CN116328798B - Method for synthesizing trifluoroiodomethane by co-conversion iodination - Google Patents
Method for synthesizing trifluoroiodomethane by co-conversion iodination Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000006192 iodination reaction Methods 0.000 title claims abstract description 16
- VPAYJEUHKVESSD-UHFFFAOYSA-N trifluoroiodomethane Chemical compound FC(F)(F)I VPAYJEUHKVESSD-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 230000026045 iodination Effects 0.000 title claims abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 239000007789 gas Substances 0.000 claims abstract description 32
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 25
- 239000011630 iodine Substances 0.000 claims abstract description 18
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- -1 alkali metal salt Chemical class 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 229910052596 spinel Inorganic materials 0.000 claims description 8
- 239000011029 spinel Substances 0.000 claims description 8
- 150000001735 carboxylic acids Chemical class 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000010574 gas phase reaction Methods 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- LRMSQVBRUNSOJL-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)F LRMSQVBRUNSOJL-UHFFFAOYSA-N 0.000 claims description 3
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 159000000009 barium salts Chemical class 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical class [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 229910052701 rubidium Inorganic materials 0.000 claims 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 229910052712 strontium Inorganic materials 0.000 claims 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000006114 decarboxylation reaction Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 150000004694 iodide salts Chemical class 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- 238000006356 dehydrogenation reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 11
- 239000000376 reactant Substances 0.000 description 10
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- GTLACDSXYULKMZ-UHFFFAOYSA-N pentafluoroethane Chemical compound FC(F)C(F)(F)F GTLACDSXYULKMZ-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000010812 external standard method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001351 alkyl iodides Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- AYTAKQFHWFYBMA-UHFFFAOYSA-N chromium(IV) oxide Inorganic materials O=[Cr]=O AYTAKQFHWFYBMA-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical group 0.000 description 1
- 159000000003 magnesium salts Chemical group 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 150000003297 rubidium Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 159000000008 strontium salts Chemical class 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011592 zinc chloride Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
-
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of organic synthesis, and relates to a method for synthesizing trifluoroiodomethane by co-conversion iodination. The catalyst is prepared by reacting carboxylic acid, trifluoromethane and iodine simple substance in a catalyst, oxygen or mixed gas of oxygen and inert gas; the catalyst is an AB type bifunctional catalyst supported on a carrier, and can catalyze decarboxylation iodination reaction and dehydrogenation iodination reaction. The single pass conversion rate of the invention based on iodine atom reaches more than 80%, and other iodides with high added value can be flexibly produced by changing the raw materials; the method has the advantages of low raw material cost, convenient source, low reaction temperature and long service life of the catalyst; and the product is simple to separate and purify, the synthesis process is safe, and the method is suitable for large-scale industrial production.
Description
Technical Field
The invention belongs to the field of organic chemical synthesis, and particularly relates to a method for synthesizing trifluoroiodomethane by co-conversion iodination.
Background
The trifluoroiodomethane (CF 3 I) is a novel clean and efficient gas extinguishing agent, an environment-friendly semiconductor etchant, insulating gas, a refrigerant, a foaming agent, a trifluoromethylating agent and the like, and has wide application prospect.
At present, the main production method of CF 3 I is a gas-phase iodination method which takes elemental iodine (I 2) as an iodine source, and the cost of I 2 almost accounts for more than 90% of the cost of raw materials, so the conversion rate in terms of iodine atoms is a main index for evaluating the advancement of the production method of CF 3 I. The gas phase iodination method mainly comprises the following steps of:
The method takes trifluoroacetyl halide (CF 3 COX, X=F, cl, br), hydrogen (H 2) and I 2 as raw materials and palladium as a catalyst, and the method synthesizes H 2 and I 2 into Hydrogen Iodide (HI) and then reacts with the CF 3 COX, so that the conversion rate of the reaction is lower because of the difficulty in HI generation, and meanwhile, a noble metal catalyst is used, so that the cost is higher.
The method takes trifluoroacetic acid (CF 3 COOH) and I 2 as raw materials, and carries out decarboxylation iodination under the action of a catalyst to synthesize CF 3 I, and meanwhile, the yield of the byproduct HI with equal quantity is only about 35 percent based on iodine atoms, and then an HI oxidation device is added to recycle I 2, so that the device investment is increased.
Takes trifluoromethane (CHF 3)、I2 and/or oxygen (O 2) as raw materials to catalyze and synthesize CF 3 I at 550 ℃,The Gibbs free energy of the reaction is large, the conversion rate calculated by iodine atoms is only about 26%, a large amount of iodine simple substances need to be recycled, meanwhile, the catalyst is fast to deactivate due to high reaction temperature, the production cost is high, and the conversion rate of the reaction is extremely low when the reaction temperature is below 450 ℃.
The conversion rate of the traditional gas-phase iodination method based on iodine atoms is generally not more than 40%, a large amount of iodine simple substances need to be recycled, and the energy consumption and the raw material waste are increased; in addition, the iodine simple substance of partial method is difficult to recycle, the reaction temperature is high, the service life of the catalyst is short, or the noble metal catalyst is used, the production cost is high, and the industrialization is not facilitated.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for synthesizing trifluoroiodomethane, which has the advantages of high iodine conversion rate, long catalyst life and low production cost.
In order to achieve the above object, the method for synthesizing trifluoroiodomethane by co-conversion iodination provided by the invention comprises the following steps:
Reactant streams of carboxylic acid (RCOOH), trifluoromethane (CHF 3), and elemental iodine (I 2), oxygen (O 2), or a mixture of oxygen and inert gases; and reacting the reactant stream in the presence of a catalyst to produce a product stream comprising trifluoroiodomethane.
Reaction of RCOOH and I 2 in the reactant stream produces in situ an alkyl iodide (RI), hydrogen Iodide (HI), and carbon dioxide (CO 2) according to reaction formula 1 below:
CHF 3 and O 2 in the reactant stream with HI generated in situ produce trifluoroiodomethane (CF 3 I), hydrogen Fluoride (HF), carbon dioxide (CO 2) and water (H 2 O) according to the following equations 2-4:
Since gibbs free energy of reaction of CHF 3 with HI is smaller than that of CHF 3 with I 2, equations 2 to 4 are more likely to occur and the conversion is higher. Meanwhile, HI is continuously consumed, so that the reaction formula 1 is continuously moved to the right, and the conversion rate of iodine atoms can be greatly improved by the interaction of the reaction formula 1 and the reaction formulas 2-4.
Further, the carboxylic acid (RCOOH) is selected from: carboxylic acids of the general formula RCOOH such as trifluoroacetic acid, pentafluoropropionic acid, acetic acid, propionic acid, naphthenic acid, and combinations thereof.
The molar ratio of the carboxylic acid to the trifluoromethane to the iodine simple substance to the oxygen is as follows: 1:0.5 to 10:0.2 to 2:0.1 to 1.
The gas phase reaction conditions are as follows: the reaction pressure is 0.05-0.5 MPa, the reaction temperature is 300-600 ℃, and the reaction temperature is preferably 350-550 ℃.
Further, the catalyst is a bifunctional catalyst consisting of at least one of an alkali metal salt or an alkaline earth metal salt and at least one of a transition metal salt, which are supported on a carrier; wherein,
The alkali metal salt is lithium salt, sodium salt, potassium salt, rubidium salt or cesium salt, the alkaline earth metal salt is magnesium salt, calcium salt, strontium salt or barium salt, and the transition metal salt is ferric salt, cupric salt or zinc salt;
and, the molar ratio of the alkali metal salt or alkaline earth metal salt to the transition metal salt is 1:0.5 to 2;
the weight ratio of the alkali metal salt or alkaline earth metal salt and the transition metal salt to the carrier is 0.05-0.35: 1.
Still further, the support is a chromium-based perovskite, chromium-based spinel, aluminum-based spinel, activated carbon, graphite, siC, and combinations thereof; wherein,
The chromium-based perovskite is one or more of La xA1-xCrO3-yF2y or Y xA1-xCrO3-yF2y, x is 0-1, Y is 0-3, A is a metal atom Mg, ca, sr, ba;
The chromium-based spinel is a compound with a chemical formula of BCr 2O4-zF2z, the aluminum-based spinel is a compound with a chemical formula of BAl 2O4-zF2z, z is 0-4, and B is one or more of metal atoms Mg, fe, zn, mn, co, cu, ti, cd, ga, ni.
Further, the contact time of the reactant stream with the catalyst is 0.1 to 120 seconds.
Moreover, the reactions can be carried out simultaneously in the same catalyst and the same reactor, or can be carried out under different catalysts in two reactors connected in series.
Compared with the prior art, the method for synthesizing trifluoroiodomethane by co-conversion iodination has the following excellent effects:
1. The single pass conversion rate of the invention based on iodine atom reaches more than 80%, and other iodides with high added value can be flexibly produced by changing the raw materials.
2. The invention has cheap raw materials and convenient sources; the reaction temperature is low, and the service life of the catalyst is long; the product is simple to separate and purify; the synthesis process is safe and suitable for large-scale industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a GCMS detection spectrum of trifluoroiodomethane product.
FIG. 2 is a graph showing the conversion in terms of iodine atoms over time.
Detailed Description
The following description of embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The embodiment of the invention discloses a method for synthesizing trifluoroiodomethane by co-conversion iodination.
The present invention will be further specifically illustrated by the following examples, which are not to be construed as limiting the invention, but rather as falling within the scope of the present invention, for some non-essential modifications and adaptations of the invention that are apparent to those skilled in the art based on the foregoing disclosure.
The technical scheme of the invention will be further described below with reference to specific embodiments.
Example 1
Liquid trifluoroacetic acid with the flow rate of 5.0ml/h and solid I 2 with the flow rate of 15.0g/h are mixed and sent into an evaporator, after being evaporated into a gas state, the mixture is mixed with CHF 3 with the flow rate of 22.0sccm and O 2 with the flow rate of 6.0sccm, a fixed bed reactor filled with 30ml of KF-CuI/La 0.6Ca0.4CrO2F2 catalyst is introduced, the reaction temperature is 400 ℃, the contact time of reactant flow and the catalyst is 10 seconds, the reacted gas is subjected to iodine removal, acid gas removal and gas drying, and then is detected by a gas inlet and gas chromatograph, the actual content of the product is calculated by adopting an external standard method, the conversion rate and the selectivity are determined through material balance of the inlet and outlet reactor, and the change condition of the conversion rate and the selectivity with the time is examined.
Experimental results: the reacted gas mainly comprises unreacted iodine simple substance, hydrogen fluoride, water, pentafluoroethane, trifluoroiodomethane, unreacted trifluoromethane and carbon dioxide, the boiling point difference between products is large, the products with the purity of more than 99% can be obtained through conventional unit operations such as cooling, liquid separation, absorption, drying, rectification and the like according to the boiling point and the acid-base difference of the products, the unreacted iodine simple substance and the trifluoromethane can be recycled through GCMS detection (see figure 1). The conversion per pass in terms of iodine atom was 90.1%, the selectivity of CF 3 I was 96.7%, and the selectivity of pentafluoroethane was 3.3%. Since the reaction temperature of the technology is greatly reduced, the service life of the catalyst is prolonged at a lower temperature, and in the embodiment, the service life of the catalyst is more than 300 hours (see figure 2).
Example 2
Liquid pentafluoropropionic acid with the flow rate of 10.0ml/h and solid I 2 with the flow rate of 15.0g/h are mixed and sent into an evaporator, after being evaporated into gas, the gas is mixed with CHF 3 with the flow rate of 45.0sccm and O 2 with the flow rate of 6.0sccm, the gas is introduced into a fixed bed reactor filled with 30ml of Na 2CO3-FeCl2/ZnCr2O3F2 catalyst, the reaction temperature is 450 ℃, the contact time of a reactant flow and the catalyst is 20s, the reacted gas is subjected to iodine removal, acid gas removal and gas phase chromatograph detection after drying, the actual content of a product is calculated by adopting an external standard method, and the conversion rate and the selectivity are determined by material balance of the inlet and outlet reactor.
Experimental results: the conversion per pass in terms of iodine atom was 95.6%, the selectivity of CF 3 I was 65.7%, and the selectivity of pentafluoroethane was 34.3%.
Example 3
Liquid naphthenic acid with the flow rate of 10.0ml/h and solid I 2 with the flow rate of 15.0g/h are mixed and sent into an evaporator, the mixture is evaporated into gas, CHF 3 with the flow rate of 67.0sccm and O 2 with the flow rate of 11.0sccm are mixed, a fixed bed reactor filled with 45ml of RbNO 3-ZnCl2/MgAl2O3F2 catalyst is introduced, the reaction temperature is 350 ℃, the contact time of the reactant flow and the catalyst is 30s, the iodine and acid removal gas of the reacted gas are removed, the gas is detected by an air inlet phase chromatograph after drying, the actual content of the product is calculated by an external standard method, and the conversion rate and the selectivity are determined by material balance of the inlet and outlet reactor.
Experimental results: the conversion per pass in terms of iodine atom was 82.3%, the selectivity to CF 3 I was 84.0%, the selectivity to pentafluoroethane was 2.9%, and the selectivity to iodocycloalkane was 13.1%.
Example 4
Liquid acetic acid with the flow rate of 7.0ml/h and solid I 2 with the flow rate of 15.0g/h are mixed and sent into an evaporator, the mixture is evaporated into a gas state and then mixed with CHF 3 with the flow rate of 90.0sccm and O 2 with the flow rate of 11.0sccm, a fixed bed reactor filled with 45ml of Mg (NO 3)2 -CuCl/activated carbon catalyst) is introduced, the reaction temperature is 450 ℃, the contact time of reactant flow and the catalyst is 60 seconds, the reacted gas is subjected to iodine removal, acid gas removal and gas intake after drying, the gas chromatograph is used for detection, the actual content of the product is calculated by adopting an external standard method, and the conversion rate and the selectivity are determined by material balance of the inlet and outlet reactor.
Experimental results: the conversion per pass in terms of iodine atom was 85.4%, the selectivity of CF 3 I was 62.1%, the selectivity of pentafluoroethane was 2.1%, and the selectivity of methyl iodide was 35.8%.
Example 5
Liquid propionic acid with the flow rate of 9.0ml/h and solid I 2 with the flow rate of 15.0g/h are mixed and fed into an evaporator, the mixture is evaporated into a gas state and then is mixed with CHF 3 with the flow rate of 67.0sccm and O 2 with the flow rate of 22.0sccm, a fixed bed reactor filled with 45mlBa (NO 3)2-FeCl3/SiC catalyst, the reaction temperature is 500 ℃, the contact time of the reactant flow and the catalyst is 90s, the iodine and acid gases of the reacted gas are removed, the gas is detected by a gas phase chromatograph after drying, the actual content of the product is calculated by an external standard method, and the conversion rate and the selectivity are determined by material balance of the inlet and outlet reactor.
Experimental results: the conversion per pass in terms of iodine atom was 87.9%, the selectivity of CF 3 I was 68.9%, the selectivity of pentafluoroethane was 2.4%, and the selectivity of iodoethane was 28.7%.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. The bifunctional catalyst is characterized in that the catalyst is an AB type bifunctional catalyst loaded on a carrier; wherein,
The molar ratio of A to B is 1: (0.5-2), and the weight ratio of AB to carrier is (0.05-0.35): 1, a step of;
and A is an alkali metal salt or alkaline earth metal salt; b is a transition metal salt;
the carrier is at least one of chromium-based perovskite, chromium-based spinel and aluminum-based spinel; wherein,
The chromium-based perovskite is a compound with a chemical formula of La xA1-xCrO3-yF2y or Y xA1-xCrO3-yF2y, x is 0-1, and Y is 0-3; a is a metal atom, at least one of Mg, ca, sr, ba;
the chromium-based spinel is a compound with a chemical formula of BCr 2O4-zF2z, the aluminum-based spinel is a compound with a chemical formula of BAl 2O4- zF2z, and z is 0-4; b is a metal atom, at least one of Mg, fe, zn, mn, co, cu, ti, cd, ga, ni.
2. The bifunctional catalyst of claim 1, wherein the alkali metal salt is a lithium, sodium, potassium, rubidium or cesium salt, the alkaline earth metal salt is a magnesium, calcium, strontium or barium salt, and the transition metal salt is an iron, copper or zinc salt.
3. A method for synthesizing trifluoroiodomethane by co-conversion iodination is characterized in that the method is obtained by gas phase reaction of carboxylic acid, trifluoromethane and iodine elementary substance in a catalyst, oxygen or a mixed gas of oxygen and inert gas; wherein,
The catalyst is a bifunctional catalyst as claimed in claim 1;
the carboxylic acid has a structural general formula of RCOOH and is at least one selected from trifluoroacetic acid, pentafluoropropionic acid, acetic acid, propionic acid and naphthenic acid;
and the molar ratio of the carboxylic acid to the trifluoromethane to the iodine simple substance to the oxygen is as follows: 1: (0.5-10): (0.2-2): (0.1-1).
4. A method for co-conversion iodination to trifluoroiodomethane according to claim 3, wherein said gas phase reaction conditions are: the reaction pressure is 0.05-0.5 MPa, and the reaction temperature is 300-600 ℃.
5. The method for synthesizing trifluoroiodomethane by co-conversion iodination according to claim 4, wherein the gas phase reaction temperature is 350-550 ℃ and the catalytic reaction contact time is 0.1-120 s.
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