CN113527048B - Method for isomerising transHFO-1234 ze and catalyst carrier therefor - Google Patents
Method for isomerising transHFO-1234 ze and catalyst carrier therefor Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 56
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 32
- CDOOAUSHHFGWSA-UPHRSURJSA-N (z)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C/C(F)(F)F CDOOAUSHHFGWSA-UPHRSURJSA-N 0.000 claims abstract description 22
- 239000013078 crystal Substances 0.000 claims abstract description 22
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 12
- 239000006227 byproduct Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000005416 organic matter Substances 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000005796 dehydrofluorination reaction Methods 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SMCNZLDHTZESTK-UHFFFAOYSA-N 2-chloro-1,1,1,2-tetrafluoropropane Chemical compound CC(F)(Cl)C(F)(F)F SMCNZLDHTZESTK-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910001026 inconel Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 description 1
- 102100028292 Aladin Human genes 0.000 description 1
- 101710065039 Aladin Proteins 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- FTBATIJJKIIOTP-UHFFFAOYSA-K trifluorochromium Chemical compound F[Cr](F)F FTBATIJJKIIOTP-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
Abstract
The present invention relates to a process for isomerising transHFO-1234 ze and a catalyst support therefor. The process for isomerising transHFO-1234 ze comprises: (1) providing a feed stream comprising transhfo-1234 ze; (2) Contacting transHFO-1234 ze with a catalyst to isomerize transHFO-1234 ze to cis HFO-1234ze, the catalyst support being Al 2 O 3 ，Al 2 O 3 Comprising theta-Al 2 O 3 And alpha-Al 2 O 3 The mixed crystal phase and the catalyst carrier are active on the isomerization reaction of transHFO-1234 ze. The organic matter of the product of the invention has high content of cis HFO-1234ze, and the byproduct HFC-245fa has very little content, thereby simplifying the process flow of the industrial amplifying and circulating process, reducing the energy consumption of the purifying step of the product and improving the purity of the product.
Description
Technical Field
The invention relates to a preparation method of fluorine-containing organic compounds, in particular to a method for isomerizing transHFO-1234 ze and a catalyst carrier thereof.
Background
With increasing concerns about global warming, and the associated possible adverse climate effects, developed countries are increasingly agreeing to reduce greenhouse gas emissions. Given the relatively high Global Warming Potential (GWP) of most Hydrofluorocarbons (HFCs), various countries are taking several actions to reduce the use of these fluids. For example, the recent F-Gas regulations in the european union specify the mandatory GWP value for refrigerants used as working fluids in almost all air conditioners and refrigerators since 2020. Some refrigerant materials in use today that have GWP values in excess of 150 will be increasingly replaced.
To date, several types of possible alternative candidates have been proposed, including synthetic and natural. Of the synthetic options, hydrofluoroolefins (HFOs) are by far the most promising option.
Fourth-generation HFO series refrigerant, e.g. cis-1, 3-tetrafluoropropene (cis-HFO-1234 ze, CF) 3 Ch=chf) has a double bond structure between carbons in a molecule, and has a high reactivity with hydroxyl radicals, so that Global Warming Potential (GWP) is extremely low, a load on the environment is small, and flame retardancy and no toxicity are provided. ODP value of cis-1, 3-tetrafluoropropene is 0, GWP 100 The value is less than 1, the atmospheric service life is only 9 days, and the valve is considered as one of the most potential alternative working media, and has good application prospects in refrigeration cycles, heat pumps and Organic Rankine Cycles (ORCs).
In recent years, synthesis of HFO-1234ze has been studied to obtain mainly a mixture of two isomers of transHFO-1234 ze and cis-HFO-1234ze, and isomerizing the cis-HFO-1234ze to transHFO-1234 ze.
Honival has been stated to achieve mass production of HFO-1234ze, resulting in low Global Warming Potential (GWP) materials useful for aerosol propellants, blowing agents and refrigerants, featuring energy conservation, safety, no ozone depletion, and extremely low global warming potential. A process for producing trans-1, 3-tetrafluoropropene is disclosed in patent CN103483143a of the ganivill application, comprising: (a) Dehydrofluorination of 1, 3-pentafluoropropane to give a product containing cis-1, 3-tetrafluoropropene a product of trans-1, 3-tetrafluoropropene and hydrogen fluoride; (b) Optionally recovering hydrogen fluoride from the product of step (a); (c) Isomerizing at least a portion of the cis-1, 3-tetrafluoropropene to trans-1, 3-tetrafluoropropene; and (d) recovering the trans-1, 3-tetrafluoropropene.
Based on the reaction of generating cis-and trans-HFO-1234 ze by gas phase dehydrofluorination of 1, 3-pentafluoropropane as raw material and further converting cis-HFO-1234ze into trans-HFO-1234 ze by gas phase isomerization, the patent CN109718814A filed by the Western Ann modern chemical research institute discloses a low-temperature ultra-high activity and environment-friendly catalyst for synthesizing trans-1, 3-tetrafluoropropene by gas phase isomerization, which is characterized in that the catalyst comprises M/MgF 2 Wherein the matrix is MgF 2 Has rutile phase and nano spherical structure, and specific surface area of more than 120m 2 High stability MgF with excellent anti-sintering performance at 500 deg.C/g 2 The active component M is selected from Co 3+ 、Ni 2+ 、Fe 3+ 、Zn 2+ 、La 3+ 、Al 3+ 、Ga 3+ 、Mn 4+ 、Cu 2+ The mass of M accounts for 5-20% of the total mass of the catalyst.
Patent CN106946647B of prolonged petroleum application from shanxi discloses a method for preparing trans-1, 3-tetrafluoropropene by normal temperature isomerization of a mixture, which comprises the steps of firstly carrying out dehydrohalogenation reaction, then carrying out isomerization reaction, introducing anhydrous hydrogen fluoride into a mixture of pentafluoropropane and tetrafluoro-monochloropropane as raw materials, and carrying out dehydrofluorination reaction in a first reactor in a gas phase of dehydrofluorination and hydrogen chloride; introducing the mixture obtained by the reaction in the first reactor into a second reactor, carrying out gas phase isomerization reaction by taking chromium fluoride as a catalyst at normal temperature and normal pressure, and separating pentafluoropropane, tetrafluoro-monochloropropane, hydrogen fluoride, hydrogen chloride and cis-1, 3-tetrafluoropropene in the reaction product to obtain a purified product, namely trans-1, 3-tetrafluoropropene.
Few cis HFO-1234ze is produced in the prior art, however, the physical and chemical properties of cis HFO-1234ze are not the same as trans HFO-1234ze, the boiling point of cis HFO-1234ze is 9℃, the boiling point of trans HFO-1234ze is-19℃, and in some applications, cis HFO-1234ze has more excellent use.
In the prior art, when transHFO-1234 ze is produced by an isomerization reaction, metal fluorides are generally used as isomerization catalysts. However, metal fluorides are used as catalysts for the isomerization of transHFO-1234 ze to cis HFO-1234ze, which produces more by-products and serious carbon deposition.
WO2019047447A1 discloses alumina supported chromium and magnesium as isomerisation catalysts but which catalyses the isomerisation of cis-1-chloro-3, 3-trifluoropropene and is not suitable for catalysing the isomerisation of transhfo-1234 ze and the chromium used is more toxic and the alumina carrier is not disclosed in crystalline form and source.
In the prior art, the alumina has more crystal forms, and the common alumina mainly comprises three crystal forms, namely gamma-Al 2 O 3 、β-Al 2 O 3 、α-Al 2 O 3 . The Al of different crystal forms is mixed and used 2 O 3 In the case of Al, al of different crystal forms 2 O 3 The powder is mixed, and the controlled production of the powder by the preparation process is less, and the powder simultaneously comprises a plurality of crystal forms of Al 2 O 3 Is a powder of (a). Alumina is more common as a catalyst support, but less common is used as a support for the isomerisation catalyst of transHFO-1234 ze.
Disclosure of Invention
The invention aims to provide a method for isomerizing transHFO-1234 ze, which has high content of cis HFO-1234ze in organic matters of products and very little content of byproduct HFC-245fa, thereby simplifying the process flow of industrial amplification circulation process, reducing the energy consumption of the purification step of the products and improving the purity of the products. The catalyst carrier of the invention has simple preparation and reasonable structure, and is suitable for being used as a catalyst carrier for isomerizing transHFO-1234 ze.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method of isomerising transhfo-1234 ze, comprising: (1) providing a feed stream comprising transhfo-1234 ze; (2) Contacting transHFO-1234 ze with a catalyst to isomerize transHFO-1234 ze to cis HFO-1234ze, the catalyst support being Al 2 O 3 ，Al 2 O 3 Comprising theta-Al 2 O 3 And alpha-Al 2 O 3 The mixed crystal phase and the catalyst carrier are active on the isomerization reaction of transHFO-1234 ze.
The feed stream comprising transHFO-1234 ze contains no or less than 18% by mass of cis HFO-1234ze.
The isomerization reaction temperature is 150-500 ℃, the reaction pressure is 0.1-5MPa, and the space velocity of the raw material is 20-2000h -1 The isomerisation reaction is carried out in the gas phase. The reaction temperature is further preferably 200 to 350 ℃. The reaction pressure is more preferably 0.1 to 0.6MPa. The space velocity of the raw material is more preferably 500 to 1000 hours -1 。
The catalyst carrier is prepared by taking aluminum isopropoxide as an aluminum source.
The specific surface area of the catalyst carrier is 10-20m 2 And/g, the average pore diameter is 20-30nm.
The pore size distribution of the catalyst carrier is concentrated, and more than 80% of the pore sizes are 15-35nm. Preferably, more than 90% of the pores have a pore size of 15-35nm.
After the isomerization reaction, the crystal form of the catalyst carrier is unchanged. The catalyst carrier has high stability.
The performance of the catalyst support meets the following requirements: when the catalyst carrier is used alone in the isomerization reaction of transHFO-1234 ze, the transHFO-1234 ze is introduced, 5mL of catalyst carrier is filled, the reaction temperature is 350 ℃ and the space velocity is 300h -1 The pressure is 0.1MPa, after the reaction is carried out for 10 hours, the content of cis HFO-1234ze in the organic matters of the product is higher than 18 percent, and the HFC-245fa containsThe amount is less than 0.1%. Preferably, the HFC-245fa content is less than 0.08%.
The preparation of the catalyst carrier specifically comprises the following steps: adding aluminum isopropoxide into ethylene glycol to prepare an aluminum solution with the aluminum content of 0.5-2mol/L, then treating for 12-48 hours at the temperature of 120-180 ℃, centrifugally separating, washing a centrifugally separated sample by absolute ethyl alcohol, drying for 10-24 hours in air at the temperature of 40-70 ℃ to obtain powder, and roasting the powder in air at the temperature of 1000-1500 ℃ for 1-5 hours to obtain the product containing theta-Al 2 O 3 And alpha-Al 2 O 3 Catalyst supports of mixed crystalline phase.
The preparation method comprises the following steps of 2 O 3 And alpha-Al 2 O 3 alpha-Al in a catalyst support of mixed crystal phase 2 O 3 The content of (C) is 70-95%, theta-Al 2 O 3 The content of alpha-Al is 5-30% 2 O 3 With theta-Al 2 O 3 The content ratio of (2) is 5-15:1.
the catalyst carrier prepared by the invention has stable crystal form structure, and the crystal form structure is very suitable for isomerization reaction of transHFO-1234 ze. The carrier surface has few acid-base centers, the L acid strength is proper, the carbon deposition resistance is good, and the selectivity to the isomerization reaction of transHFO-1234 ze is high.
The support is the main component of the transHFO-1234 ze isomerization catalyst and is also an important factor affecting the performance of the catalyst. The carrier is very suitable for loading active components and has excellent dispersion performance on the active components. The catalyst comprising the active component and the carrier of the invention is adopted to carry out the isomerization reaction of the transHFO-1234 ze, so that the synergistic effect of metal and acidity can be realized, the reaction conversion rate is high, the stability is good, the carbon deposition resistance is strong, the side reaction is obviously reduced, and the generation of the byproduct HFC-245fa is obviously reduced.
The active component of the transHFO-1234 ze isomerization catalyst consists of one or more of group VIII metal and group IB metal elements, preferably one or more of Fe, co, ni, ru, rh, pd, pt, cu, ag, au, and further the active component is preferably Pd, cu and/or Fe. Alternatively, the active component is Pd. Alternatively, the active component is Fe. In the catalyst preparation process, the raw materials of the active component are preferably chlorides, carbonates, nitrates, acetates and sulfates corresponding to the metals of the active component.
The transHFO-1234 ze isomerization catalyst may also include doping components and/or adjuvants.
The doping component is composed of one or more of alkali metal and alkaline earth metal elements, preferably one or more of Na, K, mg, ca, sr or Ba, and further preferably Ca, mg and/or Sr. Optionally, the doping component is Ca. Optionally, the doping component is Sr. The doping component may be Na, K, mg, ca, sr or an oxide, fluoride, hydroxide, preferably an oxide of Ba. The doping component has the function of regulating the acidity and acid quantity of the carrier, especially reducing the quantity of strong Lewis acid sites on the carrier, and can further reduce the production quantity of HFC-245 fa.
The auxiliary agent is composed of one or more of alkali metals, preferably at least one selected from K, cs and Na. Optionally, the auxiliary agent is K. Optionally, the auxiliary agent is Cs. The auxiliary agent can cooperate with the carrier, the active component and the doping component to effectively reduce Lewis acidity of the catalyst, promote high dispersion of metal active centers and interaction between the carriers, obviously reduce side reaction in the gas phase isomerization process of transHFO-1234 ze, reduce carbon deposition and improve stability.
In the transHFO-1234 ze isomerization catalyst, the mass percentage of the carrier, the active component, the doping component and the auxiliary agent of the catalyst is 1 (0.001-0.2): 0-0.2, preferably 1 (0.01-0.1): 0-0.15, more preferably 1 (0.01-0.05): 0.001-0.1.
The catalyst provided by the invention can be prepared according to methods commonly used in the art, such as an impregnation method, a precipitation method and a mechanical mixing method, so as to realize the combination of the carrier, the active component and the auxiliary agent.
Preferably, the catalyst provided by the invention can be subjected to an activation treatment before use. The catalyst activation treatment method is to load the prepared catalyst into a reaction area, and to perform hydrogen reduction and/or nitrogen and air roasting, preferably to perform nitrogen roasting at 250-350 ℃.
The catalyst of the invention has very proper acid strength, high reaction activity, less byproduct HFC-245fa, less carbon deposit and good long-term stability. The isomerization reaction of transHFO-1234 ze by the catalyst of the invention is carried out at the reaction temperature of 350 ℃ and the space velocity of 300h -1 After the reaction is carried out for 10 hours under the pressure of 0.1MPa, the content of HFC-245fa in the organic matters of the reaction product can still be kept below 0.01 percent, even 0 percent, and the content of cis-HFO-1234ze in the organic matters of the reaction product can still be kept above 19 percent, even above 20 percent.
Drawings
FIG. 1 is a block diagram of an embodiment 1 of a composition containing θ -Al 2 O 3 And alpha-Al 2 O 3 X-ray diffraction pattern of a mixed-phase alumina support.
FIG. 2 is a block diagram of an embodiment 1 of a composition containing θ -Al 2 O 3 And alpha-Al 2 O 3 X-ray diffraction pattern of a mixed-phase alumina support after use in the preparation of cis HFO-1234ze from trans HFO-1234ze.
Detailed Description
The invention is further illustrated by the following specific examples in conjunction with the accompanying description. It will be appreciated by those skilled in the art that the invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Example 1: comprising theta-Al 2 O 3 And alpha-Al 2 O 3 Preparation of alumina of mixed crystal phase
Adding aluminum isopropoxide into ethylene glycol to prepare a solution with aluminum content of 1.0mol/L, then treating at 150 ℃ for 24 hours, centrifuging, washing a sample obtained by centrifuging with absolute ethyl alcohol, drying in air at 50 ℃ for 12 hours to obtain powder, and roasting the powder in air at 1200 ℃ for 3 hours to obtain a powder containing theta-Al 2 O 3 And alpha-Al 2 O 3 A catalyst support in a crystalline phase, the catalyst support having a specific surface area of 15.3m 2 Per g, average pore diameter of 23.3nm, pore diameter of 15-35nm at 92% or more, wherein, alpha-Al 2 O 3 The content is 85 percent, theta-Al 2 O 3 The content was 15%, and the X-ray diffraction pattern was shown in FIG. 1.
The catalyst support itself was active against commercially available alumina (Ala-Din, gamma-Al 2 O 3 ) The evaluation results are shown in Table 1, and the catalyst carrier of the present invention has better selectivity as can be seen when 5mL of catalyst carrier is filled and the reaction pressure is 0.1 MPa.
TABLE 1
Introducing transHFO-1234 ze, filling 5mL of the catalyst carrier prepared in the embodiment, and reacting at 350 ℃ with a space velocity of 300h -1 The pressure is 0.1MPa, after the reaction is carried out for 10 hours, the crystal form is unchanged (figure 2), and the surface of the catalyst is free from carbon deposition, which shows that the catalyst has better stability and carbon deposition resistance.
Example 2:2% Cu/15% CaO-including θ -Al 2 O 3 And alpha-Al 2 O 3 Mixing CaO with the catalyst carrier prepared in example 1 according to a required proportion by ball milling, stirring and mixing uniformly, tabletting or extrusion molding to obtain a doped modified carrier, weighing a required amount of copper nitrate, dissolving in a certain amount of water, and dripping 15% CaO-containing theta-Al into the doped modified carrier 2 O 3 And alpha-Al 2 O 3 Soaking in alumina with mixed crystal phase at 60 deg.c for 18 hr and drying at 105 deg.c for 6 hr to obtain the catalyst precursor.
The catalyst precursor is placed in a Inconel tubular reactor with an inner diameter of 1 inch and a length of 90cm, 100mL/min of nitrogen is introduced, roasting is carried out for 2 hours at 200 ℃, then the temperature is raised to 500 ℃, and roasting is carried out for 3 hours, thus obtaining the fluorine-containing olefin isomerization catalyst.
Example 3:1% Pd-1% Na/comprising θ -Al 2 O 3 And alpha-Al 2 O 3 Alumina of mixed crystal phase
A certain amount of the carrier prepared in example 1 and PdCl with the metal mass percentage of 1 percent are added 2 The impregnating solution is impregnated in equal volume, baked at 120 ℃ and baked in a tube furnace at 400 ℃ for 4 hours in nitrogen atmosphereReducing for 2 hours at 200 ℃ in hydrogen atmosphere to obtain Pd/containing theta-Al 2 O 3 And alpha-Al 2 O 3 Alumina of mixed crystal phase. Pd/containing theta-Al to be prepared 2 O 3 And alpha-Al 2 O 3 And (3) mixing crystalline phase alumina to obtain NaF impregnating solution with the same volume of 1% of metal mass percentage, drying at 120 ℃, and roasting at 500 ℃ for 4 hours in a nitrogen atmosphere of a tube furnace to obtain the catalyst.
Example 4:1% Pd-1% Na/10% SrO-containing θ -Al 2 O 3 And alpha-Al 2 O 3 Alumina of mixed crystal phase
Ball-milling and mixing SrO and the catalyst carrier prepared in the example 1 according to a required proportion, uniformly stirring and mixing, tabletting or extrusion molding to obtain a doped modified carrier, and mixing the doped modified carrier and PdCl with the metal mass percentage of 1% 2 The impregnating solution is impregnated in equal volume, baked in a tube furnace at 400 ℃ for 4 hours in nitrogen atmosphere after being dried at 120 ℃, and reduced for 2 hours at 200 ℃ in hydrogen atmosphere, thus obtaining Pd/SrO-containing theta-Al 2 O 3 And alpha-Al 2 O 3 Alumina of mixed crystal phase. The prepared Pd/SrO-contains theta-Al 2 O 3 And alpha-Al 2 O 3 And (3) mixing crystalline phase alumina to obtain NaF impregnating solution with the same volume of 1% of metal mass percentage, drying at 120 ℃, and roasting at 500 ℃ for 4 hours in a nitrogen atmosphere of a tube furnace to obtain the catalyst.
Comparative example 1:2% Cu/15% CaO-commercially available alpha-Al 2 O 3
The same procedure as in example 2 was followed, except that the catalyst was 2% Cu/15% CaO-commercially available α -Al 2 O 3 (aladdin,99.99％)。
Comparative example 2:1% Pd-1% Na/commercially available alpha-Al 2 O 3
The same procedure as in example 3 was followed, except that the catalyst was 1% Pd-1% Na/commercially available α -Al 2 O 3 (aladdin,99.99％)。
Comparative example 3:15% CaO-including θ -Al 2 O 3 And alpha-Al 2 O 3 Alumina of mixed crystal phase
The same operation as in example 2 was carried out, except that the catalyst contained no active component and no step of adding copper nitrate was carried out, and the catalyst was a doping modified support, namely: 15% CaO-including θ -Al 2 O 3 And alpha-Al 2 O 3 Alumina of mixed crystal phase.
5mL of the fluoroolefin isomerization catalyst in the above examples and comparative examples was charged into a Inconel tube reactor having an inner diameter of 1/2 inch and a length of 40cm, and transHFO-1234 ze was introduced at a reaction temperature of 350℃and a space velocity of 300 hours -1 After reaction for 10 hours under the pressure of 0.1MPa, the reaction product is washed with water and alkali, organic matters are obtained by separation, and after drying and water removal, the composition of the organic matters is analyzed by gas chromatography, and the results are shown in Table 1. It can be seen that the organic material of the product of the examples of the present invention has a high cis HFO-1234ze content and low by-products.
TABLE 1
Claims (8)
1. A process for isomerising transhfo-1234 ze, characterized by: the method comprises the following steps: (1) providing a feed stream comprising transhfo-1234 ze; (2) Contacting transHFO-1234 ze with a catalyst to isomerize transHFO-1234 ze to cis HFO-1234ze, the catalyst support being Al 2 O 3 ，Al 2 O 3 Comprising theta-Al 2 O 3 And alpha-Al 2 O 3 The mixed crystal phase and the catalyst carrier are active on the isomerization reaction of transHFO-1234 ze.
2. The method according to claim 1, characterized in that: the feed stream comprising transHFO-1234 ze contains no or less than 18% by mass of cis HFO-1234ze.
3. The method according to claim 1, characterized in that: the catalyst carrier is prepared by taking aluminum isopropoxide as an aluminum source.
4. The method according to claim 1 or 2, characterized in that: the specific surface area of the catalyst carrier is 10-20m 2 And/g, the average pore diameter is 20-30nm.
5. The method according to claim 4, wherein: the pore size distribution of the catalyst carrier is concentrated, and more than 80% of the pore sizes are 15-35nm.
6. The method according to claim 1 or 2, characterized in that: after the isomerization reaction, the crystal form of the catalyst carrier is unchanged.
7. The method according to claim 1 or 2, characterized in that: the performance of the catalyst support meets the following requirements: when the catalyst carrier is used alone in the isomerization reaction of transHFO-1234 ze, the transHFO-1234 ze is introduced, 5mL of catalyst carrier is filled, the reaction temperature is 350 ℃ and the space velocity is 300h -1 After 10 hours of reaction at 0.1MPa, the content of cis HFO-1234ze in the organic matters of the product is higher than 18 percent, and the content of HFC-245fa is lower than 0.1 percent.
8. The method according to claim 1 or 2, characterized in that: the preparation of the catalyst carrier specifically comprises the following steps: adding aluminum isopropoxide into ethylene glycol to prepare an aluminum solution with the aluminum content of 0.5-2mol/L, then treating for 12-48 hours at the temperature of 120-180 ℃, centrifugally separating, washing a centrifugally separated sample by absolute ethyl alcohol, drying for 10-24 hours in air at the temperature of 40-70 ℃ to obtain powder, and roasting the powder in air at the temperature of 1000-1500 ℃ for 1-5 hours to obtain the product containing theta-Al 2 O 3 And alpha-Al 2 O 3 Catalyst supports of mixed crystalline phase.
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