GB2100729A - Production of acyl fluorides by carbonylation - Google Patents
Production of acyl fluorides by carbonylation Download PDFInfo
- Publication number
- GB2100729A GB2100729A GB08216304A GB8216304A GB2100729A GB 2100729 A GB2100729 A GB 2100729A GB 08216304 A GB08216304 A GB 08216304A GB 8216304 A GB8216304 A GB 8216304A GB 2100729 A GB2100729 A GB 2100729A
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- United Kingdom
- Prior art keywords
- organic compound
- carbon monoxide
- hydrogen fluoride
- propylene
- mole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000001265 acyl fluorides Chemical class 0.000 title abstract 2
- 238000005810 carbonylation reaction Methods 0.000 title description 6
- 230000006315 carbonylation Effects 0.000 title description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 78
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 58
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 32
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 32
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000012808 vapor phase Substances 0.000 claims abstract description 12
- -1 isobutyryl fluoride Chemical class 0.000 claims abstract description 9
- 150000001450 anions Chemical class 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 21
- 239000011541 reaction mixture Substances 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 11
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- WVRPFQGZHKZCEB-UHFFFAOYSA-N Isopropyl 2-methylpropanoate Chemical compound CC(C)OC(=O)C(C)C WVRPFQGZHKZCEB-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical compound CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 claims description 5
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 4
- 150000002222 fluorine compounds Chemical group 0.000 claims description 4
- 229940024423 isopropyl isobutyrate Drugs 0.000 claims description 4
- IJMWOMHMDSDKGK-UHFFFAOYSA-N Isopropyl propionate Chemical compound CCC(=O)OC(C)C IJMWOMHMDSDKGK-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- FSQOYWQCIXSBNP-UHFFFAOYSA-N 2-methylpropanoyl fluoride Chemical compound CC(C)C(F)=O FSQOYWQCIXSBNP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000047 product Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 8
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002895 organic esters Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-M isobutyrate Chemical compound CC(C)C([O-])=O KQNPFQTWMSNSAP-UHFFFAOYSA-M 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- IICQZTQZQSBHBY-UHFFFAOYSA-N non-2-ene Chemical group CCCCCCC=CC IICQZTQZQSBHBY-UHFFFAOYSA-N 0.000 description 1
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/38—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by addition to an unsaturated carbon-to-carbon bond
-
- 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
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
An acyl fluoride, e.g., isobutyryl fluoride, is formed by reacting carbon monoxide, an organic compound (e.g., propylene) and anhydrous hydrogen fluoride, in a liquid mixture while feeding the carbon monoxide and organic compound (e.g., propylene) into the liquid mixture's vapor phase which is maintained above the supercritical temperature of the vapor mixture at substantially the same rate as the carbon monoxide, organic compound (propylene) and anhydrous acid (hydrogen fluoride) react. The temperature is 40 to 90 DEG C and the pressure 109-340 bars. The final mole ratio of anhydrous hydrogen fluoride to organic compound in the reacting mixture is 1 to 100 moles of anhydrous hydrogen fluoride to 1 mole of organic compound and the mole ratio of carbon monoxide to organic compound is from 1 to 25 moles of carbon monoxide to 1 mole of organic compound.
Description
SPECIFICATION
Production of carboxylic acids and esters
This invention relates to the production of carboxylic acids and esters.
More particularly the invention relates to the liquid phase production of an acylium anion product (acylium fluoride), e.g., isobutyryl fluoride by feeding carbon monoxide and an organic compound described herein into the supercritical region above the liquid phase of a liquid mixture of carbon monoxide and anhydrous hydrogen fluoride acid to form the acylium anion product, e.g., isobutyryl fluoride.
The prior art such as U.S. Patents 3,167,585 and 3,703,549 as a whole stresses the requirement of an aqueous acid catalyst reaction medium for production of carboxylic acids from compounds having one or more double bonds. In these processes, serious irreversible polymerization occurs and the aqueous acid medium is corrosive so that expensive equipment is required.
For example, in the prior art, such as in U.S. Patent No. 2,831,877 (Koch), poor yields of acid fluorides are formed by reacting an olefin with carbon monoxide and anhydrous hydrogen fluoride in a dual phase reaction. The carbon monoxide being in the gaseous state and the olefin and hydrogen fluoride remaining in the liquid state. This frequently causes the olefin to dimerize or polymerize thus being taken out of the reaction, and requires separation from the products.
The prior art problems may be overcome by following the reaction conditions described herein to form the acylium anion products and their corresponding carboxylic acids or esters by the process described herein in substantially high yields.
Acylium anion products (acylium fluorides) (e.g., isobutyryl fluoride) are formed by reacting carbon monoxide an anhydrous hydrogen fluoride acid described herein (e.g., hydrogen fluoride) and an organic compound capable of adding carbon monoxide thereto described herein (e.g., propylene) in the liquid phase while feeding the carbon monoxide and the organic compound (e.g., propylene) into the vapor phase over the liquid reaction mixture at substantially the same rate as the carbon monoxide, organic compound and anhydrous hydrogen fluoride acid form the acylium anion product, while maintaining the temperature and pressure of the vapor phase of the mixture above the liquid such that the carbon monoxide is in a supercritical fluid phase and dissolves the organic compound, e.g. propylene, therein.
The reaction is conducted under conditions whereby the acylium anion products form in substantial yields. The acylium anion product can be separated and reacted with water to form carboxylic acid, e.g.
isobutyric acid, or with an alcohol to form a carboxylic ester, e.g. methyl isobutyrate, or the product mixture itself can be reacted with water to form carboxylic acid or with an alcohol to form the carboxylic ester.
The invention provides a novel process for producing acylium anion products (acylium fluorides) from carbon monoxide, an organic compound capable of adding carbon monoxide thereto described herein and an anhydrous acid described herein.
The carbon monoxide, anhydrous acid, and organic compound are reacted in a liquid mixture under conditions whereby acylium anion product forms in substantial yields; that is, with less than 10 percent formation of polymeric products or other undesirable side products. After the reaction has started, the carbon monoxide and the organic compound are fed into the vapor phase over the liquid reaction mixture at substantially the same rate (that is, fifteen (1 5), preferably ten (10) mole percent) as the carbon monoxide, organic compound, and anhydrous acid react to form the acylium anion product, e.g., isobutyryl fluoride. The temperature and pressure of the vapor phase of the mixture above the liquid mixture is maintained so that the carbon monoxide in the vapor phase of the mixture is in a supercritical fluid phase and the organic compound, e.g., propylene, dissolves therein.Preferably, the temperature and pressure is maintained at the point where the organic compound dissolves in the carbon monoxide supercritical fluid phase and both the carbon monoxide and organic compound e.g. propylene, transfers into the reaction mixture at the rate at which carbon monoxide, anhydrous acid, and organic compound react to form the acyiium anion product, thereby preventing side reactions such as polymerisation from occurring.
In one embodiment of the invention, the acylium anion product is separated from the reaction mixture, and then further reacted with water or an alcohol under conditions whereby the corresponding carboxylic acid or carboxylic ester forms.
In another embodiment of the invention, the product mixture which has the formed acylium anion product therein is further reacted with water or an alcohol under conditions whereby the corresponding carboxylic acid or carboxylic ester forms.
The carbon monoxide may be from any source, but must be substantially free from water so that an anhydrous reaction mixture is maintained. The carbon monoxide may be diluted with other substances such as hydrogen, propane, or nonreactive hydrocarbon which do not interfere with the reaction. For example, dry synthesis gas may be used as the source of carbon monoxide. It is preferred, however, that dry carbon monoxide itself be used.
Examples of organic compounds capable of reacting with carbon monoxide are organic esters described herein or olefins having at least one unsaturated bond capable of adding carbon monoxide thereto as described herein.
The organic esters are represented by the general formula
R is an alkyl group having up to twenty carbon atoms, such as methyl, ethyl, dodecyl, eicosanyl.
Preferably the alkyl group is methyl, ethyl, propyl, or isopropyl with isopropyl being the most preferred.
R' is an alkyl group having from two to twenty carbon atoms, such as ethyl, propyl, t-butyl, dodecyl eicosanyl. Preferably R' is ethyl or isopropyl, with isopropyl being the most preferred.
When an ester is used in the process described herein, any one of the esters mentioned herein may be used. It is however, preferable to use isopropyl isobutyrate (2-propanol 2-methyipropionate), ethyl isobutyrate (ethanol 2-methylpropionate), isopropyl propionate (2-propanol propionate) or ethyl propionate (ethanol propionate) and it is especially preferred to use isopropyl isobutyrate (2-propanol 2-methylpropionate).
Preferred examples of organic compounds having at least one unsaturated bond capable of adding carbon monoxide thereto which may be used in the process described herein are: olefins having at least one double bond capable of adding carbon monoxide thereto and having up to twenty carbon atoms, examples of which are ethylene, propylene, butenes, 1 ,3-butadiene, dodecene, 1 -hexylpropylene. The olefins may be substituted with substituents which do not interfere in the process described herein.
Ethylene, propylene, isobutene, 1-butene, 2-butene, and 1,3-butadiene are preferred olefins; ethylene and propylene are highly preferred, and propylene is especially preferred.
When the olefin has additional double bonds, such as 1,3-butadiene, 1,4-pentadiene additional reaction capability exists to form di- or multi-acylium anion products. For example, 1 ,3-butadiene can form
which reacts with water to form 1 ,6-hexandioic acid,
or an alcohol such as methanol to form dimethyl 1 ,6-hexanediate,
All of the organic compounds described herein may be used in the process described herein; however, it is especially preferred that propylene be used.
The anhydrous acid for the process described is anhydrous hydrogen fluoride. It is possible to use anhydrous hydrogen fluoride acids which have small amounts of water therein, less than 0.02 weight percent, provided an anhydrous acid system is maintained.
The reaction of carbon monoxide, with an organic compound described herein and an anhydrous hydrogen fluoride acid described herein, can occur at temperatures from forty degrees Centigrade (400C) to seventy degrees Centigrade (700 C), but preferably it is at about fifty degrees Centigrade (500C). The pressure at which the reaction is conducted can vary from 109 bars (1,600 psia) to 340 bars (5,000 psia), and preferably it is from 1 69 bars (2,500 psia) to 1 97 bars (2,900 psia). The pressure and temperature are increased as required for the solubility of carbon monoxide in the anhydrous acid as well as to maintain a supercritical fluid phase of carbon monoxide in which the organic compound is dissolved above the liquid phase of the reacting medium.Note the term "vapor" as used herein is equivalent to "gaseous" or "gas".
The final mole ratio of anhydrous acid to the organic compound described herein in the reacting mixture should be from 1:1 to 100:1, but generally it is from 10:1 to 20:1 and preferably about 12:1 to 16:1. The mole ratio of carbon monoxide to the organic compound is from 1:1 to 25:1 or higher, but preferably it is from 15:1 to 25:1.
The carbon monoxide and anhydrous acid, e.g., anhydrous hydrogen fluoride should be thoroughly mixed to form a single liquid phase, prior to the feeding of the organic compound described herein, e.g., propylene, and carbon monoxide as required into the reactor. The organic compound itself can be mixed and diluted with carbon monoxide or inert diluents, e.g., propane, prior to addition to the reactor.
It is very important that the addition of carbon monoxide and the organic compound to the reactor be at substantially the same rate as carbon monoxide, organic compound and anhydrous acid react; that is, the addition rate should be within fifteen (1 5) but preferably ten (10) mole percent of the rate at which they are reacting to form the acylium anion product. If the rate of addition of carbon monoxide is faster or greater than that of the organic compound, no adverse effect will generally occur; but if it is slower than the organic compound, then the yield of acylium anion product, e.g., isobutyryl fluoride, will decrease, generally because of adverse side reactions such as polymerization of the double bond of the unsaturated compound, and/or carbonylation of oligomers.Thus, it is very important that the organic compound be added at substantially the same rate as it is being used up, or if the carbon monoxide addition rate slows, then the organic compound addition rate must also slow.
The proper rate of addition is readily controlled by sampling the amount of the acylium anion product, e.g., isobutyryl fluoride, being formed under the given reaction conditions, or the amount of carbon monoxide being used, and then increasing or decreasing the addition rate in accordance with the rate of formation of the acylium anion, or rate at which carbon monoxide is used.
It is important that the liquid phase reaction mixture be stirred or agitated as rapidly as possible to ensure adequate mixing, dilution of the organic compound being added, and transfer of the carbon monoxide and organic compound from the vapor or gas phase into the liquid phase.
The reaction of the acylium anion product, e.g., isobutyryl fluoride, with water or alcohol can occur at temperatures from zero degree Centigrade (OOC) to one hundred fifty degrees Centigrade (1 500C) and at pressures from 14.7 psia to 5,000 psia, but normally it occurs at temperatures from forty degrees
Centigrade (400C) to seventy degrees Centigrade (700 C) and pressures at 500 psia to 3,000 psia. The temperature and pressure being set to avoid the decomposition of the intended products.
In one embodiment, the reaction mixture itself after the carbonylation is complete is reacted with water or an alcohol. The total amount of water or alcohol may be injected into the reaction mixture after the carbonylation reaction is complete. Since the hydrolysis or esterification is exothermic, cooling may be required. Then the carboxylic acid or esters are separated.
In another embodiment, after the carbonylation reaction is complete, from one (1) to one hundred (100) percent of the stable acylium anion product formed is separated from the product mixture.
Preferably, from eighty (80) to one hundred (100) percent of the stable acylium anion product is separated, and the remaining product mixture is recycled for reacting as in Steps (a) and (b) described herein.
In another embodiment, from one (1) to one hundred (100) percent (preferably from eighty (80) to one hundred (100) percent), of the anhydrous acid is separated from the product mixture and recycled back for further mixing with carbon monoxide in the liquid phase.
The separations described herein can be by any of the known methods of separation, such as distillation or extraction.
The process described herein can be carried out in any suitable reactor, such as a continuous stirred tank reactor (CSTR).
It is extremely important in the present invention to maintain the proper amount of carbon monoxide in solution. The amount of carbon monoxide which can be dissolved in anhydrous acid, e.g., hydrogen fluoride, or the reaction mixture, can be empirically determined by one of ordinary skill in the art at a particular temperature and a particular pressure. For example, at 3,000 psig and 800C, 9 Ibs of carbon monoxide would be dissolved in 100 Ibs of hydrogen fluoride. Based on the molar amount of the organic compound which is intended to be reacted, the amount of carbon monoxide needed for the reaction can be determined.For example, as stated above, the desired range of molar ratios of organic compound to carbon monoxide to acid is 1:1-25:1-100 and the preferred ratio is 1:25 :14, particularly for propylene, carbon monoxide, and anhydrous hydrogen fluoride.
Other information required are the reaction conditions desired, i.e., the pressure and the temperature of the reactor. From this, the molar percentage of carbon monoxide dissolved in the acid hydrogen fluoride, can be determined. From this, the amount of acid hydrogen fluoride solution required to supply sufficient carbon monoxide to react with the organic compound can also be determined.
The following examples will illustrate the process as described herein.
The carbonylation reactor was a 300 cc Autoclave Engineers Magnedrive Hastelloy (Registered
Trade Mark) C equipped with a turbine blade stirrer, a carbon monoxide inlet, a propylene inlet an outlet for depressurizing the reactor, and an external heater.
The reactor was initially flushed with carbon monoxide and then about 1 50 grams (7.5 moles) of an hydros hydrogen fluoride were charged into the reactor. Carbon monoxide was then charged to the preselected pressure into the reactor while the hydrogen fluoride was stirred and the reactor was allowed to equilibrate to the preselected temperature.
After the carbon monoxide pressure had stabilized, propylene was fed into the vapor phase of the liquid mixture (the vapor phase was a mixture of carbon monoxide and hydrogen fluoride) which was above the liquid phase, so as to form a supercritical mixture of propylene and carbon monoxide which transferred into the liquid phase. The propylene was fed through a metering pump while the carbon monoxide was added by maintaining the reactor's pressure at the preselected pressure.
After the reaction was complete; that is, the predetermined amount of propylene and carbon monoxide had been added, the reactor was stirred for an additional time, from fifteen to thirty minutes, then the reactor was cooled to about -200C with an acetone/dry ice mixture, and then 38.5 grams of water was pumped into the reactor over a five-to-ten-minute period, while cooling. The reactor was then vented, opened, and the product was further diluted with ice water, until the hydrogen fluoride was about 10 wt. percent of the mixture. Then 400 grams of sodium sulfate (Na2SO4) was added, and the isobutyric acid and oligomers extracted with 4 separate volumes of cyclohexane (400, 300, 200, 200).
The cyclohexane extracts were combined and analyzed by gas chromatography, as well as separating the products by distillation. The percentage yield of isobutyric acid formed is based on the amount of propylene added.
Table I shows the results of controlling the feed of propylene and carbon monoxide at various temperatures and pressures. Column 1 gives the example number; Column 2, the pressure range of the reaction in pounds per square inch gauge (psig); Column 3, the temperature range of the reaction in degrees Centigrade (or); Column 4 gives the time of complete addition of propylene; Column 5 gives the moles of propylene added per hour; Column 6 gives the apparent reaction time, based on the sum of the time of propylene addition and additional time for carbon monoxide pressure to stabilize; Column 7 gives the percent (%) yield of isobutyric added based on the total amount of propylene added.The examples given in Table I were run at a hydrogen fluoride-to-propylene mole ratio of 1 5 moles of hydrogen fluoride to one mole of propylene, and the carbon monoxide/propylene ratio being fed to the reaction mixture was 1.1 moles of carbon monoxide to one mole of propylene.
It is readily seen from Examples 3, 4, 5, 6, 8, 9 and 13 that substantially theoretical yields about 90 percent) of isobutyryl fluoride form when the rate of addition of propylene is at substantially the rate it is being used. The other examples illustrate that if the rate is too rapid, or the pressure too low, or the vapor phase is not above the critical point, or the carbon monoxide solubility in hydrogen fluoride is too low, then below substantial yields of isobutyryl fluoride are obtained.
While the invention has been described with reference to specific details of certain illustrative embodiments it is not intended that it shall be limited thereby except insofar as such details appear in the accompanying claims.
TABLE I
Mole Ratio of Anhydrous Hydrogen Fluoride to Propylene Added 1 5:1
Total Anhydrous HF was 1 50 grams
Carbon Monoxide Added 10% Excess
Reaction
Tempera- Rate of Apparent
ture Time of C3 Addition of Reaction Isobutyric
Pressure, Range, Addition, Propylene, Time, Acid
Example psig OC minutes moles per hr. minutes % Yield
Comparative 1 1033 26-30 31.5 1.95 40 76
Comparative 2 1595 29-31 28 2.1 30 76.5
3 1600 28-30 88 0.6 91 93
4 2800 29-32 27 2.1 34 98
5 2895 40-49 34.5 1.8 37 96
6 2919 68-72 28.5 2.1 30 96
7 2880 80-84 27 2.25 29 90
8 2830 29-32 30 1.95 32.5 97
9 2800 29-32 16.7 3.9 20 91
Comparative 10 2850 27-32 10.0 6.0 14 89
Comparative 11 2810 29-33 6.0 10.01 9 85
Comparative 12 2800 30-34 5.5 11.00 9 85
13 3690 26-30 18.5 3.3 20 93
Claims (10)
1. A process for producing an acylium anion product which comprises reacting in the liquid phase under conditions whereby an acylium anion product (acylium fluoride) forms in substantial yields, carbon monoxide, anhydrous hydrogen fluoride acid and an organic compound capable of adding carbon monoxide thereto, while feeding carbon monoxide and the organic compound into the vapor phase over the liquid reaction mixture at substantially the same rate as the carbon monoxide, organic compound and anhydrous hydrogen fluoride acid form the acylium anion product, the vapor phase over the liquid being maintained at a temperature and pressure whereby the carbon monoxide in the vapor phase of the mixture is in a supercritical fluid phase and the organic compound is dissolved therein;;
The organic compound being (a) an ester of the general formula
wherein R is an alkyl group having up to twenty carbon atoms, and R' is an alkyl group having from two to twenty carbon atoms, or (b) an oiefin having at least one double bond capable of adding carbon monoxide thereto and having up to twenty carbon atoms;
the temperature being within the range of from forty (40) degrees Centigrade to ninety (90) degrees Centigrade and the pressure being from one hundred and nine (109) bars (1,600 psia) to three hundred and forty (340) bars (5,000 psia);
the final mole ratio anhydrous hydrogen fluoride acid to organic compound in the reaction mixture being within the range of from one (1) to one hundred (100) moles of anhydrous hydrogen fluoride acid to one (1) mole of organic compound::
and the mole ratio of carbon monoxide to organic compound being within the range of from (1) to twenty-five (25) moles of carbon monoxide to one (1) mole of organic compound.
2. A process as claimed in Claim 1 wherein the organic compound is isopropyl isobutyrate, ethyl isobutyrate, isopropyl propionate or ethyl propionate.
3. A process as claimed in Claim 1 wherein the organic compound is isopropyl isobutyrate.
4. A process as claimed in Claim 1 wherein the organic compound is ethylene, propylene, isobutene, 1 -butene, 2-butene or 1 3-butadiene.
5. A process as claimed in Claim 1 wherein the organic compound is ethylene or propylene.
6. A process as claimed in Claim 1 wherein the organic compound is propylene.
7. A process as recited in any of Claims 1 to 6 wherein the temperature is within the range of forty j40) degrees Centigrade to seventy (70) degrees Centigrade and the pressure is within the range of from one hundred and sixty-nine (169) bars (2,500 psia) to one hundred and ninety-seven (197) bars (2,900 psia), the final mole ratio of an hydros hydrogen fluoride acid to organic compound in the reacting mixture is within the range of from ten (10) to twenty (20) moles of anhydrous hydrogen fluoride acid to one (1) mole of organic compound, and the mole ratio of carbon monoxide to organic compound is within the range of from fifteen (1 5) to twenty-five (25) moles of carbon monoxide to one (1) mole of organic compound.
8. A process as claimed in any of Claims 1 to 7 wherein the acylium anion product is separated from the reaction mixture.
9. A process for the production of an acylium anion product substantially as described with particular reference to any of examples 3 to 9 and 13.
10. An acylium anion product when prepared by a process as claimed in any of Claims 1 to 9.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US27876481A | 1981-06-29 | 1981-06-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2100729A true GB2100729A (en) | 1983-01-06 |
| GB2100729B GB2100729B (en) | 1985-10-30 |
Family
ID=23066263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08216304A Expired GB2100729B (en) | 1981-06-29 | 1982-06-04 | Production of acyl fluorides by carbonylation |
Country Status (12)
| Country | Link |
|---|---|
| JP (1) | JPS6024088B2 (en) |
| KR (1) | KR850001914B1 (en) |
| AT (1) | AT388160B (en) |
| AU (1) | AU532639B2 (en) |
| BE (1) | BE893419A (en) |
| CA (1) | CA1173057A (en) |
| CH (1) | CH660180A5 (en) |
| DE (1) | DE3221172C2 (en) |
| FR (1) | FR2508441B1 (en) |
| GB (1) | GB2100729B (en) |
| IT (1) | IT1195930B (en) |
| NL (1) | NL187013C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001007388A1 (en) * | 1999-07-23 | 2001-02-01 | Thomas Swan & Co. Ltd. | Carbonylation reactions |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NZ195559A (en) * | 1979-11-29 | 1984-03-16 | Ris Irrigation Syst | Butterfly sprinkler with dust protection for bearing |
| US4499029A (en) * | 1983-06-15 | 1985-02-12 | Ashland Oil, Inc. | Isobutyryl fluoride manufacture |
| DE3725428A1 (en) * | 1987-07-31 | 1989-02-09 | Basf Ag | METHOD FOR PRODUCING CARBONIC ACID HALOGENIDES |
| FR2691965A1 (en) * | 1992-06-04 | 1993-12-10 | Atochem Elf Sa | Iso-butyryl fluoride prodn. by two=stage process - comprising reacting propylene@ with hydrogen fluoride in gas phase until before pt where oligomers form, then reacting with carbon mon:oxide in liq. hydrogen |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE972291C (en) * | 1954-05-16 | 1959-07-02 | Studiengesellschaft Kohle Mbh | Process for the production of monocarboxylic acids from olefins, carbon monoxide and water |
| DE973077C (en) * | 1954-07-30 | 1959-11-26 | Studiengesellschaft Kohle Mbh | Process for the production of carboxylic acids from olefins and carbon oxide |
| DE1064941B (en) * | 1957-04-24 | 1959-09-10 | Studiengesellschaft Kohle Mbh | Process for the preparation of mixtures of saturated aliphatic or cycloaliphatic monocarboxylic acid alkyl esters |
| US3065242A (en) * | 1960-02-23 | 1962-11-20 | Du Pont | Production of acyl halides, carboxylic acids and lactones |
| US3167585A (en) * | 1960-08-25 | 1965-01-26 | Gulf Research Development Co | Process for carboxylation of iso-olefins |
| GB942367A (en) * | 1961-04-29 | 1963-11-20 | Basf Ag | Continuous production of carboxylic acids from olefines, carbon monoxide and water |
| NL6816940A (en) * | 1967-11-28 | 1969-05-30 | ||
| GB1232317A (en) * | 1968-12-30 | 1971-05-19 | ||
| BE755997A (en) * | 1969-09-11 | 1971-03-10 | Bp Chem Int Ltd | PRODUCTION OF DICARBOXYLIC ACIDS |
| DE2750719A1 (en) * | 1977-11-12 | 1979-05-17 | Roehm Gmbh | Isobutyric acid prepn. by boron tri:fluoride-catalysed carbonylation - of propylene, isopropanol, ether and/or ester deriv. in aliphatic carboxylic acid medium |
| US4224232A (en) * | 1978-12-21 | 1980-09-23 | Gulf Research & Development Company | Production of carboxylic acids from olefins and mixtures of olefins |
| EP0017441B2 (en) * | 1979-04-09 | 1987-10-28 | CHEM SYSTEMS, Inc. | Preparation of esters |
-
1982
- 1982-06-03 AT AT0215082A patent/AT388160B/en not_active IP Right Cessation
- 1982-06-04 AU AU84609/82A patent/AU532639B2/en not_active Ceased
- 1982-06-04 KR KR8202507A patent/KR850001914B1/en active
- 1982-06-04 CH CH3476/82A patent/CH660180A5/en not_active IP Right Cessation
- 1982-06-04 BE BE0/208271A patent/BE893419A/en not_active IP Right Cessation
- 1982-06-04 DE DE3221172A patent/DE3221172C2/en not_active Expired
- 1982-06-04 JP JP57096065A patent/JPS6024088B2/en not_active Expired
- 1982-06-04 FR FR8209809A patent/FR2508441B1/en not_active Expired
- 1982-06-04 IT IT21707/82A patent/IT1195930B/en active
- 1982-06-04 GB GB08216304A patent/GB2100729B/en not_active Expired
- 1982-06-04 CA CA000404487A patent/CA1173057A/en not_active Expired
- 1982-06-04 NL NLAANVRAGE8202268,A patent/NL187013C/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001007388A1 (en) * | 1999-07-23 | 2001-02-01 | Thomas Swan & Co. Ltd. | Carbonylation reactions |
| GB2367820A (en) * | 1999-07-23 | 2002-04-17 | Swan Thomas & Co Ltd | Carbonylation reactions |
Also Published As
| Publication number | Publication date |
|---|---|
| KR840000461A (en) | 1984-02-22 |
| AU8460982A (en) | 1983-03-10 |
| ATA215082A (en) | 1988-10-15 |
| GB2100729B (en) | 1985-10-30 |
| IT1195930B (en) | 1988-11-03 |
| FR2508441B1 (en) | 1987-04-30 |
| DE3221172C2 (en) | 1984-08-02 |
| NL8202268A (en) | 1983-01-17 |
| KR850001914B1 (en) | 1985-12-31 |
| AT388160B (en) | 1989-05-10 |
| CH660180A5 (en) | 1987-03-31 |
| CA1173057A (en) | 1984-08-21 |
| JPS6024088B2 (en) | 1985-06-11 |
| NL187013B (en) | 1990-12-03 |
| IT8221707A0 (en) | 1982-06-04 |
| NL187013C (en) | 1991-05-01 |
| AU532639B2 (en) | 1983-10-06 |
| DE3221172A1 (en) | 1983-01-05 |
| FR2508441A1 (en) | 1982-12-31 |
| JPS588036A (en) | 1983-01-18 |
| BE893419A (en) | 1982-10-01 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940604 |