CN104355986A - Method for producing acetic acid - Google Patents

Method for producing acetic acid Download PDF

Info

Publication number
CN104355986A
CN104355986A CN201410617867.1A CN201410617867A CN104355986A CN 104355986 A CN104355986 A CN 104355986A CN 201410617867 A CN201410617867 A CN 201410617867A CN 104355986 A CN104355986 A CN 104355986A
Authority
CN
China
Prior art keywords
acetic acid
reactor
oxidized
ethane
ethene
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.)
Pending
Application number
CN201410617867.1A
Other languages
Chinese (zh)
Inventor
朱忠良
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to CN201410617867.1A priority Critical patent/CN104355986A/en
Publication of CN104355986A publication Critical patent/CN104355986A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a method for producing acetic acid. The method comprises the following steps: oxidizing ethane in a first reactor, so as to generate first flowout material flow containing acetic and ethylene; oxidizing the first flowout material flow in a second reactor under the condition of sufficiently oxidizing at least one part of ethylene to acetic acid, to obtain a second material flow, wherein the step of oxidizing the ethane is carried out at 400DEG C-500DEG C, and the step of oxidizing the first flowout material flow in the second reactor is carried out in the second reactor at 150DEG C to 250DEG C; oxidizing ethane in a third reactor at the temperature 520-580DEG C, wherein the third reactor is a fluidized bed reactor; and mixing the generated acetic acid and the second material flow to obtain a product acetic acid. The acetic acid material flow generated by adopting the technology is especially suitable as an acetic acid raw material for synthesizing vinyl acetate, and the method has the advantages of being high in selectivity, high in yield, and low in separation cost when acetic acid material is used for synthesizing vinyl acetate.

Description

A kind of method for the production of acetic acid
Technical field
The present invention relates to a kind of method for the production of acetic acid.
Background technology
The catalytic vapor phase oxidation of ethane becomes ethene and acetic acid to be known for a long time.Reaction affects by the selection of reaction conditions substantially, and this selectivity for reaction particularly like this.Generally, acetic acid is only formed as by product, and primary product is ethene, and ethene can be oxidized to carbonic acid gas in some cases further.Usually, the method is included in fluidized-bed reactor or fixed-bed reactor and gaseous feed is reacted.Gaseous feed comprises ethane and/or ethene, and it is fed in reactor with scrubbed gas or with the form of the mixture of one or more other gases.Such additional gas or the example of vector gas are nitrogen, methane, carbon monoxide, carbonic acid gas, air and/or water vapour.The gas comprising molecular oxygen can be air, or than the gas of air containing more or less molecular oxygen, such as oxygen.Higher oxygen level is preferred, because attainable ethane conversion is higher, and therefore the productive rate of acetic acid is higher.The gas of oxygen or molecule-containing keto preferably adds, because this makes described method more easily carry out with the concentration range outside limits of explosion at reaction conditions.But, also can be used in the ratio of ethane/ethylene in limits of explosion and oxygen.Reaction is carried out at the temperature of 400-600 DEG C, and pressure can be normal pressure or higher than normal pressure, such as, in the scope of 1-50 bar.Oxygen or comprise molecular oxygen gas feed before, ethane usually first with rare gas element as nitrogen or water vapour mix.Before making gaseous mixture and catalyst exposure, mixed gas is preferably preheated to temperature of reaction in preheating zone.By condensation from the gas delivery acetic acid leaving reactor.Remaining gas re-circulation, to the entrance of reactor, in this ingress, is metered into oxygen or comprises the gas of molecular oxygen and ethane and/or ethene.The gas of recirculation always comprises ethene and ethane.
WO 98/47850 and WO 98/47851 describes and uses Mo apd bx cy din fixed bed, prepared the method for acetic acid by the partial oxidation of ethane as catalyzer.Catalyzer has high stability and highly selective in the oxidation of ethane to acetic acid.But, there is difficulty in process by the following fact: ethane is strong heat release to the oxidation of acetic acid.Particularly in larger fixed-bed reactor, remove reaction heat only unsatisfactoryly.This causes the increase of temperature in reactor and the reduction of therefore reaction preference.For head it off, carry out attempting reacting in liquid catalyst fluidized-bed, such as, at US 5,300, described in 684, wherein cooling tube is located immediately in fluidized-bed reactor to remove heat.The specific embodiments further developed of technique is described in WO 00/14047.
For the catalyzer of reaction, DE 19620542 describes at elevated temperatures from the method for the gaseous feed selective production of acetic acid of ethane, ethene or its mixture and oxygen, wherein said gaseous feed and catalyst mix, this catalyzer comprises the element of be combined with oxygen a: b: c: d: e: Mo apd bre cx dy e, wherein symbol X and Y is defined as follows: X=Cr, Mn, Nb, B, Ta, Ti, V and/or W; Y=Bi, Ce, Co, Cu, Te, Fe, Li, K, Na, Rb, Be, Mg, Ca, Sr, Ba, Ni, P, Pb, Sb, Si, Sn, Tl and/or U; Coefficient a, b, c, d and e are the grammeatom ratio of respective element, wherein a=1, b > 0, c > 0, d=0.05-2, e=0-3.In the presented embodiments, under 280 DEG C and 15 bar, ethane conversion is up to 8%, and the selectivity of acetic acid is 91% to the maximum.
DE 19630832 discloses at elevated temperatures, from the method for the gaseous feed selective production of acetic acid of ethane, ethene or its mixture and oxygen.Said charging and catalyst mix, this catalyzer is containing elements Mo, Pd, X and Y and oxygen.X is one or more elements being selected from Cr, Mn, Nb, Ta, Ti, V, Te and W herein, and Y is one or more elements being selected from B, Al, Ga, In, Pt, Zn, Cd, Bi, Ce, Co, Rh, Ir, Cu, Ag, Au, Fe, Ru, Os, K, Rb, Cs, Mg, Ca, Sr, Ba, Zr, Hf, Ni, P, Pb, Sb, Si, Sn, T1 and U.The grammeatom of respective element is than as follows: a (Mo)=1; B (Pd) > 0; C (X) > 0; D (Y)=0-2.
Invention DE 19745902 relates at elevated temperatures, from the method for the gaseous feed selective production of acetic acid of ethane, ethene or its mixture and oxygen, wherein said gaseous feed is combined with catalyzer, this catalyzer is containing the elements Mo be combined with oxygen, Pd, X and Y, and their grammeatom ratio is a: b: c: d:Mo apd bx cy d; Symbol X and Y has following implication: X is one or more elements, particularly V and W of being selected from Cr, Mn, Ta, Ti, V, Te and W; Y is one or more elements, particularly Nb, Ca, Sb and Li of being selected from B, Al, Ga, In, Pt, Zn, Cd, Bi, Ce, Co, Cu, Rh, Ir, Au, Ag, Fe, Ru, Os, K, Rb, Cs, Mg, Ca, Sr, Ba, Nb, Zr, Hf, Ni, P, Pb, Sb, Si, Sn, Tl and U.Coefficient a, b, c and d are the grammeatom ratio of respective element, wherein a=1, b=0.0001-0.01, c=0.4-1, d=0.005-1.If X and Y is multiple different element, then coefficient c and d adopts multiple different value equally.
In DE-A-19745902, catalyzer is that from the slurry of each starting elemental component containing corresponding proportion, particularly the aqueous solution is prepared from by conventional method.According to this invention, the raw material for the preparation of each component of catalyzer is, except oxide compound, and preferably water soluble substance, such as ammonium salt, nitrate, vitriol, halogenide, oxyhydroxide and the organic acid salt of corresponding oxide can be become by thermal conversion.In order to mix these components, prepare and the aqueous solution of mixed metal salt or suspension.For example for molybdenum, consider commercially available property, recommend to adopt corresponding molybdate, such as ammonium molybdate, as precursor compound.Palladium compound used is such as Palladous chloride (II), palladous sulfate (II), tetraamine palladium nitrate (II), Palladous nitrate (II) and palladium acetylacetonate (II).
A kind of acetic acid of common prior art.In this fundamental system, the stream comprising ethane and the gas comprising oxygen are together fed to ethane oxidation reactor.This reactor can be fluidized-bed reactor or fixed-bed reactor.In the reactor, ethane is oxidized to acetic acid, ethene and various oxycarbide (COx).Gas reactor effluent containing these three kinds of main ingredients is fed to recycle gas, and it produces the top stream containing ethene, ethane and COx.Top stream from described recycle gas enters the treatment step removing COx from top stream.Then the stream of purifying is recycled to oxidation reactor to change into acetic acid further.Containing acetic acid, water and heavy ends by-products, can by purifying as known in the art from the tower bottoms stream of recycle gas, to provide the acetic acid of purifying.Such as, this tower bottoms stream can be introduced into drying tower with except anhydrating, then by heavy ends column to remove propionic acid and other heavy constituent.
Summary of the invention
The object of the invention is to propose a kind of method for the production of acetic acid.
For reaching this object, the present invention by the following technical solutions:
For the production of a method for acetic acid, the method comprises: ethyl oxide in the first reactor, to produce the first effluent stream comprising acetic acid and ethene; Be oxidized first effluent stream under ethene to the condition of acetic acid with in the second reactor at least partially and obtain the second streams being enough to be oxidized, the step of wherein said ethyl oxide is carried out to 500 DEG C at 400 DEG C, and the wherein said step being oxidized first effluent stream in the second reactor is carried out to 250 DEG C at 150 DEG C, ethyl oxide in the 3rd reactor simultaneously, temperature of reaction is 520-580 DEG C, described 3rd reactor is fluidized-bed reactor, and acetic acid and second streams of generation are mixed to get acetic acid product.
The acetic acid stream of this explained hereafter is particularly suitable for the acetic acid raw material as synthesizing vinyl acetate, and adopt acetic acid stream of the present invention for the synthesis of vinyl acetate between to for plastic, have selectivity high, productive rate is high, the advantage that separation costs is low.
Embodiment
Embodiment 1
Ethyl oxide in the first reactor, to produce the first effluent stream comprising acetic acid and ethene; Be oxidized first effluent stream under ethene to the condition of acetic acid with in the second reactor at least partially and obtain the second streams being enough to be oxidized, the step of wherein said ethyl oxide is carried out at 420 DEG C, and the wherein said step being oxidized first effluent stream in the second reactor is carried out at 180 DEG C, ethyl oxide in the 3rd reactor simultaneously, temperature of reaction is 530 DEG C, described 3rd reactor is fluidized-bed reactor, and acetic acid and second streams of generation are mixed to get acetic acid product.
Embodiment 1
Ethyl oxide in the first reactor, to produce the first effluent stream comprising acetic acid and ethene; Be oxidized first effluent stream under ethene to the condition of acetic acid with in the second reactor at least partially and obtain the second streams being enough to be oxidized, the step of wherein said ethyl oxide is carried out at 420 DEG C, and the wherein said step being oxidized first effluent stream in the second reactor is carried out at 180 DEG C, ethyl oxide in the 3rd reactor simultaneously, temperature of reaction is 530 DEG C, described 3rd reactor is fluidized-bed reactor, and acetic acid and second streams of generation are mixed to get acetic acid product.
Embodiment 2
Ethyl oxide in the first reactor, to produce the first effluent stream comprising acetic acid and ethene; Be oxidized first effluent stream under ethene to the condition of acetic acid with in the second reactor at least partially and obtain the second streams being enough to be oxidized, the step of wherein said ethyl oxide is carried out at 430 DEG C, and the wherein said step being oxidized first effluent stream in the second reactor is carried out at 190 DEG C, ethyl oxide in the 3rd reactor simultaneously, temperature of reaction is 530 DEG C, described 3rd reactor is fluidized-bed reactor, and acetic acid and second streams of generation are mixed to get acetic acid product.
Embodiment 3
Ethyl oxide in the first reactor, to produce the first effluent stream comprising acetic acid and ethene; Be oxidized first effluent stream under ethene to the condition of acetic acid with in the second reactor at least partially and obtain the second streams being enough to be oxidized, the step of wherein said ethyl oxide is carried out at 440 DEG C, and the wherein said step being oxidized first effluent stream in the second reactor is carried out at 200 DEG C, ethyl oxide in the 3rd reactor simultaneously, temperature of reaction is 550 DEG C, described 3rd reactor is fluidized-bed reactor, and acetic acid and second streams of generation are mixed to get acetic acid product.
Embodiment 4
Ethyl oxide in the first reactor, to produce the first effluent stream comprising acetic acid and ethene; Be oxidized first effluent stream under ethene to the condition of acetic acid with in the second reactor at least partially and obtain the second streams being enough to be oxidized, the step of wherein said ethyl oxide is carried out at 460 DEG C, and the wherein said step being oxidized first effluent stream in the second reactor is carried out at 220 DEG C, ethyl oxide in the 3rd reactor simultaneously, temperature of reaction is 560 DEG C, described 3rd reactor is fluidized-bed reactor, and acetic acid and second streams of generation are mixed to get acetic acid product.
Embodiment 5
Ethyl oxide in the first reactor, to produce the first effluent stream comprising acetic acid and ethene; Be oxidized first effluent stream under ethene to the condition of acetic acid with in the second reactor at least partially and obtain the second streams being enough to be oxidized, the step of wherein said ethyl oxide is carried out at 480 DEG C, and the wherein said step being oxidized first effluent stream in the second reactor is carried out at 240 DEG C, ethyl oxide in the 3rd reactor simultaneously, temperature of reaction is 570 DEG C, described 3rd reactor is fluidized-bed reactor, and acetic acid and second streams of generation are mixed to get acetic acid product.
Embodiment 6
Ethyl oxide in the first reactor, to produce the first effluent stream comprising acetic acid and ethene; Be oxidized first effluent stream under ethene to the condition of acetic acid with in the second reactor at least partially and obtain the second streams being enough to be oxidized, the step of wherein said ethyl oxide is carried out at 400 DEG C, and the wherein said step being oxidized first effluent stream in the second reactor is carried out at 160 DEG C, ethyl oxide in the 3rd reactor simultaneously, temperature of reaction is 570 DEG C, described 3rd reactor is fluidized-bed reactor, and acetic acid and second streams of generation are mixed to get acetic acid product.

Claims (1)

1. for the production of a method for acetic acid, it is characterized in that the method comprises: ethyl oxide in the first reactor, to produce the first effluent stream comprising acetic acid and ethene, be oxidized first effluent stream under ethene to the condition of acetic acid with in the second reactor at least partially and obtain the second streams being enough to be oxidized, the step of wherein said ethyl oxide is carried out to 500 DEG C at 400 DEG C, and the wherein said step being oxidized first effluent stream in the second reactor is carried out to 250 DEG C at 150 DEG C, it is characterized in that: in the 3rd reactor, ethyl oxide obtains 3 material stream, temperature of reaction is 520-580 DEG C, described 3rd reactor is fluidized-bed reactor, the acetic acid produced and the second streams are mixed to get acetic acid product, the mass ratio of the second streams and the mixing of 3 material stream is 4-6:1-2.
CN201410617867.1A 2014-11-05 2014-11-05 Method for producing acetic acid Pending CN104355986A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410617867.1A CN104355986A (en) 2014-11-05 2014-11-05 Method for producing acetic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410617867.1A CN104355986A (en) 2014-11-05 2014-11-05 Method for producing acetic acid

Publications (1)

Publication Number Publication Date
CN104355986A true CN104355986A (en) 2015-02-18

Family

ID=52523325

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410617867.1A Pending CN104355986A (en) 2014-11-05 2014-11-05 Method for producing acetic acid

Country Status (1)

Country Link
CN (1) CN104355986A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1316984A (en) * 1998-09-04 2001-10-10 英国石油化学品有限公司 Process for production of acetic acid
EP1479438A1 (en) * 2002-01-31 2004-11-24 Consejo Superior De Investigaciones Cientificas Method for the oxidative dehydrogenation of ethane
WO2004108649A2 (en) * 2003-06-05 2004-12-16 Bp Chemicals Limited Oxidation process for the production of carboxylic acids and alkenes
CN1639102A (en) * 2001-12-04 2005-07-13 英国石油化学品有限公司 Oxidation process in fluidised bed reactor
CN101421038A (en) * 2006-02-07 2009-04-29 国际人造丝公司 Use of chemical reaction to separate ethylene from ethane in ethane-based processes to produce acetic acid

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1316984A (en) * 1998-09-04 2001-10-10 英国石油化学品有限公司 Process for production of acetic acid
CN1639102A (en) * 2001-12-04 2005-07-13 英国石油化学品有限公司 Oxidation process in fluidised bed reactor
EP1479438A1 (en) * 2002-01-31 2004-11-24 Consejo Superior De Investigaciones Cientificas Method for the oxidative dehydrogenation of ethane
WO2004108649A2 (en) * 2003-06-05 2004-12-16 Bp Chemicals Limited Oxidation process for the production of carboxylic acids and alkenes
CN101421038A (en) * 2006-02-07 2009-04-29 国际人造丝公司 Use of chemical reaction to separate ethylene from ethane in ethane-based processes to produce acetic acid

Similar Documents

Publication Publication Date Title
US6143928A (en) Catalysts for low temperature selective oxidation of propylene, methods of making and using the same
JP5021139B2 (en) Process for producing acrolein or acrylic acid or mixtures thereof from propane
US6160162A (en) Methods of catalytic oxidation of propane to acrylic acid
JP4377051B2 (en) Method for selective production of acetic acid by catalytic oxidation of ethane
JP2006500430A5 (en)
BR0008771B1 (en) processes for the catalytic gas phase oxidation of propene to acrylic acid, and from propene to acrolein and / or acrylic acid.
JP2001520976A5 (en)
CN101448809B (en) Production of phthalic anhydride by gas phase oxidation of o-xylol in a primary and a secondary reactor
CN101432254B (en) Integrated process for the production of acetic acid and vinyl acetate
CN101041135B (en) Method for the selective production of acetic acid by catalytic oxidation of ethane and/or ethylene
CN101448810A (en) Production of phthalic anhydride by gas phase oxidation of o-xylol
CN103071514B (en) A kind of preparation method preparing acrylic acid catalyst for propylene one step catalytic oxidation
JP2004501127A5 (en)
US20080139844A1 (en) Method Of Preparing Acrylic Acid From Propane In The Absence
US7368599B2 (en) Ethane oxidation catalyst and process utilising the catalyst
JP2013063997A (en) Use of chemical reaction to separate ethylene from ethane in ethane-based process to produce acetic acid
CN104355986A (en) Method for producing acetic acid
JP4809532B2 (en) Catalyst for catalytic oxidation of propane to acrylic acid, its production and use
KR100978775B1 (en) Mixed metal oxide catalyst and process for production of acetic acid
JPH1135519A (en) Production of acrylic acid
US7589217B2 (en) Yield improvement in the production of maleic anhydride
JP2001276618A (en) Catalyst for oxidation or ammoxidation
JP3859397B2 (en) Catalyst for production of methacrolein and methacrylic acid
WO2008010629A1 (en) Catalyst for partial oxidation of methylbenzenes, method for preparing the same, and method for producing aromatic aldehydes using the same
US9492814B2 (en) Catalyst for conversion of propylene to product comprising a carboxylic acid moiety

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20150218

RJ01 Rejection of invention patent application after publication