CN116425610B - Production method of trans-1-chloro-3, 3-trifluoropropene - Google Patents
Production method of trans-1-chloro-3, 3-trifluoropropene Download PDFInfo
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- CN116425610B CN116425610B CN202310645150.7A CN202310645150A CN116425610B CN 116425610 B CN116425610 B CN 116425610B CN 202310645150 A CN202310645150 A CN 202310645150A CN 116425610 B CN116425610 B CN 116425610B
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- trifluoropropene
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- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 77
- 239000002131 composite material Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 230000009471 action Effects 0.000 claims abstract description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 53
- 239000002808 molecular sieve Substances 0.000 claims description 37
- 239000002904 solvent Substances 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 238000010335 hydrothermal treatment Methods 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000002444 silanisation Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 238000006884 silylation reaction Methods 0.000 claims description 4
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 2
- JYVHOGDBFNJNMR-UHFFFAOYSA-N hexane;hydrate Chemical compound O.CCCCCC JYVHOGDBFNJNMR-UHFFFAOYSA-N 0.000 claims description 2
- XKUYOJZZLGFZTC-UHFFFAOYSA-K lanthanum(iii) bromide Chemical compound Br[La](Br)Br XKUYOJZZLGFZTC-UHFFFAOYSA-K 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract description 2
- 229910052731 fluorine Inorganic materials 0.000 abstract description 2
- 239000011737 fluorine Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000011069 regeneration method Methods 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006317 isomerization reaction Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- -1 alkoxy compound Chemical class 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910001293 incoloy Inorganic materials 0.000 description 1
- 229910001026 inconel Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001512 metal fluoride Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/35—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction
- C07C17/358—Preparation of halogenated hydrocarbons by reactions not affecting the number of carbon or of halogen atoms in the reaction by isomerisation
-
- 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The application belongs to the technical field of fluorine chemical engineering, and particularly relates to a production method of trans-1-chloro-3, 3-trifluoropropene. The application provides a method for producing trans-1-chloro-3, 3-trifluoropropene, which comprises the following steps: cis-1-chloro-3, 3-trifluoropropene is used as a raw material, and is reacted in a fixed bed reactor under the action of a composite catalyst to generate trans-1-chloro-3, 3-trifluoropropene. The production method of trans-1-chloro-3, 3-trifluoropropene provided by the application has the advantages of low production cost, high cis-1-chloro-3, 3-trifluoropropene conversion rate and high trans-1-chloro-3, 3-trifluoropropene yield. The composite catalyst provided by the production method has longer service life, can be continuously used for more than 240 hours, and is beneficial to industrial continuous production.
Description
Technical Field
The application belongs to the technical field of fluorine chemical engineering, and particularly relates to a production method of trans-1-chloro-3, 3-trifluoropropene.
Background
The ODP value of trans-1-chloro-3, 3-trifluoropropene (HCFO-1233 zd (E)) is 0, the GWP value is 1.0, the environment-friendly performance is excellent, the toxicity is low, the polyurethane foam is incombustible under normal state, the use is safe, the rigid polyurethane foam synthesized by adopting the HCFO-1233zd (E) foaming system has good comprehensive performance and excellent heat insulation performance, and is considered to be an ideal substitute for R141b and R245 fa.
Chinese patent CN103534227B discloses a process for preparing trans-1233 zd, which uses 243fa as raw material, takes HCl off under the action of catalyst to generate trans/cis-1233 zd, and then catalytically isomerizes cis-1233 zd to generate trans-1233 zd. Chinese patent CN103946198B discloses a process for producing trans-1-chloro-3, 3-trifluoropropene, which comprises the step of bringing cis-1-chloro-3, 3-trifluoropropene into contact with a catalyst, wherein the catalyst is a compound obtained by subjecting a fluorinated metal oxide or metal fluoride to a drying treatment at 400 to 600 ℃.
The isomerization catalysts used in the above patent documents are all metal halides, and the catalyst needs to be activated by HF before the reaction, and this method requires high requirements on the materials of the reactor, including Hastelloy, inconel, incoloy and fluoropolymer lining, which results in high investment cost. And the activity and the service life of the adopted catalyst are not ideal, and the yield of the trans-1-chloro-3, 3-trifluoropropene is lower.
Disclosure of Invention
In order to solve the problems in the prior art, the application aims to provide a production method of trans-1-chloro-3, 3-trifluoropropene, which has low cost, high cis-1-chloro-3, 3-trifluoropropene conversion rate and high trans-1-chloro-3, 3-trifluoropropene yield.
The technical scheme of the application is as follows:
a method for producing trans-1-chloro-3, 3-trifluoropropene, comprising the following steps:
taking cis-1-chloro-3, 3-trifluoropropene as a raw material, and reacting in a fixed bed reactor under the action of a composite catalyst to generate trans-1-chloro-3, 3-trifluoropropene;
the preparation method of the composite catalyst comprises the following steps:
s1, adding a solvent into a ZSM-5 molecular sieve, adding a silanization reagent and La precursor salt, uniformly stirring, heating, evaporating the solvent, drying and roasting to obtain a modified molecular sieve;
s2, carrying out hydrothermal treatment on the modified molecular sieve obtained in the step S1, and then tabletting and forming to obtain the composite catalyst.
Preferably, the ZSM-5 molecular sieve, solvent and silylating agent are added in a ratio of 10 g:90~110 mL:0.3~0.5 g in step S1, wherein ZSM-5 molecular sieve and silylating agent are present in weight (g) and solvent is present in volume (mL).
Further preferably, the ZSM-5 molecular sieve, solvent and silylating agent are added in a ratio of 10 g:100 mL:0.4 g in step S1.
Preferably, the addition amount of the precursor salt of La in the step S1 is calculated according to the load amount of La, and the load amount of La is 1-5 wt%.
Further preferably, the La is supported in an amount of 1 to 3 wt%.
Particularly preferably, the La loading is 2 wt%.
Preferably, the silylating agent in the step S1 is one of hexamethyldioxysilane, trimethylsilane chloride and tetraethylorthosilicate.
Further preferably, the silylating agent in the step S1 is one of hexamethyldioxysilane and tetraethyl orthosilicate.
Particularly preferably, the silylating agent in step S1 is ethyl orthosilicate.
Preferably, the precursor salt of La in the step S1 is one of lanthanum nitrate, lanthanum chloride, lanthanum sulfate and lanthanum bromide.
Further preferably, the precursor salt of La is one of lanthanum nitrate, lanthanum chloride and lanthanum sulfate.
Particularly preferably, the precursor salt of La is lanthanum nitrate.
Preferably, the solvent in the step S1 is one of water, methanol, ethanol, toluene and cyclohexane.
Further preferably, the solvent in the step S1 is one of water, methanol, and toluene.
Particularly preferably, the solvent in the step S1 is one of methanol and toluene.
Preferably, in the preparation method of the composite catalyst, in the step S1, a solvent is added into a ZSM-5 molecular sieve, a silylation reagent and a precursor salt of La are added, the mixture is stirred uniformly for 3-5 min at 45-55 ℃, then the mixture is heated to 80-100 ℃ and evaporated to dryness, the solvent is dried at 110-130 ℃ for 12 h, and then the mixture is baked at 450-600 ℃ for 4-7 h, so that the modified molecular sieve is obtained.
Further preferably, in the step S1, a solvent is added to the ZSM-5 molecular sieve, then a silylation agent and a precursor salt of La are added, the mixture is stirred uniformly for 3 to 5 minutes at 50 ℃, then the mixture is heated to 90 ℃ and evaporated to dryness, and then dried at 120 ℃ for 12 h, and then baked at 550 ℃ for 6 h, thereby obtaining the modified molecular sieve.
Preferably, in the preparation method of the composite catalyst, a certain amount of water and nitrogen are required to be introduced in the hydrothermal aging process in the step S2, the flow rate of the introduced water is 2 mL/min, the flow rate of the introduced nitrogen is 10 mL/min, the hydrothermal aging temperature is 450-550 ℃, and the time is 2.5-3.5 h.
Further preferably, the temperature of the hydrothermal aging in the step S2 is 500 ℃ and the time is 3 h.
Preferably, in the fixed bed reactor, the reaction temperature is 120-320 o And C, the contact time of the raw materials and the composite catalyst is 6-20 s.
Further preferably, in the fixed bed reactor, the reaction temperature is 130 to 250 o And C, the contact time of the raw materials and the catalyst is 8-15 s.
Particularly preferably, in the fixed bed reactor, the reaction temperature is 150 to 230 o And C, the contact time of the raw materials and the catalyst is 8-13 s.
In addition, the composite catalyst prepared in the application can be recycled through regeneration, and the regeneration method of the composite catalyst can adopt the conventional regeneration method in the field, for example: roasting the composite catalyst in air at 500 ℃ for 3 h, and obtaining the catalyst.
The reaction mechanism of the production method of trans-1-chloro-3, 3-trifluoropropene is as follows:
the application takes cis-1-chloro-3, 3-trifluoropropene as a raw material, and carries out isomerization reaction under the action of the composite catalyst prepared by the application to obtain trans-1-chloro-3, 3-trifluoropropene. The composite catalyst prepared by the application is based on a ZSM-5 molecular sieve, wherein the acid site B in the ZSM-5 molecular sieve is an active site of olefin isomerization reaction, and the C=C double bond of cis-1-chloro-3, 3-trifluoropropene and pi bond of proton acid site (acid site B) form weak interaction and are adsorbed on the molecular sieve to generate pi coordinated composite. After the adsorption of cis-1-chloro-3, 3-trifluoropropene is completed, the cis-1-chloro-3, 3-trifluoropropene further acts with O atoms on a molecular sieve to generate an alkoxy compound, the alkoxy compound is cis, then the alkoxy compound is twisted on a carbon chain to become a trans-alkoxy compound, and then a C-O bond is broken to generate the trans-1-chloro-3, 3-trifluoropropene which is more stable in thermodynamics.
However, the present inventors have found that during the isomerization reaction, some of cis-1-chloro-3, 3-trifluoropropene is polymerized into long-chain olefins, which are also cracked to produce HF, and on the one hand, the presence of long-chain olefins forms carbon deposits on the surface of the catalyst to block the pores of the catalyst, resulting in a decrease in the activity and life of the catalyst; on the other hand, HF generated by cracking can damage the structure of the molecular sieve, easily cause collapse of the molecular sieve framework, and further cause permanent deactivation of the catalyst.
In order to solve the two problems encountered in the reaction, the preparation method firstly carries out silanization treatment on the surface of the ZSM-5 molecular sieve in the preparation process of the composite catalyst, and the silanization reagent reacts with the silicon hydroxyl groups on the surface of the molecular sieve to graft organic functional groups on the surface, which is mainly realized through the covalent structure of Si-OH and organosilicon; simultaneously added La + Can enter into the pore canal of the molecular sieve to combine with hydroxyl in the pore canal to La (OH) 2+ The morphology and the molecular sieve framework interact to strengthen the Al-O bond and improve the framework stability of the ZSM-5 molecular sieve, thereby obviously prolonging the service life of the composite catalyst prepared by the application.
Further, in the molecular sieve silicon hydroxyl reaction process, silicon dioxide generated by decomposition can be deposited on the surface of the ZSM-5 molecular sieve to cover a part of strong acid sites; therefore, the ZSM-5 molecular sieve after silanization treatment is subjected to hydrothermal treatment, most of non-framework aluminum in the pore canal and on the surface can be removed by the hydrothermal treatment, the pore canal size of the molecular sieve is increased, the adsorption and desorption of long-chain olefin are facilitated, carbon deposition on the surface of the catalyst is reduced, and the service life of the catalyst is further prolonged.
Compared with the prior art, the application has the following beneficial effects:
(1) The production method provided by the application is simple to operate and low in production cost, and can effectively improve the conversion rate of cis-1-chloro-3, 3-trifluoropropene and the yield of trans-1-chloro-3, 3-trifluoropropene.
(2) The composite catalyst provided by the application has long service life, can be continuously used for more than 240 hours, is beneficial to industrial continuous production, can be continuously reused after being subjected to regeneration treatment, improves the service performance, and simultaneously can improve the service life of the whole catalyst and reduce the regeneration cost and the production cost of the catalyst.
(3) The catalyst of the application does not contain metal halide, does not cause the loss of reaction equipment, can avoid causing environmental pollution, and is suitable for large-scale industrialized production.
Detailed Description
The application is further illustrated by the following description of specific embodiments, which are not intended to be limiting, and various modifications or improvements can be made by those skilled in the art in light of the basic idea of the application, but are within the scope of the application as long as they do not depart from the basic idea of the application.
In the following examples and comparative examples, the reagents not specifically described were conventional reagents, which were purchased from conventional reagent manufacturing and selling companies, and the methods used, unless otherwise specified, were all prior art.
Example 1
In a fixed bed reactor, at 120 o And C, under the condition of the catalyst C, enabling the contact time of the cis-1-chloro-3, 3-trifluoropropene and the composite catalyst to be 6 s, and carrying out gas chromatography detection analysis on the reacted product.
The preparation method of the composite catalyst comprises the following steps:
s1, weighing 8 g of ZSM-5 molecular sieve, adding 90 mL water, adding 0.3 g tetraethoxysilane and 0.234 g lanthanum nitrate (according to the load of La being 1 wt percent) into a three-neck flask, uniformly stirring for 5min at 45 ℃, heating to 80 ℃, evaporating the solvent, drying at 110 ℃ to 12 h, and then adding 450 o Roasting 7 h under the condition of C to obtain a modified molecular sieve;
s2, placing the modified molecular sieve obtained in the step S1 in a hydrothermal aging furnace, introducing a certain amount of water and nitrogen, wherein the flow rate of the introduced water is 2 mL/min, the flow rate of the introduced nitrogen is 10 mL/min, performing hydrothermal treatment at 450 ℃ for 3.5 h, and performing tabletting and forming to obtain the composite catalyst.
Example 2
In a fixed bed reactor, at 320 o And C, under the condition of the catalyst C, enabling the contact time of the cis-1-chloro-3, 3-trifluoropropene and the composite catalyst to be 20 s, and carrying out gas chromatography detection analysis on the reacted product.
The preparation method of the composite catalyst comprises the following steps:
s1, weighing 12 g of ZSM-5 molecular sieve, adding 110 mL methanol, adding 0.5 g hexamethyldisiloxane and 1.17 g lanthanum nitrate (calculated according to the load of La being 5wt percent) into a three-neck flask, uniformly stirring for 5min at 55 ℃, heating to 100 ℃, evaporating the solvent, drying 12 h at 130 ℃, and then adding 600 o Roasting under C for 4 h to obtain a modified molecular sieve;
s2, placing the modified molecular sieve obtained in the step S1 in a hydrothermal aging furnace, introducing a certain amount of water and nitrogen, wherein the flow rate of the introduced water is 2 mL/min, the flow rate of the introduced nitrogen is 10 mL/min, performing hydrothermal treatment at 550 ℃ for 2.5 h, and performing tabletting and forming to obtain the composite catalyst.
Example 3
In a fixed bed reactor, at 180 o And C, under the condition of the catalyst C, enabling the contact time of the cis-1-chloro-3, 3-trifluoropropene and the composite catalyst to be 10 s, and carrying out gas chromatography detection analysis on the reacted product. .
The preparation method of the composite catalyst comprises the following steps:
s1, weighing 10 g of ZSM-5 molecular sieve, adding 100mL methanol, adding 0.4 g tetraethoxysilane and 0.468 g lanthanum nitrate (calculated according to the load of La being 2 wt percent) into a three-neck flask, uniformly stirring for 4 min at 50 ℃, heating to 90 ℃, evaporating the solvent, drying 12 h at 120 ℃, and then drying 550 o Roasting 6 h under the condition of C to obtain a modified molecular sieve;
s2, placing the modified molecular sieve obtained in the step S1 in a hydrothermal aging furnace, introducing a certain amount of water and nitrogen, wherein the flow rate of the introduced water is 2 mL/min, the flow rate of the introduced nitrogen is 10 mL/min, performing hydrothermal treatment at 500 ℃ for 3 h, and performing tabletting molding to obtain the composite catalyst.
Example 4
In a fixed bed reactor, at 230 o Under the condition of C, the contact time of cis-1-chloro-3, 3-trifluoropropene and the composite catalyst is 13 s, and the products after the reaction are subjected to gas chromatography detection analysis.
The preparation method of the composite catalyst comprises the following steps:
s1, weighing 10 g of ZSM-5 molecular sieve, adding 100mL toluene, adding 0.4 g tetraethoxysilane and 0.468 g lanthanum nitrate (calculated according to the load of La being 2 wt percent) into a three-neck flask, uniformly stirring for 4 min at 50 ℃, heating to 90 ℃, evaporating the solvent, drying 12 h at 120 ℃, and then drying 550 o Roasting 6 h under the condition of C to obtain a modified molecular sieve;
s2, placing the modified molecular sieve obtained in the step S1 in a hydrothermal aging furnace, introducing a certain amount of water and nitrogen, wherein the flow rate of the introduced water is 2 mL/min, the flow rate of the introduced nitrogen is 10 mL/min, performing hydrothermal treatment at 500 ℃ for 3 h, and performing tabletting molding to obtain the composite catalyst.
Comparative example 1
In comparison with example 3, comparative example 1 is distinguished in that the catalyst was formed by tabletting only untreated ZSM-5 molecular sieve, and in that the ZSM-5 molecular sieve was formed in a fixed bed reactor at 180 o And C, under the condition of the catalyst C, enabling the contact time of cis-1-chloro-3, 3-trifluoropropene and a ZSM-5 molecular sieve to be 10 s, and carrying out gas chromatography detection analysis on the reacted product.
Comparative example 2
In comparison with example 3, the difference of comparative example 2 is that lanthanum nitrate was not added in the step S1 in the preparation method of the composite catalyst, and other parameters and operations were the same as example 3.
Comparative example 3
In comparison with example 3, the difference in comparative example 3 is that in the preparation method of the composite catalyst, lanthanum nitrate of 0.468 g is replaced by cerium nitrate of 0.620 g in the step S1, and other parameters and operations are the same as those of example 3.
Comparative example 4
In a fixed bed reactor, at 180 o And C, under the condition of the catalyst C, enabling the contact time of the cis-1-chloro-3, 3-trifluoropropene and the composite catalyst to be 10 s, and carrying out gas chromatography detection analysis on the reacted product.
The preparation method of the composite catalyst comprises the following steps:
s1, weighing 10 g of ZSM-5 molecular sieve, adding 100mL of methanol, adding 0.4. 0.4 g tetraethoxysilane, stirring at 50 ℃ for 4 min, heating to 90 ℃ to evaporate the solvent, drying at 120 ℃ for 5 h, and then at 550 o Roasting 6 h under the condition of C to obtain a silanized molecular sieve;
s2, adding the silanized molecular sieve obtained in the step S1 into 100mL of water, adding 0.468 g lanthanum nitrate (calculated according to the La load amount of 2 wt percent), uniformly stirring, then drying at 120 ℃ for 5 h, and then at 550 o Roasting 3 h to obtain a modified molecular sieve;
s2, placing the modified molecular sieve obtained in the step S2 in a hydrothermal aging furnace, introducing a certain amount of water and nitrogen, wherein the flow rate of the introduced water is 2 mL/min, the flow rate of the introduced nitrogen is 10 mL/min, performing hydrothermal treatment at 500 ℃ for 3 h, and performing tabletting molding to obtain the composite catalyst.
Test example one yield test of trans-1-chloro-3, 3-trifluoropropene produced by the production method of the present application
The products of the production methods of examples 1 to 4 and comparative examples 1 to 4 were subjected to gas chromatography detection analysis to obtain the conversion of cis-1-chloro-3, 3-trifluoropropene (R1233 zd/Z) and the yield of trans-1-chloro-3, 3-trifluoropropene (R1233 zd/E) as shown in Table 1.
TABLE 1
As is clear from Table 1, the products obtained by the production methods of examples 1 to 4 of the present application were examined and analyzed by gas chromatography, wherein example 3 was found to have the best effect, the conversion rate of R1233zd/Z was 99.1%, and the yield of R1233zd/E was 98.1%. The composite catalyst prepared by the application can effectively improve the yield of trans-1-chloro-3, 3-trifluoropropene.
In contrast, in comparative example 1, only the ZSM-5 molecular sieve catalyst was used for catalysis, in comparative example 2, lanthanum nitrate was not added in the preparation step S1 of the composite catalyst, and in comparative example 3, when lanthanum nitrate was replaced with cerium nitrate, the obtained data of conversion rate and yield were significantly reduced. In comparative example 4, when the preparation steps of the composite catalyst are changed, the ZSM-5 molecular sieve is subjected to silanization modification, la is loaded, and finally, the hydrothermal treatment is carried out to obtain the composite catalyst, wherein the conversion rate of R1233zd/Z can reach 93.6%, but the yield of R1233zd/E is obviously reduced by only 86.1%.
Test example II, detection of service life and regeneration Performance of composite catalyst prepared by the application
(1) The catalysts prepared in examples 1 to 4 and comparative examples 1 to 4 were used for 48 hours and 240 hours, respectively, to detect the catalytic performance. The products after the reaction were analyzed by gas chromatography to obtain the conversion (%) of R1233zd/Z and the yield (%) of R1233zd/E, respectively, as shown in Table 2.
(2) The composite catalysts prepared in examples 1 to 4 and comparative examples 1 to 4 were subjected to a regeneration treatment using 240, 240h, and the regeneration treatment method was as follows: the composite catalyst after 240 and h is calcined in air at 500 ℃ for 3 h.
Continuously catalyzing cis-1-chloro-3, 3-trifluoropropene to produce trans-1-chloro-3, 3-trifluoropropene by using the regenerated composite catalyst, wherein the temperature in a fixed bed reactor is 180 DEG o C, the contact time was 10 s, and the reaction product was analyzed by gas chromatography to obtain the conversion (%) of R1233zd/Z and the yield (%) of R1233zd/E as shown in Table 2.
TABLE 2
As can be seen from Table 2, the conversion rate of R1233zd/Z is 92% or more after 48 and h is used, the conversion rate of R1233zd/E is still 90% after 240 and h is still reached, the yield of R1233zd/E is 89% or more after 48 and h is also 86.5% after 240 and h is used, and the effect of the composite catalyst after regeneration treatment is similar to that of the composite catalyst newly prepared in examples 1 to 4, the catalytic performance is excellent, and the catalytic effect before regeneration treatment can be completely recovered.
When the composite catalyst prepared in comparative examples 1-4 is used for catalyzing cis-1-chloro-3, 3-trifluoropropene, the conversion rate of the obtained R1233zd/Z and the yield of the obtained R1233zd/E are reduced to different degrees at the time of 48h and 240h and after regeneration treatment. The preparation method of the composite catalyst provided by the application can effectively improve the catalytic performance of the composite catalyst and prolong the service life of the catalyst.
The above embodiments are merely illustrative of the principles of the present application and its effectiveness, and are not intended to limit the application. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the application. Accordingly, it is intended that all equivalent modifications and variations of the application be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (5)
1. A process for the production of trans-1-chloro-3, 3-trifluoropropene comprising the steps of:
taking cis-1-chloro-3, 3-trifluoropropene as a raw material, and reacting in a fixed bed reactor under the action of a composite catalyst to generate trans-1-chloro-3, 3-trifluoropropene;
the preparation method of the composite catalyst comprises the following steps:
s1, adding a solvent into a ZSM-5 molecular sieve, adding a silanization reagent and La precursor salt, uniformly stirring, heating, evaporating the solvent, drying and roasting to obtain a modified molecular sieve;
s2, carrying out hydrothermal treatment on the modified molecular sieve obtained in the step S1, and then tabletting and forming to obtain the composite catalyst;
the silylation reagent in the step S1 is one of hexamethyl dioxysilane, trimethyl silane chloride and tetraethoxysilane;
the precursor salt of La in the step S1 is one of lanthanum nitrate, lanthanum chloride, lanthanum sulfate and lanthanum bromide;
in the step S1, adding a solvent into a ZSM-5 molecular sieve, adding a silylation reagent and a precursor salt of La, uniformly stirring for 3-5 min at 45-55 ℃, heating to 80-100 ℃, evaporating the solvent, drying for 12-h at 110-130 ℃, and roasting for 4-7 h at 450-600 ℃ to obtain a modified molecular sieve;
the solvent in the step S1 is one of water, methanol, ethanol, toluene and cyclohexane;
the temperature of the hydrothermal aging in the step S2 is 450-550 ℃ and the time is 2.5-3.5 hours.
2. The method for producing trans-1-chloro-3, 3-trifluoropropene according to claim 1, wherein the ZSM-5 molecular sieve, the solvent and the silylating agent are added in a ratio of 10 g:90~110 mL:0.3~0.5 g in step S1.
3. The method for producing trans-1-chloro-3, 3-trifluoropropene according to claim 2, wherein the ZSM-5 molecular sieve, the solvent and the silylating agent are added in a ratio of 10 g:100 mL:0.4 g in the step S1.
4. The method for producing trans-1-chloro-3, 3-trifluoropropene according to claim 1, wherein the precursor salt of La in step S1 is added in an amount of 1-5 wt% of La based on the amount of La.
5. The method for producing trans-1-chloro-3, 3-trifluoropropene according to claim 1, wherein the reaction temperature in the fixed bed reactor is 120-320 ℃, and the contact time between the raw material and the composite catalyst is 6-20 s.
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| CN103946198A (en) * | 2011-11-21 | 2014-07-23 | 中央硝子株式会社 | Method for producing trans-1-chloro-3,3,3-trifluoropropene |
| CN109627143A (en) * | 2018-12-25 | 2019-04-16 | 西安近代化学研究所 | A kind of preparation method of the chloro- 3,3,3- trifluoro propene of trans- 1- |
| CN111356670A (en) * | 2017-10-26 | 2020-06-30 | 霍尼韦尔国际公司 | Process for the catalytic conversion of a mixture of HCFO-1233zd (Z) and HCFC-244fa to HCFO-1233zd (E) |
| CN113527047A (en) * | 2020-04-22 | 2021-10-22 | 陕西中蓝化工科技新材料有限公司 | Process for co-producing trans-HFO-1234 ze and cis-HFO-1234 ze |
| WO2022138675A1 (en) * | 2020-12-22 | 2022-06-30 | セントラル硝子株式会社 | Method for producing unsaturated chlorofluorocarbon, and composition |
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| CN103946198A (en) * | 2011-11-21 | 2014-07-23 | 中央硝子株式会社 | Method for producing trans-1-chloro-3,3,3-trifluoropropene |
| CN111356670A (en) * | 2017-10-26 | 2020-06-30 | 霍尼韦尔国际公司 | Process for the catalytic conversion of a mixture of HCFO-1233zd (Z) and HCFC-244fa to HCFO-1233zd (E) |
| CN109627143A (en) * | 2018-12-25 | 2019-04-16 | 西安近代化学研究所 | A kind of preparation method of the chloro- 3,3,3- trifluoro propene of trans- 1- |
| CN113527047A (en) * | 2020-04-22 | 2021-10-22 | 陕西中蓝化工科技新材料有限公司 | Process for co-producing trans-HFO-1234 ze and cis-HFO-1234 ze |
| WO2022138675A1 (en) * | 2020-12-22 | 2022-06-30 | セントラル硝子株式会社 | Method for producing unsaturated chlorofluorocarbon, and composition |
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