US3657375A - Production of acetylene - Google Patents

Production of acetylene Download PDF

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Publication number
US3657375A
US3657375A US11390A US3657375DA US3657375A US 3657375 A US3657375 A US 3657375A US 11390 A US11390 A US 11390A US 3657375D A US3657375D A US 3657375DA US 3657375 A US3657375 A US 3657375A
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US
United States
Prior art keywords
acetylene
hydrocarbons
washing
crude
liquid
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.)
Expired - Lifetime
Application number
US11390A
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English (en)
Inventor
Erwin Brunner
Rolf Platz
Kurt Taglieber
Kurt Weinfurter
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BASF SE
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BASF SE
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Publication date
Priority claimed from DE19691908619 external-priority patent/DE1908619C3/de
Application filed by BASF SE filed Critical BASF SE
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Publication of US3657375A publication Critical patent/US3657375A/en
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Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/22—Aliphatic unsaturated hydrocarbons containing carbon-to-carbon triple bonds
    • C07C11/24—Acetylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/005—Processes comprising at least two steps in series
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/11—Purification; Separation; Use of additives by absorption, i.e. purification or separation of gaseous hydrocarbons with the aid of liquids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
    • C10G9/38—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours produced by partial combustion of the material to be cracked or by combustion of another hydrocarbon
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production
    • 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S585/00—Chemistry of hydrocarbon compounds
    • Y10S585/8995—Catalyst and recycle considerations
    • Y10S585/901—Catalyst and recycle considerations with recycle, rehabilitation, or preservation of solvent, diluent, or mass action agent

Definitions

  • This invention relates to a process for the production of acetylene by thermally cracking liquid hydrocarbons and workingup the cracked gas by removing carbon dioxide therefrom and washing out the acetylene with a selecttive solvent, the resultant crude acetylene being purified in a combined condensing and washing stage.
  • Thermal cracking of hydrocarbons and immediate quenching of the cracked gas are known to provide a gas mixture comprising hydrogen, carbon monoxide, carbon dioxide, methane, ethylene, acetylene and higher hydrocarbons.
  • Thermal cracking processes for the production of such acetylene-containing gas mixtures are described, for example, in Chem.-Ing.-Tech., 26, No. 5, 253 (1954), US. Pat. No. 3,047,371 and US. Pat. No. 2,984,695.
  • the most commonly used industrial method of thermally cracking methane provides a cracked gas containing relatively low proportions of higher hydrocarbons.
  • the acetylene is removed from this acetylene-containing cracked gas, usually following the removal of carbon dioxide by a suitable washing operation, by washingthe gas with a solvent showing 's'electivity for acetylene.
  • a particularly suitable solvent for this purpose is N-methylpyrrolidone.
  • stage (c) care must be taken to ensure that no solid Water separates during chilling of the acetylene to temperatures ranging from 10 to 30 C., since such ice would lead to blockage of the condensation apparatus.
  • an acetylene which contains only low proportions of impurities consisting of higher hydrocarbons, that is, hydrocarbons containing from 3 to 5 carbon atoms.
  • This crude acetylene which also contains higher hydrocarbons, i.e. essentially mixtures of hydrocarbons containing more than 5 carbon atoms, is unsuitable for further processing in many cases, as unsaturated impurities may often cause undesirable side reactions.
  • our new process for the production of pure acetylene is carried out by thermally cracking liquid hydrocarbons, particularly crude or heavy fuel oil, by the aforementioned submerged-flame process, that is, by effecting cracking with an oxygen-fed flame burning beneath the surface of said oil, to give a cracked gas containing the following components in the proportions stated below:
  • This gas is first treated in known manner with an aqueous solution of the potassium salt of a-methylaminopropionic acid or, preferably, diethanolamine to wash out the carbon dioxide and hydrogen sulfide.
  • the acetylene is removed in known manner by washing the gas With a suitable solvent, such as dimethylformamide, butyrolactone, tetraethyl glycol dimethyl ether and preferably N-methylpyrrolidone.
  • a suitable solvent such as dimethylformamide, butyrolactone, tetraethyl glycol dimethyl ether and preferably N-methylpyrrolidone.
  • the acetylene is washed out in the main washing column.
  • the pressures used are between 5 and 20 atmospheres and preferably between 10 and 15 atmospheres, while the temperatures range from 10 to 50 C. Less soluble components dissolved in the solvent are removed in a stripper by rising acetylene, preferably at a column pressure of from 1 to 2 atmospheres absolute,
  • Regeneration of the solvent is then carried out in a vacuum column under pressures ranging from 0.15 to 0.3 atmospheres, the temperature at the bottom of the column being from 100 to 140 C., preferably from 110 to 120 C.
  • This crude acetylene (see FIG. 1) is compressed in a blower 1 to a pressure of not more than 1.7 atmospheres absolute and chilled in heat exchangers, for example a combination of three different heat exchangers, to temperatures ranging from approximately 10 to 30 C., preferably to approximately -29 C.
  • the first heat exchanger of the combination of coolers is advantageously a water-irrigated direct-cooling apparatus 2 filled with a packing and also serving as a dissociation barrier for the acetylene.
  • the gas is countercurrent cooled by condensate and pure acetylene, while the remaining heat is extracted in the third heat exchanger 4 by refrigerating agents.
  • the crude acetylene usually contains water vapor acquired from a water wash following the wash with N- methylpyrrolidone. In order to prevent blockage of the coolers, freezing of the water vapor before the crude acetylene enters the last heat exchanger, in which it is cooled to temperatures below C., must be avoided. To this end the crude acetylene is loaded with methanol before it enters the cooler cooled by refrigerating agents.
  • This may be effected, for example, by saturating the crude acetylene with methanol vapor in a saturator or, more simply, by adding at 5 a sufficient quantity of methanol vapor, usually from 1 to 4 and preferably from 2 to 3 molar proportions based on the amount of water vapor present.
  • acetylene now partly purified by condensation of impurities in the coolers, is then subjected to countercurrent washing 6 with an organic washing liquid to remove the hydrocarbons of 3 to 5 carbon atoms which contaminate the acetylene.
  • Suitable Washing liquids are those which are inert under the reaction conditions, are preferably weakly polar, boil at temperatures above 80 C., freeze at temperatures below 40 C. and have low viscosity at temperatures ranging from 20 to 40 C.
  • organic liquids are aliphatic or aromatic hydrocarbons free from functional groups. Specific examples are n-heptane, n-octane, m-xylene, di-n-butyl ether and preferably toluene. Mixtures of such compounds are also very suitable.
  • the wash with the organic liquid boiling above C. is carried out in known types of apparatus, for example in a washing column, the crude acetylene being fed in at the bottom, whilst the organic liquid trickles down from the top.
  • the dimensions of this washing column are selected in the usual manner so as to ensure that the hydrocarbons are washed out as completely as possible.
  • the heat of solution liberated during the countercurrent wash is conveniently removed in coolers 7, 8.
  • At the top of the washing column there is thus obtained a purified acetylene still containing the following impurities: about .10 p.p.m. of propylene, 5 p.p.m. of propadiene and propyne ano about 1,000 p.p.m. of the organic washing liquid.
  • the laden organic liquid discharged at the bottom of the washing column is heated to approximately 0 to 20 C. and degassed, preferably in a stripper 9, for the recovery of the dissolved acetylene.
  • the gas thus obtained contains about 75% molar of acetylene and is recycled and mixed with the cracked gas after the latter has been freed of carbon dioxide and hydrogen sulfide but before it is subjected to selective washing.
  • the washing liquid discharged from said stripper is heated to about C. in a heat exchanger 10 and then passed to a fractionating column 11.
  • the resulting overhead product consists essentially of hydrocarbons of 3 to 5 carbon atoms and contains approximately 0.5% molar of acetylene.
  • the regenerated organic washing liquid is cooled in conventional heat exchangers 12 and recycled to the washing column.
  • the methanol added to ensure that the water is separated in the liquid state is conveniently also recovered.
  • the condensate obtained in the separator by cooling the crude acetylene is mixed with water and separated in a separating vessel 13 into a methanol/water phase and a hydrocarbon phase. Acetylene liberated during this stage is recycled through a degassing pipe to the second heat exchanger of the combination of coolers.
  • Methanol is isolated from the methanol/water phase, most conveniently by distillation in a column 14, and is then re-used in the condensation stage, Acetylene thus liberated is also recycled, together with a portion of unconcentrated methanol vapor, to the stream of crude acetylene.
  • a process for the production of pure acetylene which comprises:
  • step (b) washing the gaseous effluent from step (a) with an organic liquid showing selectivity for the absorption of acetylene and selected from the group consisting of dimethyl formamide, butyrolactone, tetraethyl dimethyl glycol ether and N-methylpyrrolidone, recovering from said organic liquid a crude acetylene containing hydrocarbons having 3 carbon atoms or more and traces of water;
  • step (c) removing from the gaseous efiluent obtained from step (c) substantially all of the hydrocarbons containing 3 to 5 carbon atoms accompanying the acetylene by washing said crude acetylene obtained from step (c) with toluene as the wash liquid at temperatures ranging from 20 C. to 40 C.;
  • step (e) recovering dissolved acetylene from the toluene obtained from step (d) by heating said toluene to temperatures ranging from C. to 40 C. and recycling the recovered acetylene to the gaseous effluent from step (b);
  • step (f) distilling the toluene Wash liquid obtained from step (e), thereby producing an overhead product consisting of hydrocarbons and a bottoms product consisting of pure toluene which is recycled to step (d) as fresh wash liquid.
  • a process as claimed in claim 1 for the purification of a water-containing crude acetylene which further comprises the steps of (ca) loading the gaseous eflluent from step (b) with methanol vapor and condensing out of said laden elfiuent a liquid mixture comprising methanol, water and a hydrocarbon mixture consisting essentially of hydrocarbons of more than 5 carbon atoms,
  • step (cd) recycling desor bed acetylene obtained from step (cc), said desorbed acetylene being laden with methanol vapor not condensed in said step (cc), to the condensation step (ca).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US11390A 1969-02-21 1970-02-16 Production of acetylene Expired - Lifetime US3657375A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19691908619 DE1908619C3 (de) 1969-02-21 Verfahren zur Gewbinung von Acetylen

Publications (1)

Publication Number Publication Date
US3657375A true US3657375A (en) 1972-04-18

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US11390A Expired - Lifetime US3657375A (en) 1969-02-21 1970-02-16 Production of acetylene

Country Status (11)

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US (1) US3657375A (ro)
JP (1) JPS5127645B1 (ro)
BE (1) BE746276A (ro)
BR (1) BR7016862D0 (ro)
CA (1) CA929960A (ro)
CH (1) CH561161A5 (ro)
ES (1) ES376749A1 (ro)
FR (1) FR2035513A5 (ro)
GB (1) GB1289757A (ro)
NL (1) NL7002148A (ro)
RO (1) RO62112A (ro)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977203A (en) * 1974-03-25 1976-08-31 Kansas University Endowment Association Purification of natural gas by liquid/liquid extraction with a polar solvent
US4325782A (en) * 1979-11-17 1982-04-20 Metallgesellschaft Aktiengesellschaft Apparatus for regenerating absorbent and method of operating the apparatus
US4367363A (en) * 1980-12-23 1983-01-04 Gaf Corporation Production of acetylene
US4695672A (en) * 1986-04-21 1987-09-22 Advanced Extraction Technologies, Inc. Process for extractive-stripping of lean hydrocarbon gas streams at high pressure with a preferential physical solvent
US4701190A (en) * 1985-11-07 1987-10-20 Linde Aktiengesellschaft Process for recovering methylacetylene and/or propadiene
US4788379A (en) * 1980-12-23 1988-11-29 Gaf Corporation Production of acetylene
CN105693452A (zh) * 2016-03-31 2016-06-22 北京神雾环境能源科技集团股份有限公司 一种天然气制乙炔的净化系统及方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58103729U (ja) * 1981-12-29 1983-07-14 グリ−ン産業株式会社 びん首飾り具

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1088477B (de) * 1959-03-11 1960-09-08 Linde Eismasch Ag Verfahren zur gleichzeitigen Gewinnung von hochreinem AEthylen und AEthan

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3977203A (en) * 1974-03-25 1976-08-31 Kansas University Endowment Association Purification of natural gas by liquid/liquid extraction with a polar solvent
US4325782A (en) * 1979-11-17 1982-04-20 Metallgesellschaft Aktiengesellschaft Apparatus for regenerating absorbent and method of operating the apparatus
US4367363A (en) * 1980-12-23 1983-01-04 Gaf Corporation Production of acetylene
US4788379A (en) * 1980-12-23 1988-11-29 Gaf Corporation Production of acetylene
US4701190A (en) * 1985-11-07 1987-10-20 Linde Aktiengesellschaft Process for recovering methylacetylene and/or propadiene
US4695672A (en) * 1986-04-21 1987-09-22 Advanced Extraction Technologies, Inc. Process for extractive-stripping of lean hydrocarbon gas streams at high pressure with a preferential physical solvent
CN105693452A (zh) * 2016-03-31 2016-06-22 北京神雾环境能源科技集团股份有限公司 一种天然气制乙炔的净化系统及方法
CN105693452B (zh) * 2016-03-31 2017-11-14 北京华福工程有限公司 一种天然气制乙炔的净化系统及方法

Also Published As

Publication number Publication date
FR2035513A5 (ro) 1970-12-18
BE746276A (fr) 1970-08-20
GB1289757A (ro) 1972-09-20
BR7016862D0 (pt) 1973-02-15
CH561161A5 (ro) 1975-04-30
ES376749A1 (es) 1972-05-16
NL7002148A (ro) 1970-08-25
JPS5127645B1 (ro) 1976-08-13
CA929960A (en) 1973-07-10
DE1908619B2 (de) 1976-09-30
DE1908619A1 (de) 1970-09-03
RO62112A (ro) 1977-08-15

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