US2472086A - Carburetor process for acetylene reactions - Google Patents
Carburetor process for acetylene reactions Download PDFInfo
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- US2472086A US2472086A US621622A US62162245A US2472086A US 2472086 A US2472086 A US 2472086A US 621622 A US621622 A US 621622A US 62162245 A US62162245 A US 62162245A US 2472086 A US2472086 A US 2472086A
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- acetylene
- reaction
- acid
- volatile
- organic
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- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title description 57
- 238000006243 chemical reaction Methods 0.000 title description 53
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title description 52
- 238000000034 method Methods 0.000 title description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 23
- 239000002253 acid Substances 0.000 description 21
- 229920001567 vinyl ester resin Polymers 0.000 description 17
- 239000003085 diluting agent Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000002360 explosive Substances 0.000 description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 10
- 238000004880 explosion Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- 150000002894 organic compounds Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 239000004246 zinc acetate Substances 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229940093915 gynecological organic acid Drugs 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001661 cadmium Chemical class 0.000 description 2
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical class C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZGUNAGUHMKGQNY-ZETCQYMHSA-N L-alpha-phenylglycine zwitterion Chemical compound OC(=O)[C@@H](N)C1=CC=CC=C1 ZGUNAGUHMKGQNY-ZETCQYMHSA-N 0.000 description 1
- 101150048797 LIPH gene Proteins 0.000 description 1
- 108091006503 SLC26A1 Proteins 0.000 description 1
- 241001417495 Serranidae Species 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical class [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- LPUZTLKYAOOFDX-QXMHVHEDSA-N ethenyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC=C LPUZTLKYAOOFDX-QXMHVHEDSA-N 0.000 description 1
- BLZSRIYYOIZLJL-UHFFFAOYSA-N ethenyl pentanoate Chemical compound CCCCC(=O)OC=C BLZSRIYYOIZLJL-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical class C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
Definitions
- the present invention relates to a process for of a volatile, normally liquid, organic diluent in producing vinyl esters of carboxylic acids. any desired manner. It is preferable to intro- A process for producing vinyl esters of carduce into the acetylene the required amount of boxylic acids by reacting acetylene, at elevated vapors of a volatile, normally liquid, organic temperatures and preferably elevated pressures, 5 diluent-while the acetylene is at a relatively low with carboxylic acids in liquid phase and in the pressure and/or temperature, 1.
- a mixture of 2 volumes of acetylen with diluent is in liquid phase and is maintained at 1 volume of nitrogen, hydrogen or another of the such a temperature that the acetylene will take aforesaid gaseous diluents usually has been emup or become carbureted with a suflicient amount ployed.
- acetyaromatic or naphthenic hydrocarbons such as lene is saturated or carbureted with the vapors benzene, toluene, xylene and the like, and in addition, certain heterocyclic compounds.
- ethers, esters, etc. A wide variety of such compounds as ethers, esters, etc.,
- acetylene gas together with a predetermined amount of diluent vapor may be enclosed in a pressure vessel under test pressure and heated to the test temperature and any possible explosion initiated by means of an electrically heated wire provided within the pressure vessel.
- the reaction may be carried out in the presence of an inert liquid diluent or solvent which may be the same as or diflerent from the diluent employed for the acetylene.
- suitable solvents may be mentioned aliphatic, aromatic or hydroaromatic hydrocarbons, such as benzene, petroleum fractions, toluene, xylene, cyclohexane, tetrahydronaphthalene.
- esters for instance, the vinyl esters obtainable according to the present process, or such esters as methyl, ethyl, n-butyl, isobutyl or am] acetate or butyrate.
- the process of the present invention is applicable to the production of vinyl esters of organic acids, as for example, sallcyclic acid or hydroxy naphthoic acid; and in addition, heterocyclic acids, such as pyridine and quinoline carboxylic acids, and hydroaromatic carboxylic acids, for example, hydrophthalic acid.
- heterocyclic acids such as pyridine and quinoline carboxylic acids, and hydroaromatic carboxylic acids, for example, hydrophthalic acid.
- partially esterified acids or resins showing a high acid value, such as colophony, or mixtures of acids may be employed, as for example, the acids obtainable by saponiflcation of natural fats and fatty oils containing esters and all fatty acids or the mixtures of acids obtainable by the partial oxidation of selected petroleum fractions, for instance, paraflln wax, and the like.
- the reaction is catalyzed by zinc and cadmium salts of organic acids, and suitable catalysts are such compounds as zinc acetate, zinc stearate, zinc benzoate or the corresponding cadmium salts. These salts may be added, as such, to the acid treated with acetylene or they may be prepared by dissolving the zinc or cadmium oxides in the acids to be employed. In practicing the present process, it is preferable to employ at least 7.5% of catalyst, calculated as ZnO or CdO with reference to the acid employed, and generally speaking, the quantity of the catalyst is between 0.5 and about 5%.
- the vinyl esters produced in accordance with the present invention may be recovered in any suitable manner from the reaction mass, for instance, by extraction with suitable solvents or by distillation, under vacuum, if necessary.
- Suitable solvents for instance, by extraction with suitable solvents or by distillation, under vacuum, if necessary.
- Various l polymerization inhibitors such as hydroquinone,
- aliphatic-aromatic acids as for example, phenyl acetic acid, cinnamic acid, phenyl glycine and polybasic cyclic acids or their acid esters, such as phthalic acid and phthalic acid monoalkyl esters, for example, mono-ethyl, normal or naphthols, or amines may be added during the distillation or on subsequent storage of the vinyl esters.
- the vinyl esters obtained according to this invention may be polymerized by the usual methods.
- Example 1 Acetylene at a pressure of 4 pounds per square inch, free from moisture and other impurities, is passed through a bath of acetic acid maintained at 118 C. The acetylene is saturated with acetic acid and is then compressed to 45 pounds per square inch and then heated to a temperature of C. It is then introduced into the bottom of a tower filled with glacial acetic acid, held at a temperature of C. in which is dissolved approximately 4% by weight of zinc acetate. The acetylene reacts rapidly with the acetic acid, in accordance with the following equation:
- Example 2 Acetylene at a pressure of 4 pounds per square isobutyl esters; also cyclohydroxy carboxylic 75 therewith and is then compressed to a pressure of .45 pounds per square inch and heated to a temperature of 145 C. It is then passesgbinto a closed reaction vessel, filled with Valerie acid.
- the method of eliminating the danger of acety- --lene explosion which comprises contacting the acetylene which is supplied to said reaction zone while it is under non-explosive conditions of temperature and pressure with a volatile normally liquid organic compound selected from the group consisting of volatile organic liquid diluents which are inert in said reaction and volatile organic acids employed in said reaction, said contacting being eflected while said volatile normally liquid 7 organic compound is in liquid phase and is main 'atained at such a predetermined temperature that the-acetylene on contact therewith becomes sat- 1 -s,.4va,oec
- the method of eliminating the danger of acetylene explosion which comprises contacting the acetylene supplied to said reaction zone while it is under non-explosive conditions of temperature and pressure with a non-explosive volatile normally liquid organic compound which is inert to both the acetylene and the organic acid under the conditions of reaction, while said volatile normally liquid organic compound is in liquid phase and is maintained at such a predetermined temperature that the acetylene on contact therewith becomes saturated with the vapors of said normally liquid organic compound in such an amount as to form a mixture of acetylene and such vapors in ,such predetermined ratio that said mixture is non-explosive at said normally explo-.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Patented June 1, 1949 2 472 035,
' CARBI IRETOR PROCESS FOR ACETYLENE I REACTIONS Hans Beller, Crawford, and Robert E. Christ and Fritz Wuerth, Elizabeth, N. J assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application October-10, 1945,
Serial No. 521,622 a s cnhmi. (Cl. 260-468) 1 2 The present invention relates to a process for of a volatile, normally liquid, organic diluent in producing vinyl esters of carboxylic acids. any desired manner. It is preferable to intro- A process for producing vinyl esters of carduce into the acetylene the required amount of boxylic acids by reacting acetylene, at elevated vapors of a volatile, normally liquid, organic temperatures and preferably elevated pressures, 5 diluent-while the acetylene is at a relatively low with carboxylic acids in liquid phase and in the pressure and/or temperature, 1. e., conditions at presence of a small amount of a cadmium or zinc which it is non-explosiv and thereafter comsalt of a carboxylic acid as a, catalyst, has been press it to the pressure desired for the reaction described in United States Patent No. 2,066,075 and, if necessary, heat it to the reaction temto Reppe. perature. However, by employing slow acting While it is preferable to employ elevated temcompressors and cooling during compression, it is peratures and pressures in practicing the abovepossible to bring undiluted acetylene to a relamentioned process, and, in fact, such reaction tively high pressure with reasonable safety, and conditions arenecessary if a satisfactory rate the vapors of the volatile, normally liquid, orof reaction and yield are to be obtained, the inganic diluent may then be introduced into the herent instability of acetylene under such reaccompressed acetylene. While the particular tion conditions has heretofore introduced numet d of ntrodu ng t e d u nt p s to th merous difiiculties in practicing this process. In acetylene does not, per m a P f the order to render the acetylene reasonably safe unpr n nv n i n. d n m r us ns f r acder the preferred reaction conditions, it has been eompllshing, this introduction e e necessary to dilute it sufiiciently with inert gases, scri ed in our v -m nt eopendil'lg app such as nitrogen, hydrogen, carbon monoxide, Cation, d t y, e acetylene maybe methane 0r ethane in order to preclude x locontacted with the desired diluent, while the sions. A mixture of 2 volumes of acetylen with diluent is in liquid phase and is maintained at 1 volume of nitrogen, hydrogen or another of the such a temperature that the acetylene will take aforesaid gaseous diluents usually has been emup or become carbureted with a suflicient amount ployed. This dilution of the acetylene with inert f v pors f the diluent that it will be non-exgaseous diluents has resulted in a substantial inl p ive at t e reaction i i n to e p y crease in the over-all pressure which is required n practicing t e p e n invention, i Sh ld be and has materially lowered the rate of reaction r e in i d t a in r r t pr ude th P08- and yield at any given reaction conditions. In sibllity of explosion, not only should the ac tyaddition to these and th u d i b pr clene which is supplied to the reaction be diluted ess effects, it has substantially increased the size h the Vapors of a V l lly iq 0 of the plant and auxiliary equipment required for ni l nt but ny nr d etylene recarrying out the reactio moved from the reaction mixture should be simi- We have now found that this reaction ma be larly diluted so long as it is under an elevated carried out at relatively lower pressures and with P e t mp ur a relatively higher rate of reaction and yield The Volatile, norm y Organic C p d under any given reaction conditions if the acety- Which is empl to dilute 01 r urize he lene employed in th process i mi t acetylene may, in case the vinyl ester to be prosuificient amount of the vapors of a volatile, norduced is that of a volatile organl a i e the man liquid, organic d m m; t eliminate the vapors of the acid itself or a-volatile ester, which danger of explosion in the manner described in tllrll y be a Product O lihe reaction. if our copending application Serial No, 621,620 sired, thereof. In addition, practically any vola- When the acetylene is diluted in this manner tile organic compound which is inert under the with the vapors of a volatile, normally liquid, or- Conditions Of the r c n may be empl s ganic diluent, not only are the desired process e dill-lent Carbureting agentit e eflects of elimination of the dangers of explosion pounds o such se ay be i ed t e overcome and, at any given reaction conditions, lower aliphatic q i r o s, S ch as a ithe improvement in yield and rate of reaction ph llic 01 y l liph fi hydrocarbons, for obtained, but in addition, the capital cost of plant ple, hexan h p a ane, cyolohexane and necessary for practicing the process may be subothers, their isomers or mixtures thereof, for instantiallyreduced. stance, volatile petroleum fractions, also many In practicing the present invention, the acetyaromatic or naphthenic hydrocarbons, such as lene is saturated or carbureted with the vapors benzene, toluene, xylene and the like, and in addition, certain heterocyclic compounds. A wide variety of such compounds as ethers, esters, etc.,
with the reaction conditions to be used and also with the specific compound being employed as a diluent a suillcient amount of diluent or carburizing agent being employed to preclude the possibility of explosions. The limits of explosability or the degree of dilution which is necessary may be determined readily for any particular conditions by simple preliminary test. Thus, for instance, acetylene gas, together with a predetermined amount of diluent vapor may be enclosed in a pressure vessel under test pressure and heated to the test temperature and any possible explosion initiated by means of an electrically heated wire provided within the pressure vessel. The reaction may be carried out in the presence of an inert liquid diluent or solvent which may be the same as or diflerent from the diluent employed for the acetylene. As examples of suitable solvents may be mentioned aliphatic, aromatic or hydroaromatic hydrocarbons, such as benzene, petroleum fractions, toluene, xylene, cyclohexane, tetrahydronaphthalene. esters, for instance, the vinyl esters obtainable according to the present process, or such esters as methyl, ethyl, n-butyl, isobutyl or am] acetate or butyrate.
when the acetylene, diluted with a suflicient amount of vapors of a volatile, normally liquid, organic diluent to preclude the possibility of explosion, is admixed with a carboxylic acid in the presence of a small amount of a suitable catalyst, and the reaction mixture maintained at predetermined reaction conditions, the acetylenereadily reacts with the carboxylic acid to form vinyl esters. It appears that the probable course of reaction is in accordance with the following equation:
Zn 202E:
The process of the present invention is applicable to the production of vinyl esters of organic acids, as for example, sallcyclic acid or hydroxy naphthoic acid; and in addition, heterocyclic acids, such as pyridine and quinoline carboxylic acids, and hydroaromatic carboxylic acids, for example, hydrophthalic acid. Instead of pure acids, partially esterified acids or resins showing a high acid value, such as colophony, or mixtures of acids may be employed, as for example, the acids obtainable by saponiflcation of natural fats and fatty oils containing esters and all fatty acids or the mixtures of acids obtainable by the partial oxidation of selected petroleum fractions, for instance, paraflln wax, and the like.
The reaction is catalyzed by zinc and cadmium salts of organic acids, and suitable catalysts are such compounds as zinc acetate, zinc stearate, zinc benzoate or the corresponding cadmium salts. These salts may be added, as such, to the acid treated with acetylene or they may be prepared by dissolving the zinc or cadmium oxides in the acids to be employed. In practicing the present process, it is preferable to employ at least 7.5% of catalyst, calculated as ZnO or CdO with reference to the acid employed, and generally speaking, the quantity of the catalyst is between 0.5 and about 5%.
The vinyl esters produced in accordance with the present invention may be recovered in any suitable manner from the reaction mass, for instance, by extraction with suitable solvents or by distillation, under vacuum, if necessary. Various l polymerization inhibitors, such as hydroquinone,
acid and the different isomers of naphthoic acid,
also mixed aliphatic-aromatic acids, as for example, phenyl acetic acid, cinnamic acid, phenyl glycine and polybasic cyclic acids or their acid esters, such as phthalic acid and phthalic acid monoalkyl esters, for example, mono-ethyl, normal or naphthols, or amines may be added during the distillation or on subsequent storage of the vinyl esters. The vinyl esters obtained according to this invention may be polymerized by the usual methods.
The following examples will further illustrate how this invention may be carried out in practice, but the invention is not restricted to these examples: I
Example 1 Acetylene at a pressure of 4 pounds per square inch, free from moisture and other impurities, is passed through a bath of acetic acid maintained at 118 C. The acetylene is saturated with acetic acid and is then compressed to 45 pounds per square inch and then heated to a temperature of C. It is then introduced into the bottom of a tower filled with glacial acetic acid, held at a temperature of C. in which is dissolved approximately 4% by weight of zinc acetate. The acetylene reacts rapidly with the acetic acid, in accordance with the following equation:
and vinyl acetate, along with unreacted acetic acid and acetylene are continuously withdrawn from the reaction zone, while fresh acetic acid and catalyst, if necessary, are continuously introduced into the reaction zone. The pressure on the products withdrawn from the reaction zone may be released and the acetylene separated therefrom, and thereafter, the vinyl acetate separatedfrom the acetic acid by fractional distillation, vinyl acetate being obtained as a colorless liquid boiling at 73 C. in 85-95% yield.
Example 2 Acetylene at a pressure of 4 pounds per square isobutyl esters; also cyclohydroxy carboxylic 75 therewith and is then compressed to a pressure of .45 pounds per square inch and heated to a temperature of 145 C. It is then passegbinto a closed reaction vessel, filled with Valerie acid.
containing about 2.5% zinc acetate and mainv tained at a temperature of approximately 170 C.
. The acetylene reacts readily with the valeric acid to produce vinyl valerate in accordance with the' following equation:
- moor1+1icEcn-+cimco-o cH=cm 1)urlng the reaction, acetylene, diluted with cy- --clohexane, is continuously removed from the reaction zone and fresh diluted acetylene intro- J duced thereinto. When the acetylene is no longer Example 3 Acetylene at 4 pounds per square inch is passed through a bath of cyclohexane maintained at- 79 0., and becomes saturated therewith and is-then --compressed to 45 pounds per square inch and heated to 145 C. It is then introduced into a closed reaction vessel charged with 200 pounds oleic acid, 40 pounds cyclohexane and 14 pounds "of zinc acetate from which oxygen has been removed by flushing with nitrogen and the nitrogen removed by evacuation. The mixture in the reaction vessel is maintained at 160 C. The acetylene readily reacts with the oleic acid to formvlnyl oleate in accordance with the following equation:
"During the reaction, unreacted acetylene and -cyclohexane may be continuously withdrawn from the reaction zone while fresh diluted acetylene is continuously introduced thereinto. When the theoretical amount of acetylene has been absorbed, the reaction mixture isthen allowed to" cool, then filtered to remove zinc acetate and the filtrate fractionally distilled. After separating -'oif the cyclohexane, vinyl oleate boiling at 173- 175 C. at 2 mm. pressure is obtained in 90-95% y eld. 1 We claim: 1. In a process of producing vinyl esters wherein acetylene is introduced into a reaction zone and reacted therein with an organic carboxylic acid maintained in said reaction zone under elevated conditions of temperature and pressure at which the acetylene is normally explosive, the method of eliminating the danger of acety- --lene explosion which comprises contacting the acetylene which is supplied to said reaction zone while it is under non-explosive conditions of temperature and pressure with a volatile normally liquid organic compound selected from the group consisting of volatile organic liquid diluents which are inert in said reaction and volatile organic acids employed in said reaction, said contacting being eflected while said volatile normally liquid 7 organic compound is in liquid phase and is main 'atained at such a predetermined temperature that the-acetylene on contact therewith becomes sat- 1 -s,.4va,oec
urated with the vapors c! said volatile normally liquid organic compound in such an amount as to form a mixture of acetylene and such vapors in such predetermined ratio that said mixture is non-explosive at said normally explosive reaction conditions, adjusting the pressure and temperature of the thus formed mixture to said normally explosive reaction conditions, introducing the at which said vapors will condense and therein thus obtained mixture into said reaction zone while maintaining it at a temperature above that eflecting the desired reaction between said acetylene and said organic carboxylic acid to produce a vinyl ester and recovering the same. 15v
2. In a process of producing vinyl esters or volatile organic carboxylic acids wherein-acetylene is introduced into a reaction zone and reacted therein with a volatile organic carboxylicv acid maintained therein under elevated conditions of temperature and pressure at which the acetylene is normally explosive, the method of eliminating the danger of acetylene explosion which com-- prises contacting the acetylene which is supplied to said reaction zone while it is under non-explosive conditions of temperature and pressure with a body of said volatile organic carboxylic acid in liquid phase and maintained at such a predetermined temperature that the acetylene on contact therewith becomes saturated with the vapors of said volatile organic carboxylic acid in such an amount as to form a mixture of acetylene and such vapors in such predetermined ratio that said mixture is non-explosive at said normally explosive reaction conditions, adjusting the pressure and temperature of the thus formed mixture to said normally explosive reaction conditions, introducing the thus obtained mixture into said reaction zone while maintaining it at a temperature above that-at which said vapors will condense, eifecting the desired reaction between said acetylene and said volatile organic carboxylic acid in said reaction zone to produce a vinyl ester and recovering the same.
3. A process as defined in claim 2, wherein the volatile organic carboiwlic acid specified is acetic acid and the vinyl ester produced is vinyl acetate.
4. In a process of producing a vinyl ester wherein acetylene is introduced into a reaction zone and reacted therein with an organic carboxylic acid under elevated conditions of temperature and pressure at which the acetylene is normally explosive, the method of eliminating the danger of acetylene explosion which comprises contacting the acetylene supplied to said reaction zone while it is under non-explosive conditions of temperature and pressure with a non-explosive volatile normally liquid organic compound which is inert to both the acetylene and the organic acid under the conditions of reaction, while said volatile normally liquid organic compound is in liquid phase and is maintained at such a predetermined temperature that the acetylene on contact therewith becomes saturated with the vapors of said normally liquid organic compound in such an amount as to form a mixture of acetylene and such vapors in ,such predetermined ratio that said mixture is non-explosive at said normally explo-.
dense and therein efiecting the desired reaction between the acetylene and said organic carboxylic 4 7 acid to produce a. vinyl ester and recoverinl the REFERENCES CITED same.
5. 'A procees as defined in claim 4, wherein the y: figw fi m organic ccrboxylic acid specified is Valerie acid and the vinyl ester progxced 11s vinzl 1mg. h 5 UNITED STATES PATENTS 6.Aprocessasdefln incaim .were te be "m organic carboxylic acid specified is oleic acid and 2 3 g at a] i? 1928 vinyl Pmduced vinyl 1 1,786,647 mum. et '11. L Dec: 30, 1930 gg fi g'fi 1,822,525 Herman et a1. Sept. e, 1931 10 2,066,075 Reppe Dec. 29, 1938 m m' 2,176,958 Dreyfus on. 24, 1939
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US621622A US2472086A (en) | 1945-10-10 | 1945-10-10 | Carburetor process for acetylene reactions |
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US621622A US2472086A (en) | 1945-10-10 | 1945-10-10 | Carburetor process for acetylene reactions |
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2770650A (en) * | 1956-11-13 | Process fortheeproduction of | ||
US3062863A (en) * | 1959-03-25 | 1962-11-06 | Hoechst Ag | Process for the manufacture of vinylesters |
US3125593A (en) * | 1964-03-17 | Process for the production of | ||
US4091005A (en) * | 1976-10-04 | 1978-05-23 | The United States Of America As Represented By The Secretary Of Agriculture | Continuous process for preparation of isopropenyl stearate |
US20100286440A1 (en) * | 2009-05-07 | 2010-11-11 | Celanese International Corporation | Vinyl Ester production from Acetylene and Carboxylic Acid utilizing homogeneous catalyst |
US20100286441A1 (en) * | 2009-05-07 | 2010-11-11 | Kimmich Barbara F M | Vinyl Ester production from Acetylene and Carboxylic Acid utilizing heterogeneous catalyst |
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US1666482A (en) * | 1928-04-17 | Ebich baitm | ||
US1786647A (en) * | 1928-09-22 | 1930-12-30 | Du Pont | Process of preparing vinyl esters of organic acids |
US1822525A (en) * | 1927-02-12 | 1931-09-08 | Consortium Elektrochem Ind | Method for the manufacture of esters of vinyl alcohol |
US2066075A (en) * | 1932-03-05 | 1936-12-29 | Ig Farbenindustrie Ag | Vinyl esters of carboxylic acids and their production |
US2176958A (en) * | 1935-01-28 | 1939-10-24 | Dreyfus Henry | Vinyl acetate, ethylidine diacetate, and homologous esters |
-
1945
- 1945-10-10 US US621622A patent/US2472086A/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1666482A (en) * | 1928-04-17 | Ebich baitm | ||
US1822525A (en) * | 1927-02-12 | 1931-09-08 | Consortium Elektrochem Ind | Method for the manufacture of esters of vinyl alcohol |
US1786647A (en) * | 1928-09-22 | 1930-12-30 | Du Pont | Process of preparing vinyl esters of organic acids |
US2066075A (en) * | 1932-03-05 | 1936-12-29 | Ig Farbenindustrie Ag | Vinyl esters of carboxylic acids and their production |
US2176958A (en) * | 1935-01-28 | 1939-10-24 | Dreyfus Henry | Vinyl acetate, ethylidine diacetate, and homologous esters |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2770650A (en) * | 1956-11-13 | Process fortheeproduction of | ||
US3125593A (en) * | 1964-03-17 | Process for the production of | ||
US3062863A (en) * | 1959-03-25 | 1962-11-06 | Hoechst Ag | Process for the manufacture of vinylesters |
US4091005A (en) * | 1976-10-04 | 1978-05-23 | The United States Of America As Represented By The Secretary Of Agriculture | Continuous process for preparation of isopropenyl stearate |
US20100286440A1 (en) * | 2009-05-07 | 2010-11-11 | Celanese International Corporation | Vinyl Ester production from Acetylene and Carboxylic Acid utilizing homogeneous catalyst |
US20100286441A1 (en) * | 2009-05-07 | 2010-11-11 | Kimmich Barbara F M | Vinyl Ester production from Acetylene and Carboxylic Acid utilizing heterogeneous catalyst |
US7982065B2 (en) | 2009-05-07 | 2011-07-19 | Celanese International Corporation | Vinyl ester production from acetylene and carboxylic acid utilizing heterogeneous catalyst |
US8173830B2 (en) | 2009-05-07 | 2012-05-08 | Celanese International Corporation | Vinyl ester production from acetylene and carboxylic acid utilizing homogeneous catalyst |
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