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WO2016036655A1 - Procédé amélioré de récupération du formaldéhyde - Google Patents

Procédé amélioré de récupération du formaldéhyde Download PDF

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Publication number
WO2016036655A1
WO2016036655A1 PCT/US2015/047711 US2015047711W WO2016036655A1 WO 2016036655 A1 WO2016036655 A1 WO 2016036655A1 US 2015047711 W US2015047711 W US 2015047711W WO 2016036655 A1 WO2016036655 A1 WO 2016036655A1
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WO
WIPO (PCT)
Prior art keywords
steam
column
formaldehyde
stream
condenser
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.)
Ceased
Application number
PCT/US2015/047711
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English (en)
Inventor
Graham R. AIRD
Philip N. WARD
Darren Gobby
Dena Ghiasy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Invista North America LLC
Original Assignee
Invista North America LLC
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Invista North America LLC filed Critical Invista North America LLC
Priority to CN201580047127.1A priority Critical patent/CN107074711A/zh
Publication of WO2016036655A1 publication Critical patent/WO2016036655A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/44—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon double or triple bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation

Definitions

  • the present invention relates to an improved method for optimizing energy use in the recycle of unreacted formaldehyde from butynediol reactor product.
  • the method involves feeding a stream comprising unreacted formaldehyde downstream from a butynediol synthesis reactor to a column maintained at specific conditions, removing a top stream from the column comprising formaldehyde, water and methano!, for recycle and treatment to remove some methanol, and removing a bottom stream from the column comprising butynediol, water, methanol and less than 1 wt % by weight formaldehyde, for further processing to create butanediol of the required quality.
  • Energy optimization is achieved by raising steam from steam condensate, which has been generated in the column reboiler, in a column overheads product condenser/steam raiser unit, and passing the steam from the condenser/steam raiser unit through a compressor for use in the column reboiler, or by simply raising steam from steam condensate generated in the column reboiier in the column overheads product
  • butynediol In current processes for manufacturing butanediol, acetylene and formaldehyde are converted into butynediol, which is in turn hydrogenated to form butanediol.
  • the synthesis of butynediol from acetylene and formaldehyde has been described, for example, in K. Weisserme!, H.-J. Arpe, harmonyie Organische Chemie [Industrial Organic Chemistry], 5th Edition, 1998, Wiley-VCH, pages 110 and 111).
  • the catalysts typically used in this synthesis may, if appropriate, comprise bismuth and also silica (Si0 2 ) or alumina (Ai 2 0 3 ).
  • Patent publication DD-A 272 644 discloses the suspension hydrogenation of aqueous butynediol over nickel-Si0 2 catalyst, and EP-B 0 319 208, DE-A 19 41 633 and DE-A 20 40 501 disclose general hydrogenation processes which may be applicable to butynediol.
  • Butynedioi may be manufactured from a reaction mixture comprising an aqueous solution containing formaidehyde, acetylene and suspended catalyst in a reaction vessel.
  • 4,584,418A describes a means for making a copper acetyiide cataiyst for synthesis of butynedioi in a single vessel wherein acetylene is bubbled through the reactor at 90 °C and atmospheric pressure.
  • 5,444, 169A discloses a process for synthesizing butynedioi from an aqueous solution containing formaldehyde by reaction with acetylene in the presence of a suspended catalyst, wherein the solution is conveyed in a cascade by several reactors, the solution drawn off from the first through the penultimate reactor of the cascade being fed to the next reactor in the cascade, acetylene being introduced into each of the reactors, and a butynedio!-rich solution being drawn off only from the last reactor in the cascade.
  • the catalyst is separated from the solution in each individual reactor of the cascade above the last reactor to prevent the catalyst from escaping the reactor.
  • unreacted formaldehyde is a valuable component which should be recovered and recycled to make the overall process more commercially advantageous.
  • This is typically done by feeding the butynedio! synthesis reactor effluent ultimately to a distillation column in which methanol, formaldehyde and water are removed from the top, while butynedioi, water and methanol and a small amount of formaldehyde are removed from the bottom.
  • This can be an energy intensive operation; particularly if the butynedioi reactor is operated at a comparatively low formaldehyde conversion.
  • To achieve low concentrations of formaldehyde requires longer residence times and requires use of large butynedio!
  • the present invention provides an economical improved method for recovering and recycling unreacted formaldehyde from a butynedioi synthesis reaction product stream.
  • An embodiment of the invention method involves the steps of: a) feeding the reaction product comprising unreacted formaldehyde to a column maintained at specific conditions, the column associated with a reboiler, b) removing a vapor phase top stream comprising formaldehyde, water and methanol from the column of step a), and passing at least a portion thereof to a condenser/steam raiser maintained at specific conditions, wherein steam is raised from steam condensate or boiler feed water by heat interchange with the vapor phase top stream and a process condensate stream is generated from the vapor phase top stream, c) removing a liquid phase bottom stream comprising butynediol, water, formaldehyde and methanol from the coiumn of step a), d) removing the process condensate stream of step b), and passing
  • Another embodiment of the invention method involves the steps of: a) feeding the reaction product composition comprising unreacted formaldehyde to a coiumn maintained at specific conditions including a top temperature of from 115 to 150 °C, and a bottom temperature of from 130 to 170 °C, the column associated with a reboiler, b) removing a vapor phase top stream comprising water, methanol and at least 25 wt % formaldehyde, from the column of step a), and passing an 80 to 100 wt % portion thereof to a
  • condenser/steam raiser maintained at specific conditions, wherein steam is raised from steam condensate or boiler feed water by heat interchange with the vapor phase top stream and a process condensate stream is generated from the vapor phase top stream, c) removing a liquid phase bottom stream comprising butynediol, water, methanol and at most 1 wt % formaldehyde from the column of step a), d) removing the process condensate stream of step b), and passing a 50 to 70 wt % portion thereof back to the column of step a) as reflux, e) removing steam from the condenser/steam raiser of step b), and passing the steam through a compressor and to the reboiler of the coiumn of step a), and f) passing a portion of steam condensate from the reboiler of the coiumn in step a) to the
  • Another embodiment of the invention involves the above steps wherein the compressor of step e) increases the pressure of the condenser/steam riser product by a factor of from 2 to 10.
  • Another embodiment of the invention involves the above steps preceded by reacting a mixture comprising an aqueous solution containing formaldehyde, acetylene and suspended catalyst in a reaction vessel at reaction conditions to yield the reaction product composition comprising unreacted formaldehyde.
  • another embodiment of the invention comprises the steps of: 1) reacting a mixture comprising an aqueous solution containing formaldehyde, acetylene and suspended catalyst in a reaction vessel at reaction conditions to yield a reaction product comprising butynediol, water, unreacted formaldehyde and methanol, 2 ⁇ feeding the reaction product of step 1) comprising butynediol, water, unreacted formaidehyde and methanol to a column maintained at specific conditions, the column associated with a reboiler, 3) removing a vapor phase top stream comprising formaldehyde, water and methanol from the column of step 2), and passing an 80 to 100 wt % portion thereof to a condenser/steam raiser maintained at conditions, wherein steam is raised from steam condensate or boiler feed water by heat interchange with the vapor phase top stream and a process condensate stream is generated from the vapor phase top stream, 4) removing a liquid phase bottom stream comprising but
  • Fig. 1 shows a diagrammatic flow of an embodiment of the present method.
  • the method involves feeding the reaction product composition comprising unreacted formaldehyde to a column maintained at specific conditions, the column associated with a reboiler, removing a vapor phase top stream from the column comprising formaldehyde, water and methanol, and passing at least a portion of the recovered top stream to a condenser/steam riser maintained at specific conditions, removing a liquid phase stream from the column condenser/steam raiser comprising butynediol, water, methanol and unreacted formaldehyde for recycle to the butynediol reactor and providing column reflux, raising steam in the condenser/steam raiser by heat interchange with the column vapor phase top steam, removing the steam from the condenser/steam raiser and passing it through a compressor to increase the steam pressure prior to passing it to the column reboiler, and then passing the higher pressure steam condensate from the reboiler back to the condenser/steam raiser
  • An embodiment of this method comprises feeding the reaction product composition comprising unreacted formaldehyde to a column maintained at specific conditions, removing a vapor phase top stream comprising formaldehyde, water and methano!, and passing at ieast a portion of the recovered top stream to a condenser/steam riser maintained at specific conditions, removing a liquid phase bottom stream from the column comprising butynediol, water, methanoi and unreacted formaldehyde, and passing at ieast a portion thereof to a reboiier maintained at specific conditions, removing steam product and condensate from the condenser/steam riser, and passing the steam product from the condenser/steam riser through a compressor and to the reboiier, removing a top stream from the condenser/steam riser, and passing at ieast a portion thereof to the top of the column as reflux, passing condensate from the reboiier to the top
  • BYD butynedioi
  • BDO butanediol
  • an embodiment of such a process involves manufacturing BYD from a reaction mixture comprising an aqueous solution containing formaldehyde, acetylene and suspended catalyst in a single or series of reaction vessels containing internal filters, such as candle filters, for separation of suspended catalyst from reaction product.
  • reaction vessels catalyst solids build up on the fi!ters as cake which can be removed by back flushing each filter reguiar!y to avoid plugging the reactor vessel
  • recovered product comprising BYD, water, unreacted formaldehyde and methanol.
  • Another embodiment of such a process involves manufacturing BYD from a reaction mixture comprising an aqueous solution containing formaldehyde, acetylene and suspended catalyst in a reaction vessel whereby a product slurry stream comprising BYD, water, unreacted formaldehyde, methanol and suspended catalyst is passed from the reaction vessel to a filter external from the reaction vessel where the suspended catalyst is removed, allowing for recovery of product comprising BYD, water, unreacted formaldehyde and methanol.
  • the BYD synthesis reaction product composition downstream from a BYD synthesis reactor for use herein typically comprises from 30 to 50 wt % BYD, 40 to 60 wt % water, 1 to15 wt % unreacted formaldehyde, and 2 to 7 wt % methanol, on a solids free basis.
  • the reaction vessel for use in a process for manufacturing BYD may comprise one of current use in such a process.
  • Such a reaction vessel may be a bubble column wherein acetylene and other gases are injected at the base of the reactor both to conduct the reaction and to maintain the catalyst solids in suspension, or a stirred tank reactor which uses an agitator to maintain catalyst soiids in suspension and to assist in gas dispersion, or some combination thereof.
  • Reaction conditions in such a reaction vessel include a temperature of from 40 to 1 10 °C, for example, from 60 to 1 10 °C, pressure from 0 to 200 kPa.A, for example from 9 to 1 10 kPa.A, and pH from 3 to 9. Contents of the reaction vessel are agitated by either or both of mechanical means, for example a stirrer, or gaseous injection.
  • Catalyst for use in the reaction vessel for manufacturing BYD and suspended as solids in the product slurry stream comprising BYD, water, unreacted formaldehyde and methanol may be added to the reaction zone or produced in the reaction zone.
  • the catalyst may comprise copper, and a catalyst precursor may comprise a compound of copper, such as, for example, copper carbonate.
  • the new improved method of this invention involves recovering unreacted formaldehyde from a BYD synthesis reaction product composition downstream from a BYD synthesis reactor using a formaldehyde recycle column ("column") in a method designed to reduce the variable costs associated with such an effort.
  • the column used is a conventional distillation column with steam heating applied at the base of the column by way of a reboiler, and water cooling applied at the top of the column by way of a condenser/steam riser.
  • This method utilizes the heat available in the column overheads using water as an external working fluid. The working fluid is vaporized by exchanging heat with the overheads in the condenser/steam riser.
  • This low pressure steam is then compressed in a compressor and subsequently used as the heating medium for the column reboiler.
  • the high pressure condensate from the column reboiler is then sent back to the condenser/steam riser to be vaporized and recompressed.
  • This vapor recompression scheme (loop) results in significant reductions in consumption of high pressure steam and cooling water usage.
  • the column used herein may comprise one of current use in such a unit operation, such as, for example, a trayed or packed column.
  • the conditions maintained for the column include a top temperature of from 1 15 to 50 °C, and bottom temperature of from 130 to 170 °C.
  • the column top pressure will be from 100 to 600 kPa.A.
  • most of the column energy demand is supplied by the loop described above; however, when the heat available in the condenser/steam riser is lower than that required by the reboi!er, for examp!e if a vapor purge is taken from the column, the difference between the two duties is provided by utility steam supplied directly to the reboi!er.
  • the use of water as the working fluid allows direct injection of utility steam in the same heat exchanger. This not only eliminates the need for having a separate auxiliary reboiler, it also increases the degrees of freedom in control and operation of the heat pump loop.
  • the condenser/steam riser used herein may comprise one of current use in such a unit operation, such as, for example, a shell and tube heat exchanger with steam generation in the shell side.
  • the conditions maintained for the condenser/steam riser for use herein include a pressure from 0 to 400 kPa.A raising saturated steam.
  • the coiumn reboiler used herein may comprise one of current use in such a unit operation, such as, for example, a vertical thermosyphon or a forced circulation heater.
  • the conditions maintained for the reboiler for use herein include a pressure from 400 to 1400 kPa.A.
  • the compressor of step e) used herein may comprise one of current use in such a unit operation, such as, for example, a reciprocating or axial compressor or a steam ejector or thermocompressor.
  • the compressor increases the pressure of the steam raised in the condenser/steam raiser by a factor of from 2 to 10, such as, for example from 3 to 5.
  • the top stream recovered from the column in the present method comprises at least 25 wt % formaldehyde and the bottom stream recovered from the column comprises at most 1 wt % formaldehyde. More specifically, the top stream recovered from the column comprises from 25 to 35 wt % formaldehyde, 50 to 60 wt % water, and 5 to 15 wt % methanol; and the bottom stream recovered from the column comprises 50 to 60 wt % BYD, 40 to 50 wt % water, from 0 to ⁇ 0.1 wt % methanol, and 0.2 to 1 wt % formaldehyde.
  • step b) of the present improved method an 80 to 100 wt % portion, for example a 93 to 100 wt % portion, of the top stream removed from the column of step a) is passed to the condenser/steam riser, where steam is raised by heat interchange with the condensing stream.
  • This may be accomplished by, for exampie, flow split control using a simple control ioop.
  • Raising steam in the condenser/steam riser may be accomplished by, for example, utilizing a shell and tube heat exchanger to raise steam on the shell side.
  • a 0 to 100 wt % portion, for example an 80 to 100 wt % portion, of the steam raised in the condenser/steam raiser is compressed for use in the reboiler of the column of step a).
  • This may be accomplished by, for example, a reciprocating or turbo compressor and a thermosyphon or forced circulation reboiler.
  • Fig. 1 shows an embodiment of the present invention wherein a liquid phase effluent from a BYD manufacturing step of a BYD manufacturing process comprising 37 wt % BYD, 10 wt % unreacted formaldehyde, 49 wt % water and 4 wt % methanol (on a soiids free basis) is passed via line 1 to a formaldehyde recycle column 00 maintained at a top temperature of 148 °C and a bottom temperature of 160 °C.
  • a formaldehyde recycle column 00 maintained at a top temperature of 148 °C and a bottom temperature of 160 °C.
  • a vapor phase product comprising 30 wt % formaldehyde, 58 wt % water and 12 wt % methanol is removed via line 2 from the top of column 100, whereby a 7 wt % portion thereof is removed via line 4 by way of a flow split control using a simple control ioop (not shown), and the remainder is passed via line 5 to the condenser/steam raiser 1 10 maintained at 250 kPa.A on the steam raising side.
  • a liquid phase bottoms stream comprising approximately 54 wt % BYD, 45 wt % water, ⁇ 0.1 wt % methanol and ⁇ 1 wt % formaldehyde is recovered from column 100 via line 6.
  • the remainder of the liquid phase bottoms stream i.e. 95 to 00 wt %, for example 98 to 100 wt %, is recovered as refined butynediol for further processing to butanediol.
  • the column side (process side) of the reboiler 130 As accepted engineering practice, the reboiler 130 provides sufficient steam to maintain the column 100 base temperature at 160 °C.
  • Any required fresh boiler feed water at about 800 kPa.A at its bubble point temperature is fed to condenser/steam raiser 1 10 via line 14.
  • a steam product is removed from condenser/steam raiser 10 via line 8 at a pressure of about 250 kPa.A, and steam condensate purge is removed from condenser/steam raiser 1 10 via line 13.
  • a process condensate stream comprising 30 wt % formaldehyde, 58 wt % water and 12 wt % methanol from condenser/steam raiser 1 10 is withdrawn via line 10, whereby a 35 wt % portion thereof is removed via line 1 1 for recycle by way of a flow split control using a simple control loop (not shown), and a 65wt % portion thereof is passed via tine 12 to the top of column 100 as reflux.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé amélioré de récupération du formaldéhyde n'ayant pas réagi à partir d'un produit de réaction de la synthèse du butynediol en aval d'un réacteur de synthèse du butynediol.
PCT/US2015/047711 2014-09-04 2015-08-31 Procédé amélioré de récupération du formaldéhyde Ceased WO2016036655A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201580047127.1A CN107074711A (zh) 2014-09-04 2015-08-31 改进的甲醛回收方法

Applications Claiming Priority (2)

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US201462046079P 2014-09-04 2014-09-04
US62/046,079 2014-09-04

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WO2016036655A1 true WO2016036655A1 (fr) 2016-03-10

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107089901A (zh) * 2017-06-27 2017-08-25 查都（上海）科技有限公司 一种1,4‑丁炔二醇提纯系统
CN110092711A (zh) * 2019-05-20 2019-08-06 中国石化长城能源化工（宁夏）有限公司 一种丁醇提纯工艺的甲醛分离方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3129252A (en) * 1960-12-29 1964-04-14 Gen Aniline & Fihn Corp Purification of butynediol
US3154589A (en) * 1960-06-27 1964-10-27 Allied Chem Process for butynediol
US20080242897A1 (en) * 2005-09-06 2008-10-02 Basf Se Method For The Separation Of Polymeric By-Products From 1,4-Butynediol
US7538254B2 (en) * 2005-09-06 2009-05-26 Basf Aktiengesellschaft Method for the separation of polymeric by-products from 1,4-butynediol
WO2013081713A1 (fr) * 2011-11-28 2013-06-06 Invista Technolgies S.A.R.L. Traitement caustique d'une alimentation de colonne de recyclage de formaldéhyde

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5068468A (en) * 1990-10-19 1991-11-26 Basf Aktiengesellschaft Hydrogenation of acetylenic alcohols
DE4120446A1 (de) * 1991-06-20 1992-12-24 Linde Ag Verfahren und vorrichtung zur synthese von butindiol
DE19508751A1 (de) * 1995-03-10 1996-09-12 Linde Ag Verfahren zum Abtrennen der Schwersiederfraktion aus einer Roh-Butindiollösung

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3154589A (en) * 1960-06-27 1964-10-27 Allied Chem Process for butynediol
US3129252A (en) * 1960-12-29 1964-04-14 Gen Aniline & Fihn Corp Purification of butynediol
US20080242897A1 (en) * 2005-09-06 2008-10-02 Basf Se Method For The Separation Of Polymeric By-Products From 1,4-Butynediol
US7538254B2 (en) * 2005-09-06 2009-05-26 Basf Aktiengesellschaft Method for the separation of polymeric by-products from 1,4-butynediol
WO2013081713A1 (fr) * 2011-11-28 2013-06-06 Invista Technolgies S.A.R.L. Traitement caustique d'une alimentation de colonne de recyclage de formaldéhyde

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107089901A (zh) * 2017-06-27 2017-08-25 查都（上海）科技有限公司 一种1,4‑丁炔二醇提纯系统
CN110092711A (zh) * 2019-05-20 2019-08-06 中国石化长城能源化工（宁夏）有限公司 一种丁醇提纯工艺的甲醛分离方法

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