US3325972A - Separating acetylene from gas mixtures - Google Patents

Separating acetylene from gas mixtures Download PDF

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Publication number
US3325972A
US3325972A US360548A US36054864A US3325972A US 3325972 A US3325972 A US 3325972A US 360548 A US360548 A US 360548A US 36054864 A US36054864 A US 36054864A US 3325972 A US3325972 A US 3325972A
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acetylene
line
washing
wash liquor
gas
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US360548A
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English (en)
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Friz Hans
Reichert Martin
Wagner Ulrich
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BASF SE
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BASF SE
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    • 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

Definitions

  • This invention relates to a process of purifying gases containing acetylene. More particularly, the invention relates to a process of recovering pure acetylene from gas mixtures containing acetylene.
  • Methods are known for the separation of acetylene from gas mixtures, particularly from gas mixtures which have been obtained by thermal or electric cracking of hydrocarbons with or without oxygen, in which the acetylene is washed out from the gas mixture by a solvent.
  • washing is carried out at superatmospheric pressure so that a maximum quantity of acetylene is dissolved.
  • the dissolved acetylene is liberated from the wash liquor by decreasing the pressure or by raising the temperature or by both measures together. It can then be freed from compounds having lower solubility than acetylene in countercurrent to the washing liquid.
  • acetylene When acetylene is washed out in this way, not only acetylene but also compounds having better solubility than acetylene (for example methylacetylene, vinylacetylene and diacetylene) are separated. These may be expelled from the wash liquor after the acetylene has been gassed out, at elevated temperature and preferably at subatmospheric pressure by means of steam and withdrawn as a mixture with steam. The degassed wash liquor is then used again for washing out acetylene (Chem. Ing.technik, 26, 253 1954)).
  • compounds having better solubility than acetylene for example methylacetylene, vinylacetylene and diacetylene
  • the gas obtained by cracking hydrocarbons may be washed, prior to the compression and the washing out of the acetylene, with a small amount of the same solvent (preliminary washing) so that compounds are removed from the gas which would cause soiling and stoppages in the compressor.
  • these are particularly polycyclic hydrocarbons, for example naphthalene, methylnaphthalenes, acenaphthalene and acenaphtheme.
  • the small amounts of wash liquor laden with these compounds obtained by the preliminary washing are freed from the absorbed substances together with the larger amounts of wash liquor used for washing out the acetylene under pressure (main washing).
  • Combination of the two wash liquors in the said method advantageously takes place after the acetylene liberated from the larger amount of wash liquor has been purified countercurrent to the wash liquor from the main washing.
  • Another proposal has been first to wash out from the acetylene-containing gas mixture at atmospheric pressure or at superatrnospheric pressure, the whole of the diacetylene with a small amount of solvent, to free the wash liquor laden with diacetylene from the diacetylene by stripping with a gas or steam, to wash out the acetylene from the gas mixture free from diacetylene with a larger amount of the same solvent under the same pressure, and to expel the dissolved acetylene again by heating the wash liquor.
  • Suitable solvents for this process are for example butyrolactone and N-methylpyrrolidone.
  • polymerisation products form in the wash liquor and cannot be removed from the wash liquor by degassing. A portion of these polymers remain dissolved in the Wash liquor and must be removed therefrom by complete or partial distillation of the wash liquor. Another portion of the polymers is deposited in solid form, for example in heat exchangers and columns, so that heat transfer is impaired and passage of gas and liquids made more difiicult.
  • the said objects are achieved by bringing the wash liquor obtained from the preliminary washing into contact, preferably countercurrent, with the mixture of steam and/ or solvent vapor and compounds having better solubility than acetylene which is obtained by expelling the compounds having better solubility than acetylene from the solvent of the main washing.
  • the wash liquor from the preliminary washing which has been treated in this way is advantageously used again as wash liquor either alone or together with the wash liquor from the main washing which has been freed from acetylene and compounds having better solubility than acetylene.
  • the amount of solvent for the preliminary washing is such that only a portion of the diacetylene is absorbed in the preliminary washing.
  • the same effect is however achieved if the whole of the diacetylene is washed out from the cracked gas in the preliminary washing.
  • Any small amount of acetylene absorbed during the preliminary washing may be removed again from the solvent in a conventional way by stripping the solvent from the preliminary washing with an inert gas (for example a portion of the lean gas practically free from acetylene obtained in the main washing) and returned in front of the compressor.
  • Naphthalene, acenaphthene and acenaphthylene are also detected in small concentration in the gas mixture.
  • the constituents of the gas which are more soluble than acetelene escape from degassing tower 12 through line 16 and enter at the bottom of column 17 as a mixture with water vapor and N-methylpyrrolidone vapor.
  • the laden Wash liquor from the pro-scrubber is in-' troduccd into the top of column 17 through line 29.
  • the mixture of vapor and gas Withdrawn from the top of the column 17 through line 18 is passed into column 19 to which 100 kg.
  • the wash liq-nor contains 0.06% by weight of dissolved polymers at the bottom of degassing tower 12 and 0.2% by weight of dissolved polymers at the bottom of column 17.
  • a gas mixture having the, following average composi tion in percent by volume is producedby partial oxidation of hydrocarbons:
  • Naphthalene, acenaphthylene and acenaphthene are al- 'so detected in small concentration in the gas mixture.
  • the laden wash liquor from the pre-scrubber leaves column 2 through line 29 and is mixed in line 11 with the solution from countercurrent stripper 10.
  • the bulk of the wash liquor degassed in degassing tower 12 is resupplied through line 23 and 7 or v3 to the two washing stages, while a bleed stream of 60 kg. per hour is withdrawn for distillation in still 25.
  • the distillate from still 25 is condensed and cooled and passed through line 27 and united with the wash liquor flowing in line 23. 0.52 kg. per hour of non-volatile polymers is withdrawn at 28.
  • the wash liquor at the bottom of degassing tower 12 contains 0.87% by weight of dissolved polymers. kg. per hour of water, is supplied at 20.
  • EXAMPLE 2 640 cubic meters (S.T.P.) per hour of the same acetylene-containing cracked gas as is described in Example 1 is washed with 200 kg. per hour of N-methylpyrrolidone in column 2 of the apparatus illustrated in FIGURE 3 under otherwise the same conditions.
  • the gas withdrawn through line 4 contains 0.0069% by volume of diacetylene so that 97% of the diacetylene has been washed out.
  • the laden wash liquor leaving pre-scrubber 2 through line 29 is freed from dissolved acetylene in column 30 by means of 8 cubic meters (S.T.P.) per hour of the gas escaping from absorber 6 after the absorption of acetylene, which is introduced through line 31.
  • the gas containing acetylene leaving the top of column 30 is recycled through line 32 to the suction side of compressor 5.
  • the solvent flowing away from column 30 is passed through line 33 to the top of column 17. 0.162 kg. per hour of dissolved polymers is withdrawn at 28.
  • the wash liquor contains 0.073% by weight of nonvolatile polymers at the bottom of the degassing tower 12, and 0.27% by weight of non-volatile polymers at the bottom of column 17.
  • the amounts, pressures and temperatures and also the function of the apparatus in FIG- URE 3 correspond to those given in Example 1 and FIG- URE 1. Again, the low content of polymers in the wash liquor when working according to the invention is evident.
  • EXAMPLE 3 640 cubic meters (S.T.P.) per hour of the same cracked gas as is described in Example 1 but in which no polycyclic aromatics are contained is compressed to atm. abs. in compressor 5 of an apparatus as shown diagrammatically in FIGURE 4 and passed through line 34 into scrubber 35. 116 kg. per hour of N-methylpyrrolidone is added at a temperaature of 30 C. to the top of the scrubber 35. Diacetylene cannot be detected in the pre-washed gas flow through line 37 into absorber 6.
  • the laden wash liquor from pre-scru'bber 35 flows through line 38 into column 30 while being flashed to 1.2 atm. abs. 4.3 cubic meters (S.T.P.) of the gas leaving absorber 6 is introduced per hour into column 30.
  • the wash liquor leaving column 30 is passed through line 33 to the top of column 17 and the discharge from column 17 passes through line 40 into degassing tower 12.
  • the degassed wash liquor from the bottom of column 12 is for the most part recycled through lines 23 and 7 or 36 to the two scrubbers, while a bleed stream of 60 kg. per hour is withdrawn for distillation in still 25. After condensation and cooling, the distillate is withdrawn through line 27 and united with the wash liquor flowing in line 23.
  • the wash liquor in the bottom of column 12 contains 0.12% by weight of dissolved polymers and 0.126 kg. per hour of non-volatile polymers is withdrawn at 28.
  • the expelled gas passes through line 44 in admixture with steam and N-methylpyrrolidone vapor into column 45 where the N-methylpyrrolidone vapor is washed out by washing with 5 kg. per hour of water which flows through line 48 to the top of column 45.
  • the degassed Wash liquor is removed from the bottom of column 40 through line 41. kg. per hour thereof is passed through line 43 to the top of pre-scrubber 2, while 60 kgs. per hour flows through line 42 for distillation in still 25.
  • the distillated from still 25 is condensed and cooled and passed through lines 27 and 7 to the top of the absorber 6.
  • the bulk of the wash liquor leaving degassing tower 12 is returned through lines 23 and 7 to absorber 6, while 60 kg. per hour thereof is passed through lines 49 and 3 into pre-scrubber 2.
  • wash liquor from the preliminary washing which has been thus treated is freed from absorbed constituents of poor volatility by distillation and is recycled together with the degassed main washing liquor from the main Washing and any remainder of degassed wash liquor from the preliminary washing to the two washings.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Extraction Or Liquid Replacement (AREA)
US360548A 1963-05-07 1964-04-17 Separating acetylene from gas mixtures Expired - Lifetime US3325972A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEB71781A DE1184335B (de) 1963-05-07 1963-05-07 Verfahren zur Gewinnung von Acetylen aus Gasgemischen

Publications (1)

Publication Number Publication Date
US3325972A true US3325972A (en) 1967-06-20

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US360548A Expired - Lifetime US3325972A (en) 1963-05-07 1964-04-17 Separating acetylene from gas mixtures

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US (1) US3325972A (xx)
AT (1) AT245150B (xx)
BE (1) BE647589A (xx)
DE (1) DE1184335B (xx)
GB (1) GB1051764A (xx)
NL (2) NL143729B (xx)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3894942A (en) * 1971-03-23 1975-07-15 Gen Am Transport Volatile gasoline vapor recovery system
US4701190A (en) * 1985-11-07 1987-10-20 Linde Aktiengesellschaft Process for recovering methylacetylene and/or propadiene
CN101628844A (zh) * 2008-07-18 2010-01-20 巴斯夫欧洲公司 氢化丁二炔的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE373123B (xx) * 1972-10-23 1975-01-27 Aga Ab

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2685941A (en) * 1951-01-31 1954-08-10 Universal Oil Prod Co Method for concentrating hydrogen
US2738859A (en) * 1950-10-14 1956-03-20 Basf Ag Separation of acetylene from gaseous mixtures
US2796951A (en) * 1955-11-22 1957-06-25 Lummus Co Production of olefins
US2870867A (en) * 1955-01-27 1959-01-27 Basf Ag Separation of acetylene from gas mixtures

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2738859A (en) * 1950-10-14 1956-03-20 Basf Ag Separation of acetylene from gaseous mixtures
US2685941A (en) * 1951-01-31 1954-08-10 Universal Oil Prod Co Method for concentrating hydrogen
US2870867A (en) * 1955-01-27 1959-01-27 Basf Ag Separation of acetylene from gas mixtures
US2796951A (en) * 1955-11-22 1957-06-25 Lummus Co Production of olefins

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3894942A (en) * 1971-03-23 1975-07-15 Gen Am Transport Volatile gasoline vapor recovery system
US4701190A (en) * 1985-11-07 1987-10-20 Linde Aktiengesellschaft Process for recovering methylacetylene and/or propadiene
CN101628844A (zh) * 2008-07-18 2010-01-20 巴斯夫欧洲公司 氢化丁二炔的方法
US20100016646A1 (en) * 2008-07-18 2010-01-21 Basf Se Process for hydrogenating butadiyne
US8487150B2 (en) * 2008-07-18 2013-07-16 Basf Se Process for hydrogenating butadiyne

Also Published As

Publication number Publication date
GB1051764A (xx)
NL143729B (nl) 1974-10-15
NL129845C (xx)
NL6404968A (xx) 1964-11-09
AT245150B (de) 1966-02-10
DE1184335B (de) 1964-12-31
BE647589A (xx) 1964-11-06

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