CN113522285A - Trans-fluorine-containing olefin isomerization catalyst and preparation method and application thereof - Google Patents
Trans-fluorine-containing olefin isomerization catalyst and preparation method and application thereof Download PDFInfo
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- CN113522285A CN113522285A CN202110418779.9A CN202110418779A CN113522285A CN 113522285 A CN113522285 A CN 113522285A CN 202110418779 A CN202110418779 A CN 202110418779A CN 113522285 A CN113522285 A CN 113522285A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 37
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 28
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 26
- 239000011737 fluorine Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000006227 byproduct Substances 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 4
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 8
- 239000012018 catalyst precursor Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 2
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- 150000003839 salts Chemical class 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 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 description 26
- 229910052594 sapphire Inorganic materials 0.000 description 26
- 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 description 19
- 229910052799 carbon Inorganic materials 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 229910006415 θ-Al2O3 Inorganic materials 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 230000008021 deposition Effects 0.000 description 11
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- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000463 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000005796 dehydrofluorination reaction Methods 0.000 description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000003507 refrigerant Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 208000012839 conversion disease Diseases 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000005057 refrigeration Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- GDPWRLVSJWKGPJ-UPHRSURJSA-N (z)-1-chloro-2,3,3,3-tetrafluoroprop-1-ene Chemical compound Cl\C=C(/F)C(F)(F)F GDPWRLVSJWKGPJ-UPHRSURJSA-N 0.000 description 1
- LDTMPQQAWUMPKS-UPHRSURJSA-N (z)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C/Cl LDTMPQQAWUMPKS-UPHRSURJSA-N 0.000 description 1
- AUCISWTVFIKMCZ-UHFFFAOYSA-N 1-chloro-1,1,2,2-tetrafluoropropane Chemical compound CC(F)(F)C(F)(F)Cl AUCISWTVFIKMCZ-UHFFFAOYSA-N 0.000 description 1
- PRDFNJUWGIQQBW-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-yne Chemical compound FC(F)(F)C#C PRDFNJUWGIQQBW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910021563 chromium fluoride Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 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
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
-
- B01J35/394—
-
- 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
Abstract
The invention relates to a trans-fluorine-containing olefin isomerization catalyst, and a preparation method and application thereof. The catalyst comprises a carrier, a doping component and an active component, wherein the carrier is alumina, the doping component is composed of one or more of alkali metal and alkaline earth metal elements, the active component is composed of one or more of VIII group metal and IB group metal elements, when the catalyst is prepared, the catalyst carrier and the doping component are mixed to prepare a doping modified carrier, the active component is loaded on the doping modified carrier, and the mass ratio of the doping component metal elements to the catalyst carrier is 0.01-0.2: 1, the mass ratio of the active component metal elements to the doped modified carrier is 0.002-0.1: 1. the catalyst of the invention has high conversion rate and good stability in isomerization reaction, and can obviously reduce the generation of byproducts.
Description
Technical Field
The invention relates to an isomerization catalyst, in particular to a trans-fluorine-containing olefin isomerization catalyst.
Background
With increasing concerns about global warming, and the associated possible adverse climate effects, there is increasing concern in developed countries to reduce emissions of greenhouse gases. 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 values of refrigerants used as working fluids in almost all air conditioners and refrigerators from 2020. Some refrigeration media used today with GWP values in excess of 150 will be gradually 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.
Fourth generation HFO series refrigerant, e.g. cis-1, 3,3, 3-tetrafluoropropene (cis-HFO-1234ze, CF)3CH ═ CHF) has a double bond structure between carbon and carbon in a molecule, and has a very low Global Warming Potential (GWP) due to its high reactivity with hydroxyl radicals, and causes little burden on the environment, and is nonflammable and nontoxic. The cis-1, 3,3, 3-tetrafluoropropene has an ODP value of 0 and a GWP100The value is less than 1, the atmospheric service life is only 9 days, the air-conditioning system is considered to be one of the most potential alternative working mediums, and the air-conditioning system has a good application prospect in refrigeration cycles, heat pumps and Organic Rankine Cycles (ORC).
In recent years, most studies on the synthesis of HFO-1234ze have been conducted to obtain transHFO-1234 ze and a mixture of two isomers of cis HFO-1234ze, and isomerize cis HFO-1234ze therein to transHFO-1234 ze.
HONEYWELL has announced that HFO-1234ze is produced in large quantities, and has obtained a material with low Global Warming Potential (GWP) that can be used for aerosol propellant, foaming agent and refrigerant, and has the characteristics of energy saving, safety, no damage to ozone layer and extremely low global warming potential. Patent CN103483143A in the application of honeywell discloses a process for producing trans-1, 3,3, 3-tetrafluoropropene, comprising: (a) dehydrofluorinating 1,1,1,3, 3-pentafluoropropane to obtain a product containing cis-1, 3,3, 3-tetrafluoropropene, trans-1, 3,3, 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, 3,3, 3-tetrafluoropropene to trans-1, 3,3, 3-tetrafluoropropene; and (d) recovering the trans-1, 3,3, 3-tetrafluoropropene.
Based on the reaction of taking 1,1,1,3, 3-pentafluoropropane as a raw material and carrying out gas phase dehydrofluorination to generate HFO-1234ze with cis-form and trans-form configurations, and further adopting gas phase isomerization to convert the cis-HFO-1234ze into the trans-HFO-1234 ze, a low-temperature ultrahigh-activity environment-friendly catalyst for synthesizing the trans-1, 3,3, 3-tetrafluoropropene by gas phase isomerization is disclosed in a patent CN109718814A applied by the Seian recent chemical research institute, and is characterized in that the catalyst component is M/MgF2Wherein the matrix MgF2Has rutile phase and nanoThe rice spherical structure and the specific surface area are more than 120m2High-stability MgF with excellent sintering resistance at 500 DEG C2The active component M is selected from Co3+、Ni2+、Fe3+、Zn2+、La3+、Al3+、Ga3+、Mn4+、Cu2+Wherein the mass of M accounts for 5 to 20 percent of the total mass of the catalyst.
Patent CN106946647B of Shanxi's extended oil application discloses a method for preparing trans-1, 3,3, 3-tetrafluoropropene by mixture normal temperature isomerization, the method firstly carries out dehydrohalogenation reaction and then carries out isomerization reaction, the method takes the mixture of pentafluoropropane and tetrafluoro-chloropropane as raw materials, anhydrous hydrogen fluoride is introduced, and gas phase dehydrohalogenation reaction of dehydrofluorination and hydrogen chloride is carried out in a first reactor; and (2) introducing the mixture obtained by the reaction in the first reactor into a second reactor, carrying out gas phase isomerization reaction by using chromium fluoride as a catalyst at normal temperature and normal pressure, and then separating pentafluoropropane, tetrafluoromonochlorohydrin, hydrogen fluoride, hydrogen chloride and cis-1, 3,3, 3-tetrafluoropropene in the reaction product to obtain a purified product, namely trans-1, 3,3, 3-tetrafluoropropene.
cis-HFO-1234ze is rarely produced in the prior art, however, the physical and chemical properties of cis-HFO-1234ze are different from those of trans-HFO-1234 ze, the boiling point of cis-HFO-1234ze is 9 ℃, the boiling point of trans-HFO-1234 ze is-19 ℃, and cis-HFO-1234ze has more excellent use effect in some applications.
In the prior art, when transHFO-1234 ze is produced by isomerization, metal fluorides are generally used as isomerization catalysts. However, the use of metal fluorides as catalysts for the isomerization of transHFO-1234 ze to cis HFO-1234ze produces more by-products and severe carbon deposition.
WO2019047447A1 discloses alumina-supported chromium and magnesium as isomerization catalysts, but it catalyzes the isomerization of cis-1-chloro-3, 3, 3-trifluoropropene, is not suitable for catalyzing the isomerization of transHFO-1234 ze, and the chromium used is toxic.
Many cis-fluoro olefins have excellent properties, such as cis-HCFO-1233 zd, cis-HFO-1225 ye, etc., have very excellent thermal physical properties, the atmospheric lifetime is obviously shorter than HFCs refrigerant, and it is very environment-friendly, and the existing methods for preparing cis-HCFO-1233 zd, cis-HFO-1225 ye, etc. by direct fluorination, coupling reaction, etc. all have the disadvantages of low product selectivity, etc. The preparation difficulty of the cis-fluorine-containing olefin is larger, and the preparation of the cis-fluorine-containing olefin by carrying out isomerization reaction on the trans-fluorine-containing olefin under the action of an isomerization catalyst is a breakthrough of the preparation method.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a catalyst with good activity, high selectivity and carbon deposition resistance, which has high conversion rate and good stability in trans-fluorine-containing olefin isomerization reaction, and can obviously reduce the generation of byproducts, thereby simplifying the process flow of industrial amplification cycle process, reducing the energy consumption of product purification step and improving the product purity.
The trans-fluorine-containing olefin isomerization catalyst can be used for isomerizing trans-fluorine-containing olefin into cis-fluorine-containing olefin. Trans-fluoroolefins include transHFO-1234 ze, transHFO-1225 ye, transHCFO-1224 yd, transHCFO-1233 zd, and the like. The cis-fluoro olefin obtained by the isomerization reaction is cis-HFO-1234ze, cis-HFO-1225 ye, cis-HCFO-1224 yd, cis-HCFO-1233 zd and the like.
Applicants have found that catalysts with strong Lewis acidity have higher reactivity and high conversion of trans-fluorinated olefins, but also produce more by-products. Taking transHFO-1234 ze as an example, the by-product HFC-245fa of the isomerization reaction is close to the boiling point of the target product cis HFO-1234ze, is an azeotrope-like substance and is difficult to separate. With catalysts having weak Lewis acidity, the amount of by-products formed during the reaction is somewhat lower, but the reaction conversion decreases. In addition, the strong L acid catalyst was found to have severe carbon deposition after reaction, while the weak L acid catalyst did not have significant carbon deposition.
Applicants believe that strong L acid sites on the catalyst initiate the dehydrofluorination of trans fluorine-containing olefins. For example, dehydrofluorination of HFO-1234ze to produce 3,3, 3-trifluoropropyne and HF, which is addition reacted with HFO-1234ze to give HFC-245 fa. Meanwhile, the strong L acid site is also one of the main active sites for initiating the carbon deposition reaction.
Therefore, the catalyst needs to be adjusted to a proper L acid strength, so that the generation of byproducts is reduced and the conversion rate of trans fluorine-containing olefin is improved. The suitable L acid strength catalyst can also obviously reduce the formation of carbon deposition, and is beneficial to improving the stability of the catalyst.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a trans-fluorine-containing olefin isomerization catalyst comprises a carrier, a doping component and an active component, wherein the carrier is alumina, the doping component is composed of one or more of alkali metal and alkaline earth metal elements, the active component is composed of one or more of VIII group metal and IB group metal elements, when the catalyst is prepared, the catalyst carrier and the doping component are mixed to prepare a doping modified carrier, the doping modified carrier is loaded with the active component, and the mass ratio of the doping component metal elements to the catalyst carrier is 0.01-0.2: 1, the mass ratio of the active component metal elements to the doped modified carrier is 0.002-0.1: 1.
preferably, the mass ratio of the doping component metal element to the catalyst carrier is 0.02-0.1: 1, the mass ratio of the active component metal elements to the doping modified carrier is 0.005-0.05: 1.
the doping component is 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 an oxide, fluoride, hydroxide of Na, K, Mg, Ca, Sr or Ba, preferably an oxide.
The active component is preferably one or more of Fe, Co, Ni, Ru, Rh, Pd, Pt, Cu, Ag and Au, and further the active component is preferably Pd, Cu and/or Fe. Optionally, the active component is Pd. Optionally, the active component is Fe. In the preparation process of the catalyst, the raw materials of the active component are preferably chlorides, carbonates, nitrates, acetates and sulfates corresponding to the metals of the active component. When a chloride is selected, the catalyst precursor is reduced with a hydrogen atmosphere.
The catalyst is used for isomerizing the trans-fluorine-containing olefin to produce cis-fluorine-containing olefin.
The preparation method of the trans-fluorine-containing olefin isomerization catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) ball-milling and mixing the catalyst carrier and the doping component, uniformly stirring and mixing, and then tabletting or extruding for molding to obtain a doping modified carrier; the doping component has the function of adjusting the acidity and the acid amount of the carrier, particularly reducing the number of strong Lewis acid sites on the carrier, and can further reduce the generation amount of byproducts.
(2) Dissolving soluble salt of the active component in water, soaking the doped modified carrier in the same volume, and loading the active component on the doped modified carrier to obtain a catalyst precursor; the active component has the functions of improving the conversion rate of the catalyst to trans-fluorine-containing olefin isomerization reaction, realizing the fracture of pi bonds in double bonds in fluorine-containing olefin, and triggering the spatial rotation of C-C bonds, thereby realizing isomerization.
(3) Roasting the catalyst precursor to prepare the catalyst;
when the step (2) is immersed in the same volume, the temperature is 10-80 ℃ and the time is 1-24 hours, and the drying is carried out for 6-24 hours at the temperature of 105-120 ℃ after the immersion.
In the step (3), the roasting is carried out at the temperature of 150 ℃ and 250 ℃ for 1-3h, then the temperature is raised to 400 ℃ and 600 ℃ and the roasting is carried out for 1-5 h.
The support of the present invention is preferably alpha-Al2O3Or contains theta-Al2O3And alpha-Al2O3Alumina in mixed crystal phases. More preferably, the carrier of the present invention is obtained by calcining aluminum isopropoxide as an aluminum source.
α-Al2O3The preparation process of (a) may comprise the steps of:
adding aluminum isopropoxide into ethylene glycol to prepare an aluminum solution with the aluminum content of 0.5-2mol/L, dropwise adding a nitric acid solution into the solution until the pH value of the solution is 2-4, slowly heating the solution to 70-90 ℃, and keeping the temperature until the solution gradually becomes viscous; then the gel-like material is dried at the temperature of 110-130 ℃, the temperature is programmed to 1100-1300 ℃ after drying, and the gel-like material is roasted for 3-5 hours,obtaining the carrier alpha-Al2O3. Carrier alpha-Al2O3Has a specific surface area of 10-20m2(ii)/g, the average pore diameter is 20-30nm, and more than 80% of the pores have a diameter of 15-35 nm.
The temperature programming method can be as follows: firstly, the temperature is raised from room temperature to 550-700 ℃ at the temperature raising rate of 2-4 ℃/min, and the temperature is maintained at 550-700 ℃ for roasting for 2-4 hours, then the temperature is raised to 1100-1300 ℃ at the temperature raising rate of 3-5 ℃/min, and the temperature is maintained at 1100-1300 ℃ for roasting for 3-5 hours, so as to obtain the carrier alpha-Al2O3。
Containing theta-Al2O3And alpha-Al2O3The process for preparing mixed crystal phase alumina may include the steps of: adding aluminum isopropoxide into ethylene glycol to prepare an aluminum solution with the aluminum content of 0.5-2mol/L, then treating at 120-180 ℃ for 12-48 hours, centrifugally separating, washing a sample obtained by centrifugal separation with absolute ethyl alcohol, drying in air at 40-70 ℃ for 10-24 hours to obtain powder, and roasting the powder in an air atmosphere at 1000-1500 ℃ for 1-5 hours to obtain the product containing theta-Al2O3And alpha-Al2O3A catalyst support of mixed crystal phases. Containing theta-Al2O3And alpha-Al2O3The specific surface area of the catalyst carrier of the mixed crystal phase is 10-20m2(ii)/g, the average pore diameter is 20-30nm, and more than 80% of the pores have a diameter of 15-35 nm. Preferably, 90% or more of the pores have a diameter of 15 to 35 nm.
Prepared by the invention and containing theta-Al2O3And alpha-Al2O3Of mixed-phase alumina, alpha-Al2O3The content of (A) is 70-95%, theta-Al2O3The content of (A) is 5-30%, alpha-Al2O3And theta-Al2O3The content ratio of (A) is 5-15: 1.
the surface of the catalyst carrier has few acid-base centers, and is further combined with a doping component, so that the number of strong Lewis acid sites on the carrier is further reduced. After the active component is loaded, the catalyst has very proper acid strength, and the metal-acid synergistic effect is realized. By selecting the types and the contents of the components of the catalyst and combining the preparation process of the catalyst, the obtained catalyst has high conversion rate, good stability and strong anti-carbon deposition capability in the gas phase isomerization reaction of the trans-fluorine-containing olefin, the side reaction is obviously reduced, and the generation of by-products is obviously reduced.
The preparation process of the catalyst provided by the invention has the advantages that the acidity of the carrier is lower, the acid amount is more uniform, the loading of the active component is uniform, the combination of the active component and the carrier is more stable, the metal and the acidity are better cooperated, the prepared catalyst has higher reaction activity, fewer byproducts and less carbon deposition, and the long-term stability of the catalyst is better.
Taking the isomerization reaction of transHFO-1234 ze as an example, the main process for producing cis HFO-1234ze by isomerizing transHFO-1234 ze is as follows:
main reaction:
side reaction:
the catalyst has excellent performance, overcomes the problem that the reaction conversion rate and the byproduct generation amount cannot be controlled simultaneously, ensures that the byproducts are hardly generated while the reaction conversion rate and the catalytic activity are high, simplifies the process flow of the industrial amplification cycle process, and reduces the energy consumption of the product purification step. Meanwhile, the catalyst has stable performance and good anti-carbon deposition performance, the surface of the catalyst still has no obvious change even if the catalyst reacts at the high temperature of 450 ℃, the carbon deposition is less after the reaction, and the problem of inactivation caused by easy carbon deposition of the catalyst is avoided.
The catalyst of the invention produces almost no byproduct HF and HFC-245fa in the process of producing cis HFO-1234ze by isomerizing trans HFO-1234 ze. At the reaction temperature of 350 ℃ and the space velocity of 300h-1The pressure is 0.1MPa, the content of HFC-245fa in the organic matters of the reaction products can still be kept below 0.01 percent even to be 0 after the reaction is carried out for 10 hours, and the organic matters of the reaction productsThe cis-HFO-1234ze content can still be kept above 19%, even above 20%.
Detailed Description
The following specific examples further illustrate the invention. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
First, catalyst preparation
Example 1: alpha-Al2O3Preparation of
Weighing 204.3 g of aluminum isopropoxide, placing the aluminum isopropoxide in a polytetrafluoroethylene beaker, adding 1L of ethylene glycol solvent, and uniformly dispersing the aluminum isopropoxide in the polytetrafluoroethylene beaker by magnetic stirring; dropwise adding a nitric acid solution into the solution until the pH value of the solution is 2, and continuously stirring; slowly heating the solution to 80 ℃ and maintaining the temperature until the solution becomes gradually viscous; the gel-like material was then transferred to a stainless steel tray and dried in an oven at 120 ℃. The dried material is heated to 650 ℃ from room temperature by a temperature-raising rate of 3 ℃/min in a box-type furnace, is kept at 650 ℃ for roasting for 3 hours, is heated to 1200 ℃ by a temperature-raising rate of 3 ℃/min, is kept at 1200 ℃ for roasting for 3 hours, and the carrier alpha-Al is obtained2O3Specific surface area 15.53m2(ii)/g, the average pore diameter is 24.2nm, and the pore diameter of more than 88% is 15-35 nm.
Example 2: containing theta-Al2O3And alpha-Al2O3Preparation of mixed crystal phase alumina
Adding aluminum isopropoxide into ethylene glycol to prepare a solution with the aluminum content of 1.0mol/L, then treating at 150 ℃ for 24 hours, centrifugally separating, washing a sample obtained by centrifugal separation 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 the product containing theta-Al2O3And alpha-Al2O3A catalyst carrier in the crystal phase, the catalyst carrier having a specific surface area of 15.3m2(ii)/g, the average pore diameter is 23.3nm, and more than 92% of the pores have a diameter of 15-35nm, wherein the alpha-Al2O3The content of theta-Al is 85 percent2O3The content is 15%.
Example 3: 2% Fe/20% SrO-self-made alpha-Al2O3
The SrO and the catalyst carrier prepared in the example 1 are ball-milled and mixed according to the required proportion, stirred and mixed evenly, then the mixture is tableted or extruded to form a doped modified carrier, and the required amount of Fe (NO) is weighed3)3·9H2Dissolving O in a certain amount of water, and dropwise adding 20 percent SrO-self-made alpha-Al doped with a modified carrier2O3Soaking at 60 ℃ for 18h, and drying at 105 ℃ for 6h to obtain a catalyst precursor 2% Fe/Sr-self-made alpha-Al2O3。
The catalyst precursor is placed in an Incan alloy tubular reactor with the inner diameter of 1 inch and the length of 90cm, nitrogen is introduced into the Incan alloy tubular reactor for 100mL/min, the mixture is roasted for 2 hours at the temperature of 200 ℃, then the temperature is raised to 500 ℃, and the mixture is roasted for 3 hours to prepare the fluorine-containing olefin isomerization catalyst.
Example 4: 2% Fe/20% SrO-contains theta-Al2O3And alpha-Al2O3Mixed crystal phase alumina
The same procedure as in example 3, except that the catalyst was 2% Fe/20% SrO-containing theta-Al2O3And alpha-Al2O3Alumina of mixed crystal phase containing theta-Al2O3And alpha-Al2O3Mixed phase alumina was prepared by example 2.
Example 5: 2% Fe/20% SrO-commercially available alpha-Al2O3
Same procedure as in example 3, except that commercially available α -Al was used2O3Replace self-made alpha-Al2O3The catalyst prepared was 2% Fe/20% SrO-commercially available alpha-Al2O3(aladdin,99.99％)。
Example 6: 1 Pd%/10% MgO-self-made alpha-Al 2O3
The same operation as in example 3, except that the catalyst was 1 Pd%/10% MgO-self-made α -Al2O3Self-made alpha-Al2O3Prepared by example 1.
Comparative example 1: 2% Fe/commercial alpha-Al2O3
Same as in example 3The same operation is carried out, except that no doping component is added into the carrier, the active component is directly loaded on the carrier, and the catalyst 2% Fe/commercial alpha-Al is prepared2O3。
Comparative example 2: 1% Pd/C
The 1% Pd/C catalyst is commercially available.
Second, testing the application performance of the catalyst
Test example 1:
5mL of the trans-fluoroalkene isomerization catalyst in the above examples and comparative examples was charged in a tubular reactor made of Incar alloy having an inner diameter of 1/2 inches and a length of 40cm, and transHFO-1234 ze was introduced at a reaction temperature of 350 ℃ at a space velocity of 300 hours-1And the pressure is 0.1MPa, after the reaction is carried out for 10 hours, the reaction product is washed by water and alkali, organic matters are obtained by separation, and after drying and dewatering, the composition of the organic matters is analyzed by gas chromatography, and the result is shown in Table 1.
TABLE 1
Test example 2:
5mL of the trans-fluorinated olefin isomerization catalyst of example 4 was charged in a tubular reactor made of Incar alloy having an inner diameter of 1/2 inches and a length of 40cm, and trans-1-chloro-2, 3,3, 3-tetrafluoropropene was introduced thereinto at a reaction temperature of 350 ℃ and a space velocity of 250 hours-1And the pressure is 0.1MPa, after the reaction is carried out for 10 hours, the reaction product is washed by water and alkali, an organic matter is obtained by separation, and after drying and dewatering, the composition of the organic matter is analyzed by gas chromatography, so that the conversion rate of the isomerization of the trans-1-chloro-2, 3,3, 3-tetrafluoropropene into the cis-1-chloro-2, 3,3, 3-tetrafluoropropene is 15.56%.
Claims (10)
1. A trans-fluorine-containing olefin isomerization catalyst is characterized in that: the catalyst comprises a carrier, a doping component and an active component, wherein the carrier is alumina, the doping component is composed of one or more of alkali metal and alkaline earth metal elements, the active component is composed of one or more of VIII group metal and IB group metal elements, when the catalyst is prepared, the catalyst carrier and the doping component are mixed to prepare a doping modified carrier, the active component is loaded on the doping modified carrier, and the mass ratio of the doping component metal elements to the catalyst carrier is 0.01-0.2: 1, the mass ratio of the active component metal elements to the doped modified carrier is 0.002-0.1: 1.
2. the catalyst of claim 1, wherein: the doped component is one or more of Na, K, Mg, Ca, Sr or Ba.
3. The catalyst of claim 1, wherein: the active component is one or more of Fe, Co, Ni, Ru, Rh, Pd, Pt, Cu, Ag and Au.
4. The catalyst of claim 1, wherein: the catalyst is used for isomerizing the trans-fluorine-containing olefin to produce cis-fluorine-containing olefin.
5. A preparation method of a trans-fluorine-containing olefin isomerization catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) ball-milling and mixing the catalyst carrier and the doping component, uniformly stirring and mixing, and then tabletting or extruding for molding to obtain a doping modified carrier;
(2) dissolving soluble salt of the active component in water, soaking the doped modified carrier in the same volume, and loading the active component on the doped modified carrier to obtain a catalyst precursor;
(3) roasting the catalyst precursor to prepare the catalyst;
wherein: the carrier is alumina, the doping component is composed of one or more of alkali metals and alkaline earth metals, the active component is composed of one or more of VIII group metals and IB group metals, and the mass ratio of the doping component metal elements to the catalyst carrier is 0.01-0.2: 1, the mass ratio of the active component metal elements to the doped modified carrier is 0.002-0.1: 1.
6. the method of claim 5, wherein: the doped component is one or more of Na, K, Mg, Ca, Sr or Ba.
7. The method of claim 5, wherein: the active component is one or more of Fe, Co, Ni, Ru, Rh, Pd, Pt, Cu, Ag and Au.
8. The method of claim 5, wherein: when the step (2) is immersed in the same volume, the temperature is 10-80 ℃ and the time is 1-24 hours, and the drying is carried out for 6-24 hours at the temperature of 105-120 ℃ after the immersion.
9. The method of claim 5, wherein: in the step (3), the roasting is carried out at the temperature of 150 ℃ and 250 ℃ for 1-3h, then the temperature is raised to 400 ℃ and 600 ℃ and the roasting is carried out for 1-5 h.
10. Use of the catalyst according to any one of claims 1 to 4 or the catalyst prepared by the preparation method according to any one of claims 5 to 9 in isomerization of trans-fluorine-containing olefin, characterized in that the catalyst has high conversion rate and good stability in isomerization, and can significantly reduce the generation of by-products.
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