and gather a product every 1h, quantitative analysis is carried out with gas-chromatography, the yield for reacting 6h pyridines is
75.0%, pyridine base yield is 85.1%.
Embodiment 4：
A kind of method with CoSAPO-34 molecular sieves as catalyst preparation pyridine, step is as follows：
1) preparation of CoSAPO-34 molecular sieve catalysts：
A. diatomite pretreatment：Natural diatomaceous earth is calcined at 750 DEG C；
B. prepared by gel：By the phosphoric acid solution of 23.6g phosphoric acid preparation 45% soluble in water, by 13.8g boehmites point 8
In secondary addition phosphoric acid solution, time control is added in 1.5h, then add water stirring 3h, obtains slurry；By tetraethyl ammonium hydroxide,
The mixing of coffee quinoline, pretreated diatomite and water, stirs 1.5h, obtains mixed liquor；Slurry is added drop-wise in mixed liquor, add water stirring
8h, obtains gel, and gained pH of latex gel is 6.8；
C. crystallization：Gel is added in polytetrafluoro liner reactor, crystallization is then centrifuged for, filters, washs, dries, roasted
Burn to obtain SAPO-34 molecular sieves；
D. ion exchange：The cobalt nitrate solution of 5g SAPO-34 molecular sieves and 100g 5% is carried out into ion exchange, is controlled
Ion-exchange temperature is 120 DEG C, obtains CoSAPO-34 molecular sieves；
2) pyridine is catalyzed and synthesized：
4g 10-20 mesh CoSAPO-34 molecular sieves are loaded the constant temperature of the stainless steel reaction pipe of fixed-bed micro-reactor
Area, 550 DEG C of activation, is then down to 430 DEG C, and pressure is 0.15MPa, and nitrogen flow rate is 20mL/min, question response system components
Temperature starts charging 85.7g formaldehyde, 125.8g acetaldehyde, 97.2g ammonias when being raised to design temperature, from outflow first drip product when
Between be calculated as the t=0 moment, and gather a product every 1h, quantitative analysis is carried out with gas-chromatography, the yield for reacting 6h pyridines is
75.3%, pyridine base yield is 85.5%.
Embodiment 5：
A kind of method with CoSAPO-34 molecular sieves as catalyst preparation pyridine, step is as follows：
1) preparation of CoSAPO-34 molecular sieve catalysts：
A. diatomite pretreatment：Natural diatomaceous earth is calcined at 500 DEG C；
B. prepared by gel：By the phosphoric acid solution of 23.6g phosphoric acid preparation 45% soluble in water, by 13.8g boehmites point 3
In secondary addition phosphoric acid solution, add time control to be added water in 1h, then and stir 2h, obtain slurry；By tetraethyl ammonium hydroxide,
The mixing of coffee quinoline, pretreated diatomite and water, stirs 1h, obtains mixed liquor；Slurry is added drop-wise in mixed liquor, add water stirring
6h, obtains gel, and gained pH of latex gel is 7.5；
C. crystallization：Gel is added in polytetrafluoro liner reactor, crystallization is then centrifuged for, filters, washs, dries, roasted
Burn to obtain SAPO-34 molecular sieves；
D. ion exchange：SAPO-34 molecular sieves are controlled with mass concentration for 8% cobalt acetate solution carries out ion exchange
Ion-exchange temperature is 120 DEG C, obtains CoSAPO-34 molecular sieves；
2) pyridine is catalyzed and synthesized：
1g 30-40 mesh CoSAPO-34 molecular sieves are loaded the constant temperature of the stainless steel reaction pipe of fixed-bed micro-reactor
Area, 550 DEG C of activation, is then down to 430 DEG C, and pressure is 0.03MPa, and nitrogen flow rate is 20mL/min, question response system components
Temperature starts charging 85.7g formaldehyde, 104.8g acetaldehyde, 89.0g ammonias when being raised to design temperature, from outflow first drip product when
Between be calculated as the t=0 moment, and gather a product every 1h, quantitative analysis is carried out with gas-chromatography, the yield for reacting 6h pyridines is
70.8%, pyridine base yield is 78.5%.
Embodiment 6：
A kind of method with CoSAPO-34 molecular sieves as catalyst preparation pyridine, step is as follows：
1) preparation of CoSAPO-34 molecular sieve catalysts：
A. diatomite pretreatment：Natural diatomaceous earth is calcined at 800 DEG C；
B. prepared by gel：By the phosphoric acid solution of 23.6g phosphoric acid preparation 50% soluble in water, by 13.8g boehmites point 3
In secondary addition phosphoric acid solution, add time control to be added water in 5h, then and stir 3h, obtain slurry；By tetraethyl ammonium hydroxide,
The mixing of coffee quinoline, pretreated diatomite and water, stirs 1h, obtains mixed liquor；Slurry is added drop-wise in mixed liquor, add water stirring
6h, obtains gel, and gained pH of latex gel is 7.0；
C. crystallization：Gel is added in polytetrafluoro liner reactor, crystallization is then centrifuged for, filters, washs, dries, roasted
Burn to obtain SAPO-34 molecular sieves；
D. ion exchange：SAPO-34 molecular sieves are controlled with mass concentration for 3% cobalt acetate solution carries out ion exchange
Ion-exchange temperature is 60 DEG C, obtains CoSAPO-34 molecular sieves；
2) pyridine is catalyzed and synthesized：
6g 5-20 mesh CoSAPO-34 molecular sieves are loaded the flat-temperature zone of the stainless steel reaction pipe of fixed-bed micro-reactor,
550 DEG C of activation, are then down to 400 DEG C, and pressure is 0.15MPa, and nitrogen flow rate is 40mL/min, question response system components temperature
Start charging 85.7g formaldehyde, 114.3g acetaldehyde, 92.5g ammonias when being raised to design temperature, the time meter of product is dripped from outflow first
It is the t=0 moment, and a product is gathered every 1h, quantitative analysis is carried out with gas-chromatography, the yield for reacting 6h pyridines is
75.0%, pyridine base yield is 85.1%.
It should be noted that herein, such as first and second or the like relational terms are used merely to a reality
Body or operation make a distinction with another entity or operation, and not necessarily require or imply these entities or deposited between operating
In any this actual relation or order.And, term " including ", "comprising" or its any other variant be intended to
Nonexcludability is included, so that process, method, article or equipment including a series of key elements not only will including those
Element, but also other key elements including being not expressly set out, or also include being this process, method, article or equipment
Intrinsic key element.In the absence of more restrictions, the key element limited by sentence "including a ...", it is not excluded that
Also there is other identical element in process, method, article or equipment including the key element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
The present invention has been described in detail, it will be understood by those within the art that：It still can be to foregoing each implementation
Technical scheme described in example is modified, or carries out equivalent to which part technical characteristic；And these modification or
Replace, do not make the spirit and scope of the essence disengaging various embodiments of the present invention technical scheme of appropriate technical solution.
Claims (8)
1. a kind of method with CoSAPO-34 molecular sieves as catalyst preparation pyridine, it is characterised in that step is as follows：
1) preparation of CoSAPO-34 molecular sieve catalysts：
A. diatomite pretreatment：Natural diatomaceous earth is calcined at 500-800 DEG C；
B. prepared by gel：The phosphoric acid solution of 45-50% is prepared, 3-8 addition boehmite is divided thereto, add time control
In 1-5h, then add water stirring 2-3h, obtains slurry；By tetraethyl ammonium hydroxide, morpholine, pretreated diatomite and water
Mixing, stirs 1-1.5h, obtains mixed liquor；Slurry is added drop-wise in mixed liquor, add water stirring 6-8h, obtains gel, gained pH of latex gel
In 6.7-7.5；
C. crystallization：Gel is added in polytetrafluoro liner reactor, crystallization is then centrifuged for, filters, washs, dries, and is calcined
SAPO-34 molecular sieves；
D. ion exchange：SAPO-34 molecular sieves and soluble cobalt solution are carried out into ion exchange, controls the ion-exchange temperature to be
60 DEG C -120 DEG C, obtain CoSAPO-34 molecular sieves；
2) pyridine is catalyzed and synthesized：
E., CoSAPO-34 molecular sieves are loaded the flat-temperature zone of the reaction tube of fixed-bed micro-reactor, heat up activation, then lowers the temperature
To reaction temperature, and the CoSAPO-34 molecular sieves after activation are placed in the beds of fixed-bed micro-reactor；
F. the beds of formaldehyde, acetaldehyde and ammonia injection fixed-bed micro-reactor are reacted, reaction temperature is
400-430 DEG C, pressure be 0.01-0.15MPa, nitrogen flow rate be 10-40ml/min.
2. as claimed in claim 1 is the method for catalyst preparation pyridine with CoSAPO-34 molecular sieves, it is characterised in that institute
State step 1) in sintering temperature be 650-750 DEG C.
3. as claimed in claim 1 is the method for catalyst preparation pyridine with CoSAPO-34 molecular sieves, it is characterised in that institute
State step 1) in boehmite add time control in 1.5-2.5h.
4. as claimed in claim 1 is the method for catalyst preparation pyridine with CoSAPO-34 molecular sieves, it is characterised in that institute
Soluble cobalt solution is stated for cobalt nitrate or cobalt acetate, mass concentration is 3%-8%.
5. as claimed in claim 1 is the method for catalyst preparation pyridine with CoSAPO-34 molecular sieves, it is characterised in that institute
State step 1) in obtained CoSAPO-34 molecular sieves cobalt content in 0.1%-0.5%.
6. as claimed in claim 1 is the method for catalyst preparation pyridine with CoSAPO-34 molecular sieves, it is characterised in that institute
State step 2) in formaldehyde, acetaldehyde and ammonia mol ratio be 0.95-1.2：1：1.9-2.2.
7. as claimed in claim 1 is the method for catalyst preparation pyridine with CoSAPO-34 molecular sieves, it is characterised in that institute
State step 2) in CoSAPO-34 molecular sieve catalysts consumption be formaldehyde and acetaldehyde gross mass 0.5%-3%.
8. as claimed in claim 1 is the method for catalyst preparation pyridine with CoSAPO-34 molecular sieves, it is characterised in that institute
State step 2) in CoSAPO-34 molecular sieve catalysts particle size be 5-40 mesh.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308019A (en) * | 1999-12-30 | 2001-08-15 | 中国科学院大连化学物理研究所 | Porous metal-silicon aluminium phosphate molecular sieve and its synthesis process |
| CN101161343A (en) * | 2007-11-22 | 2008-04-16 | 天津大学 | A novel catalyst for synthesizing pyridine base as well as its preparing and using method |
| CN102219731A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Production method of pyridine base |
| CN102219730A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing pyridine alkali |
| CN105712924A (en) * | 2016-03-24 | 2016-06-29 | 广西新天德能源有限公司 | Method for catalyzing and producing pyridine and picoline with modified molecular sieve |
-
2017
- 2017-01-04 CN CN201710005417.0A patent/CN106748975A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1308019A (en) * | 1999-12-30 | 2001-08-15 | 中国科学院大连化学物理研究所 | Porous metal-silicon aluminium phosphate molecular sieve and its synthesis process |
| CN101161343A (en) * | 2007-11-22 | 2008-04-16 | 天津大学 | A novel catalyst for synthesizing pyridine base as well as its preparing and using method |
| CN102219731A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Production method of pyridine base |
| CN102219730A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for preparing pyridine alkali |
| CN105712924A (en) * | 2016-03-24 | 2016-06-29 | 广西新天德能源有限公司 | Method for catalyzing and producing pyridine and picoline with modified molecular sieve |
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