EP0000566B1 - Process for recovery of olefinic nitriles - Google Patents

Process for recovery of olefinic nitriles Download PDF

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Publication number
EP0000566B1
EP0000566B1 EP78100473A EP78100473A EP0000566B1 EP 0000566 B1 EP0000566 B1 EP 0000566B1 EP 78100473 A EP78100473 A EP 78100473A EP 78100473 A EP78100473 A EP 78100473A EP 0000566 B1 EP0000566 B1 EP 0000566B1
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EP
European Patent Office
Prior art keywords
column
stream
water
liquid
quench
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
Application number
EP78100473A
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German (de)
English (en)
French (fr)
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EP0000566A1 (en
Inventor
William Owen Fitzgibbons
Hsin Chih Wu
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Standard Oil Co
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Standard Oil Co
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Application filed by Standard Oil Co filed Critical Standard Oil Co
Publication of EP0000566A1 publication Critical patent/EP0000566A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/32—Separation; Purification; Stabilisation; Use of additives
    • C07C253/34—Separation; Purification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/26—Multiple-effect evaporating
    • 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
    • Y10S203/00—Distillation: processes, separatory
    • Y10S203/03—Acrylonitrile
    • 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
    • Y10S203/00—Distillation: processes, separatory
    • Y10S203/20—Power plant

Definitions

  • the liquid stream from the bottom of the absorber containing the various nitriles, water and some impurities is then sent to a distillation column.
  • Solvent water is used to extractively distill this stream, producing an overhead vapor stream of acrylonitrile.
  • the bottoms of the extractive distillation column may the be sent to a second stripping column.
  • the overhead of this stripping column contains acetonitrile with a minor amount of water, and the liquid bottoms stream contains water and impurities.
  • An alternative method of recovery also found in this reference, is the removal of a side-stream from the extractive distillation column.
  • the liquid bottoms stream from the extractive distillation column is mostly water and impurities with traces of acetonitrile.
  • German Patent No. 050,722 discloses a method for purification of this waste water using a separate distillation column and large amounts of steam to evaporate the water, thus reducing the size of the latter specialized waste treatment facilities.
  • the present invention provides a unique method for reducing the size of these troublesome streams with very little capital investment or operating costs.
  • the invention may be additionally stated as in the process for the recovery and purification of acrylonitrile or methacrylonitrile produced by the ammoxidation reaction of propylene or isobutylene, molecular oxygen and ammonia in the presence of ammoxidation catalysts, comprising:
  • the reactor effluent gas usually at a temperature between 371 °C. (700°F.) and 482°C. (900°F.) is first passed to a quench system.
  • the purpose of the quench system is to remove excess ammonia, polymers and heavier impurities produced by the reaction, and to cool the reactor effluent gas.
  • water with some sulfuric acid is used as a quench liquid.
  • the reactor effluent gas leaves the quench system at a temperature of about 32.2°C (90°F.) to about 110°C (230°F.).
  • a bottom stream containing water, acid, polymers and other impurities is removed from the quench system. This stream poses very difficult waste disposal problems.
  • the reactor effluent gases are then passed to an . absorber or wash column.
  • the effluent gases are contacted with water.
  • the water absorbs acrylonitrile or methacrylonitrile, acetonitrile and some impurities.
  • This aqueous solution is removed from the bottom of the wash column.
  • Non-absorbed gases are removed as a vapor stream from the top of the wash column.
  • the aqueous solution from the bottom of the absorber is then sent to further processing to recover acrylonitrile or methacrylonitrile and acetonitrile.
  • This processing is normally done in one of two ways.
  • the aqueous solution is sent to an extractive distillation column.
  • This column typically contains 60-120 trays.
  • Solvent water is added to the top of the column and passes countercurrent to the feed. Heat is applied to the bottom of the column, usually by an indirect heat exchanger.
  • Acrylonitrile or methacrylonitrile and HCN are removed as a vapor stream from the top of the column. This stream then goes to further processing to purify the acrylonitrile.
  • Acetonitrile, water and impurities are removed from the bottom of the extractive distillation column and passed to a stripper. In the stripper, large amounts of steam are used to separate the acetonitrile from the water. Acetonitrile is removed as a vapor stream overhead.
  • a bottom stream containing water and impurities is then removed from the stripper and used as the quench liquid in the quench column.
  • the present invention greatly reduces the size of the bottom stream by removing a vapor stream from the lower fourth of the stripper.
  • This vapor stream is mainly water with very little if any acetonitrile or impurities.
  • the vapor stream when condensed, is thus free of solids and hence can be fed to such waste disposal systems as an activated sludge processor or biopond for further treatment.
  • the much reduced bottom stream from the stripper is then sent to the quench column as previously described.
  • the vapor stream should be removed from below this liquid stream.
  • a second method of purifying the aqueous solution from the absorber is to pass this solution to a somewhat different extractive distillation column.
  • This column similar to the one previously described, removes a sidestream containing from the lower half of the column.
  • This sidestream is sent to a much smaller stripping column, usually consisting of 20-30 trays.
  • Acetonitrile is removed as an overhead vapor while the liquid bottoms is returned to the extractive distillation column:
  • the bottoms of this modified extractive distillation column is similar to the bottoms stream issuing from the stripper as discussed above.
  • the present invention is also applicable to this method of recovery by removing a vapor stream from the lower fourth of the extractive distillation column. This again has the advantage of greatly reducing the bottoms stream.
  • Figures 1 and 2 are schematic representations of the present invention as applied to acrylonitrile showing two methods of recovery.
  • the reactor effluent gas in conduit 100 containing acrylonitrile, HCN, acetonitrile, water vapor and impurities is first passed to a quench column 102.
  • the gas is contacted with quench liquid fed through line 130 in the quench column.
  • a bottoms stream containing water and impurities is removed through conduit 106 and sent to waste treatment.
  • the cooled reactor effluent gases leave the quench system through line 108 and pass as feed to the absorber 110. Wash water enters the absorber at the top through line 112. Noncondensible gases are removed from the absorber through line 114. An aqueous solution containing water, acrylonitrile, acetonitrile and impurities is removed as a bottoms stream through line 116 and passed to the extractive distillation column 118.
  • Solvent water is introduced to the top of column 118 through line 120 to perform extractive distillation. Acrylonitrile and HCN is removed as an overhead vapor through line 122 and sent to further purification (not shown). A bottoms stream containing acetonitrile and water is removed through line 124 and passed to stripper 126. Heat is added to the stripper to remove acetonitrile as an overhead vapor through line 128. The bottoms stream containing water, polymers and other impurities is removed through line 130 and sent back to the quench system. A vapor stream is removed via line 132 just below the first tray of this column. This vapor stream, containing mostly water, can then be condensed and sent to typical waste treatment facilities such as a sludge proessor or biopond. The removal of this vapor stream greatly reduces the amount of water issuing from the bottom of the stripper.
  • a liquid stream is removed from the lower half of the stripper through line 120 and used as a solvent water to the extractive distillation column.
  • FIG. 2 shows a second embodiment of the invention.
  • the aqueous solution from the absorber 110 is passed through line 116 to a modified extractive distillation column 150.
  • Solvent water is introduced to the top of this column through line 152 to absorb the acetonitrile.
  • Acrylonitrile and HCN is removed overhead as a vapor through line 154.
  • a liquid stream containing acetonitrile and water is removed from the bottom half of this column through line 158 and sent to a small stripping column 160.
  • Acetonitrile passes overhead as a vapor through line 162.
  • a liquid stream containing mostly water is removed from the bottom of column 160 through line 164 and returned to the extractive distillation column.
  • the present invention's vapor stream is removed from below the first tray of the distillation column through line 166 and condensed in condenser 168.
  • the condensed stream containing mostly water is then passed through line 170 to waste treatment as described above.
  • a bottoms stream containing water, polymers and impurities is removed through line 156 and sent back to the quench system.
  • a liquid stream is removed from the bottommost trays and returned to the extractive distillation column as solvent water through line 152.
  • Example 1 An acrylonitrile recovery is performed substantially as shown in Figure 2.
  • Comparative Example A the total liquid bottoms streams from the extractive distillation column is sent to the quench system.
  • Example 1 is identical to Comparative Example A except that a vapor stream is removed from below the first tray of the extractive distillation column. The amount of this vapor stream was equal to 45% by weight of the original bottoms stream in Comparative Example A. Because of this vapor removal, the amount of heat necessary to perform the distillation was increased by 12%.
  • the Table below shows the weight per cent polymer contained in the various process streams of both examples.
  • the vapor stream removed from the distillation column contains extremely small amounts of polymer.
  • the effects of the present invention can easily be seen by the dramatic increase in polymer concentration in the quench bottoms stream. This concentration of polymer has been doubled through the use of the invention. Additionally, the quench bottoms stream is reduced by approximately 60%. Thus, a much smaller stream more highly concentrated in polymer is obtained. This has the advantage of greatly reducing the cost and further disposal of this stream.
  • the amount of vapors that may be removed when using the present invention is related to the bottom stream of the column.
  • the amount of vapors removed can be 10 to 70 weight per cent of the bottoms stream prior to vapor removal. It is preferred, however, that 30-50 weight per cent be removed. This will leave a sufficient quantity of water for use in the quench system.
  • the vapor stream can be condensed and because of its extremely low polymer concentration be sent to typical waste water purification systems such as biopond or activated sludge treatment.
  • the use of the present invention greatly reduces the amount of quench bottoms to be purified and also increases its polymer concentration. This makes waste treatment of this stream far more economical and reduces the size of the associated equipment.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP78100473A 1977-07-29 1978-07-21 Process for recovery of olefinic nitriles Expired EP0000566B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US05/820,479 US4166008A (en) 1977-07-29 1977-07-29 Process for recovery of olefinic nitriles
US820479 1977-07-29

Publications (2)

Publication Number Publication Date
EP0000566A1 EP0000566A1 (en) 1979-02-07
EP0000566B1 true EP0000566B1 (en) 1981-09-02

Family

ID=25230894

Family Applications (1)

Application Number Title Priority Date Filing Date
EP78100473A Expired EP0000566B1 (en) 1977-07-29 1978-07-21 Process for recovery of olefinic nitriles

Country Status (30)

Country Link
US (1) US4166008A (it)
EP (1) EP0000566B1 (it)
JP (1) JPS5427524A (it)
AR (1) AR222800A1 (it)
AT (1) AT364814B (it)
AU (1) AU519153B2 (it)
BG (1) BG51249A3 (it)
BR (1) BR7804802A (it)
CA (1) CA1117978A (it)
CS (1) CS205131B2 (it)
DD (1) DD140037A5 (it)
DE (1) DE2861004D1 (it)
DK (1) DK336978A (it)
EG (1) EG13388A (it)
ES (2) ES472142A1 (it)
FI (1) FI782217A (it)
GR (1) GR64946B (it)
HU (1) HU184180B (it)
IE (1) IE47217B1 (it)
IL (1) IL55009A (it)
IN (1) IN147953B (it)
IT (1) IT1097152B (it)
MX (1) MX149220A (it)
NO (1) NO144487C (it)
PH (1) PH16172A (it)
PL (1) PL115232B1 (it)
PT (1) PT68308A (it)
RO (1) RO74849A (it)
TR (1) TR20028A (it)
ZA (1) ZA783858B (it)

Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4269667A (en) * 1979-08-02 1981-05-26 Standard Oil Company Acrylonitrile purification by extractive distillation
US4334965A (en) * 1980-12-31 1982-06-15 Standard Oil Company Process for recovery of olefinic nitriles
JPS58124753A (ja) * 1982-01-20 1983-07-25 ザ・スタンダ−ド・オイル・カンパニ− オレフインニトリルの回収法
JPS58225048A (ja) * 1982-06-22 1983-12-27 Asahi Chem Ind Co Ltd メタクリロニトリルの製造法
US4404064A (en) * 1982-12-30 1983-09-13 Monsanto Company Water extractive distillation of olefinically unsaturated nitriles
EP0938469B1 (en) * 1996-10-23 2001-06-20 Solutia Inc. Process for purifying acrylonitrile
EP0937707B1 (en) * 1998-02-23 2003-04-16 The Standard Oil Company Improved purification and recovery of acetonitrile
US5869730A (en) * 1998-05-13 1999-02-09 The Standard Oil Company Oxidant reduction by manipulation and/or treatment of aqueous acrylonitrile process streams
WO1999065583A1 (en) * 1998-06-15 1999-12-23 Solutia Inc. Process for recovery of olefinically unsaturated nitriles
US6197855B1 (en) * 1998-09-29 2001-03-06 Solutia Inc. Nucleation of Polyamides in the presence of hypophosphite
US6107509A (en) * 1999-03-31 2000-08-22 The Standard Oil Company Process for the recovery of acrylonitrile and methacrylontrile
JP2004217656A (ja) * 2003-01-14 2004-08-05 Solutia Inc アクリロニトリル精製プロセスにおける凝縮させた冷却オーバーヘッドの再循環
US20090299087A1 (en) * 2008-05-28 2009-12-03 Solutia, Inc. Process for manufacturing unsaturated mononitriles to improve on-stream time and reduce fouling
JP5476774B2 (ja) * 2009-04-07 2014-04-23 三菱レイヨン株式会社 （メタ）アクリロニトリルの回収方法
CN104941419A (zh) 2014-03-31 2015-09-30 英尼奥斯欧洲股份公司 反应器流出物的改进的氨移除
CN104941380A (zh) 2014-03-31 2015-09-30 英尼奥斯欧洲股份公司 用于淬冷流出物的改进的烟雾消除器操作
CN109499085A (zh) 2014-06-11 2019-03-22 英尼奥斯欧洲股份公司 丙烯腈回收的乙腈移除步骤中的污染减轻
CN113813622A (zh) * 2014-09-29 2021-12-21 英尼奥斯欧洲股份公司 用于工艺流的蒸发***
CN105521615A (zh) * 2014-09-29 2016-04-27 英尼奥斯欧洲股份公司 用于工艺流的蒸发***
CN104587684A (zh) 2014-09-30 2015-05-06 英尼奥斯欧洲股份公司 用于工艺流的蒸发***

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3149055A (en) * 1962-08-22 1964-09-15 Standard Oil Co Purification of olefinically unsaturated nitriles
FR1427860A (fr) * 1964-12-24 1966-02-11 Electrochimie Soc Perfectionnements aux procédés d'obtention d'acrylonitrile et d'acétonitrile purs
US3399120A (en) * 1965-12-09 1968-08-27 Monsanto Co Purification of olefinically unsaturated nitriles by water extractive distillation
US3352764A (en) * 1966-05-02 1967-11-14 Standard Oil Co Absorption and distillation process for separating crude unsaturated nitriles from acetonitrile with selective solvent recycle
US3507755A (en) * 1967-10-17 1970-04-21 Bayer Ag Process for the purification of acrylonitrile by distillation with side stream withdrawal and decantation
US3936360A (en) * 1971-04-07 1976-02-03 The Standard Oil Company Process for distillation and recovery of olefinic nitriles
US3734943A (en) * 1971-05-06 1973-05-22 Standard Oil Co Deep well disposal process for acrylonitrile process waste water
CA964434A (en) * 1971-08-02 1975-03-18 Badger Company Disposal of waste material from unsaturated nitrile plant
US3862890A (en) * 1971-09-03 1975-01-28 Robert D Presson Fractional distillation using a vapor side stream to control hcn concentration in purificatin of crude nitriles

Also Published As

Publication number Publication date
CS205131B2 (en) 1981-04-30
PT68308A (en) 1978-08-01
IT7825630A0 (it) 1978-07-12
GR64946B (en) 1980-06-10
ES472882A1 (es) 1979-02-16
IE47217B1 (en) 1984-01-25
IT1097152B (it) 1985-08-26
PH16172A (en) 1983-07-21
CA1117978A (en) 1982-02-09
JPS6141346B2 (it) 1986-09-13
HU184180B (en) 1984-07-30
NO782598L (no) 1979-01-30
RO74849A (ro) 1980-10-30
DD140037A5 (de) 1980-02-06
IL55009A (en) 1981-06-29
PL115232B1 (en) 1981-03-31
NO144487C (no) 1981-09-09
EG13388A (en) 1981-06-30
IL55009A0 (en) 1978-08-31
JPS5427524A (en) 1979-03-01
EP0000566A1 (en) 1979-02-07
DE2861004D1 (en) 1981-11-26
AT364814B (de) 1981-11-25
TR20028A (tr) 1980-07-01
AU519153B2 (en) 1981-11-12
BG51249A3 (en) 1993-03-15
PL208705A1 (pl) 1979-07-02
ATA555578A (de) 1981-04-15
FI782217A (fi) 1979-01-30
ES472142A1 (es) 1979-03-16
NO144487B (no) 1981-06-01
AU3770178A (en) 1980-01-10
US4166008A (en) 1979-08-28
IE781525L (en) 1979-01-29
IN147953B (it) 1980-08-23
DK336978A (da) 1979-01-30
AR222800A1 (es) 1981-06-30
MX149220A (es) 1983-09-27
ZA783858B (en) 1979-07-25
BR7804802A (pt) 1979-04-24

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