CN103896770B - A kind of method of producing methyl acetate - Google Patents

A kind of method of producing methyl acetate Download PDF

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Publication number
CN103896770B
CN103896770B CN201210571440.3A CN201210571440A CN103896770B CN 103896770 B CN103896770 B CN 103896770B CN 201210571440 A CN201210571440 A CN 201210571440A CN 103896770 B CN103896770 B CN 103896770B
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aromatic amine
dme
mordenite
molecular sieve
unstripped gas
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CN103896770A (en
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倪友明
朱文良
刘红超
刘勇
刘中民
孟霜鹤
李利娜
刘世平
周慧
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to MYPI2015702092A priority patent/MY172224A/en
Priority to SG11201504630QA priority patent/SG11201504630QA/en
Priority to PCT/CN2014/000124 priority patent/WO2014101897A1/en
Priority to BR112015014700-3A priority patent/BR112015014700B1/en
Priority to EA201591207A priority patent/EA027396B1/en
Priority to EP14733065.8A priority patent/EP2940000B1/en
Priority to US14/650,589 priority patent/US9440226B2/en
Priority to PL14733065T priority patent/PL2940000T3/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide

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

The invention provides a kind of method preparing methyl acetate, comprising the unstripped gas containing aromatic amine, dme, carbon monoxide and optional hydrogen by being loaded with the reactor of h-mordenite molecular sieve catalyst, preparing methyl acetate; Wherein said h-mordenite molecular sieve catalyst is the h-mordenite molecular sieve catalyst of aromatic amine absorption.In the method for the invention, with absorption aromatic amine h-mordenite molecular sieve be catalyzer, in unstripped gas, add aromatic amine component, the desorption making up aromatic amine in reaction process can be stablized, improve the stability of catalyzer, extend catalyzer work-ing life.

Description

A kind of method of producing methyl acetate
Technical field
The present invention relates to a kind of method of producing methyl acetate, particularly by the method for dme through preparing methyl acetate by carbonylating.
Background technology
Methyl acetate is a kind of important Organic Chemicals and solvent.Methyl acetate may be used for the derivative of synthesis of acetic acid and the acetic acid such as diacetyl oxide and vinyl acetate.Current acetic acid carries out suitability for industrialized production mainly through the even phase methanol carbonylation of Monsanto and BP, utilizes the noble metal catalyst containing Rh or Ir etc. and have corrosive CH in reaction process 3the promotors such as I [J.Catal.245 (2007) 110 ~ 123].Methyl acetate can also pass through hydrogenating reduction synthesizing alcohol [ChemSusChem3 (2010) 1192 ~ 1199].Ethanol has the octane value higher than gasoline, can perfect combustion in oil engine, separately or can mix the fuel used as automobile with gasoline, present ethanol content be the ethanol petrol commercialization of 5% ~ 85% [CN 101965324A].Be mixed into the discharge that ethanol can also reduce greenhouse gases in the oil.Present stage, ethanol carried out suitability for industrialized production mainly through the biological fermentation of corn or sugarcane and these two approach of ethylene hydration method.Biological fermentation produces the low-concentration ethanol that ethanol generally can only obtain about 14%, therefore also need the energy dropping into a large amount of funds and at substantial to carry out rectifying and just can obtain fuel-grade ethanol, biological fermentation consumes the cash crop such as grain for cost in addition, in order to not affect grain security, the output of biological fermentation ethanol is restricted.The ethene that ethylene hydration method uses obtains mainly through petrochemical complex, but petroleum resources are day by day exhausted, price can be in any more, so method loses economic competitiveness [Energy & Fuels 22 (2008) 814 ~ 839] gradually.In addition, methyl acetate as a kind of solvent of green, can also be widely used in the industries such as weaving, spices, medicine and food.
Methyl acetate can be obtained by the carbonylation reaction of dme and carbon monoxide, and dme can pass through methanol dehydration or synthetic gas one-step synthesis, therefore just can obtain methyl acetate by the derivative of synthetic gas.It is standby that present synthetic gas can pass through the non-oil resource vaporizing systems such as coal, Sweet natural gas and biomass, industrialization technology very ripe [CN 101613274A].
In the catalyzer of the preparing methyl acetate by carbonylating dimethyl ether reaction that present stage is reported, that most study, activity are the highest is mordenite (the Mordenite) [WO2010/061169A1 with octatomic ring and ten-ring structure, WO2010/067043A1, WO2010/130972A2, WO2010/130973A2, Angew.Chem.Int.Ed.45 (2006) 1617 ~ 1620, Ind.Eng.Chem.Res.49 (2010) 5485 ~ 5488, Phys.Chem.Chem.Phys.13 (2011) 2603 ~ 2612].Iglesia etc. [J.Am.Chem.Soc.129 (2007) 4919 ~ 4924] find, the active centre of catalyzed carbonylation is at the B acidic site of octatomic ring, the selectivity of methyl acetate more than 99%, but does not study life-span and the inactivation of catalyzer in great detail.[the Chin.J.Catal.31 (2010) 729 ~ 738 such as Shen Wenjie, CN101613274A] research show, the stability of dimethyl ether carbonylation reaction greatly can be improved to mordenite preadsorption pyridine, and the methyl acetate yield of about 30% can be kept after 200 DEG C of reaction 48h, pyridine adsorption is in twelve-ring, inhibit the generation of carbon deposit in twelve-ring, and acidic site in octatomic ring is substantially interference-free.But, at reaction conditions, be adsorbed on pyridine in mordenite can slowly desorption out, the carbon distribution of zeolite molecular sieve also slowly can increase thus cause catalyst activity to decline gradually, poor catalyst stability and the life-span short, seriously constrain its application in large-scale industrial production.
Summary of the invention
The object of the present invention is to provide a kind of method of being produced methyl acetate by Dimethyl ether carbonylation.It is characterized in that: its catalyzer adopted is the h-mordenite of aromatic amine absorption, unstripped gas is the gas mixture of dme, carbon monoxide and optional hydrogen containing aromatic amine, at reaction conditions, unstripped gas can produce methyl acetate by stability and high efficiency by catalyzer.The present invention, by adding aromatic amine component in unstripped gas, while further increasing the stability of catalyzer, substantially increases catalyst life.
For achieving the above object, the invention provides a kind of method preparing methyl acetate, comprise by the unstripped gas containing aromatic amine, dme, carbon monoxide and optional hydrogen by being loaded with the reactor of h-mordenite molecular sieve catalyst, at temperature of reaction 150 ~ 320 DEG C (preferably 200 ~ 280 DEG C), reaction pressure 0.1 ~ 8MPa (preferably 3 ~ 5MPa), gas volume air speed 500 ~ 10000h -1(preferably 2000 ~ 5000h -1) under reaction, prepare methyl acetate; Wherein said h-mordenite molecular sieve catalyst is the h-mordenite molecular sieve catalyst of aromatic amine absorption; In described unstripped gas, the mol ratio of carbon monoxide and dme is 1: 1 ~ 45: 1 (preferably 2: 1 ~ 10: 1), the mol ratio of aromatic amine and dme is 0.00001: 1 ~ 0.2: 1, and the mol ratio of hydrogen and dme is 0: 1 ~ 20: 1 (preferably 1: 1 ~ 10: 1).
In the present invention, in described unstripped gas, the mol ratio of aromatic amine and dme is 0.0001: 1 ~ 0.01: 1.
In the present invention, the h-mordenite of described aromatic amine absorption, its preparation process is, h-mordenite is filled in reactor, aromatic amine and carbon monoxide, hydrogen, air, nitrogen, helium or argon gas or they two or more gas mixture is passed under the adsorption temp of 90 ~ 420 DEG C, adsorb 0.5 ~ 48 hour, then purge 0.5 ~ 6 hour with carbon monoxide, hydrogen, air, nitrogen, helium or argon gas or they two or more gas mixture at such a temperature, namely obtain the h-mordenite of aromatic amine absorption.
In the present invention, described adsorption temp is 160 ~ 320 DEG C.
In the present invention, the sial atomic ratio of described h-mordenite is 4: 1 ~ 60: 1 (preferably 5: 1 ~ 20: 1).
In the present invention, described aromatic amine is any one or mixtures several arbitrarily in aniline or aniline substituent.
In the present invention, described aniline substituent is that in totally seven H one, two, three, four, five, six or seven of two H on phenyl ring in five H and amido are selected from F, Cl, Br, I, CH independently 3, CF 3or CH 3cH 2in substituting group replaced.
In the present invention, the aromatic amine in the aromatic amine adsorbed in described catalyzer and described unstripped gas can be identical or different.
In the present invention, the aromatic amine adsorbed in described catalyzer is aniline or 4-monomethylaniline, and the aromatic amine in described unstripped gas is aniline or 4-monomethylaniline.
In the present invention, the aromatic amine in described unstripped gas is the fresh aromatic amine added, and also can be the recycle of gained aromatic amine in product separation process.
In the present invention, described reactor is the fixed-bed reactor of continuous flow, moving-burden bed reactor or fluidized-bed reactor.
In the present invention, described acetic acid product methyl esters can be used for hydrogenating reduction and produces ethanol.
The beneficial effect that the present invention can produce comprises: on the h-mordenite molecular sieve catalyst of absorption aromatic amine, dimethyl ether carbonylation reaction is utilized to prepare methyl acetate, aromatic amine component is added in unstripped gas, can stablize make up/inhibited reaction process in the desorption of aromatic amine, thus improve the stability of catalyzer, extend the life-span of catalyzer.
Embodiment
In embodiment, the transformation efficiency of dme and the selectivity of methyl acetate all calculate based on the carbon mole number of dme:
Dimethyl ether conversion rate=[(in unstripped gas dme carbon mole number)-(in product dme carbon mole number)] ÷ (in unstripped gas dme carbon mole number) × (100%)
Methyl acetate selectivity=(2/3) × (in product methyl acetate carbon mole number) ÷ [(in unstripped gas dme carbon mole number)-(in product dme carbon mole number)] × (100%)
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to these embodiments.
Comparative example 1:
Be h-mordenite 550 DEG C of roastings 5 hours under the air atmosphere of retort furnace of 4: 1 by 50g silica alumina ratio, get wherein a part of pressed powder pellet, be ground into 20 ~ 40 orders, for active testing.Take this h-mordenite sample 10g, loading internal diameter is in the stainless steel reaction pipe of 8.5mm, normal pressure, at 300 DEG C with nitrogen activation 1 hour, then 250 DEG C are dropped to, pass into carbon monoxide: dme=15: 1, slowly boost to reaction pressure 2MPa, control reaction velocity GHSV=1000h -1, analyze tail gas with gas-chromatography on-line checkingi, calculate the transformation efficiency of dme and the selectivity of methyl acetate, reaction result is in table 1.
Comparative example 2:
Be h-mordenite roasting 5 hours at 550 DEG C under the air atmosphere of retort furnace of 4: 1 by 50g silica alumina ratio, get wherein a part of pressed powder pellet, be ground into 20 ~ 40 orders, for active testing.Take this h-mordenite sample 10g, loading internal diameter is in the stainless steel reaction pipe of 8.5mm, normal pressure, at 300 DEG C with nitrogen activation 1 hour, then with nitrogen bubble aniline liquid, aniline is blown in h-mordenite, processes 2 hours, then use nitrogen purging 1 hour, then 250 DEG C are dropped to, pass into carbon monoxide: dme=15: 1, slowly boost to reaction pressure 2MPa, control reaction velocity GHSV=1000h -1, analyze tail gas with gas-chromatography on-line checkingi, calculate the transformation efficiency of dme and the selectivity of methyl acetate, reaction result is in table 1.
Comparative example 3:
The silica alumina ratio of the h-mordenite in comparative example 1 is changed to 6: 1, and all the other experimental procedures are consistent with comparative example 1, and reaction result is in table 1.
Comparative example 4:
The silica alumina ratio of the h-mordenite in comparative example 2 is changed to 6: 1, and all the other experimental procedures are consistent with comparative example 2, and reaction result is in table 1.
Comparative example 5:
The silica alumina ratio of the h-mordenite in comparative example 1 is changed to 60: 1, and all the other experimental procedures are consistent with comparative example 1, and reaction result is in table 1.
Comparative example 6:
The silica alumina ratio of the h-mordenite in comparative example 2 is changed to 60: 1, and on catalyzer, adsorption of aniline changes aniline and the 4-ethylaniline that mol ratio is 1: 1 into, and experimental procedure is consistent with comparative example 2, and reaction result is in table 1.
Embodiment 1:
Be h-mordenite roasting 5 hours at 550 DEG C under the air atmosphere of retort furnace of 4: 1 by 50g silica alumina ratio, get wherein a part of pressed powder pellet, be ground into 20 ~ 40 orders, for active testing.Take this h-mordenite sample 10g, loading internal diameter is in the stainless steel reaction pipe of 8.5mm, normal pressure, at 300 DEG C with nitrogen activation 1 hour, then with nitrogen bubble aniline liquid, aniline is blown in h-mordenite, processes 2 hours, then use nitrogen purging 1 hour, then 250 DEG C are dropped to, pass into carbon monoxide: dme: aniline=15: 1: 0.001, slowly boost to reaction pressure 2MPa, control reaction velocity GHSV=1000h -1, analyze tail gas with gas-chromatography on-line checkingi, calculate the transformation efficiency of dme and the selectivity of methyl acetate, reaction result is in table 1.
Embodiment 2:
Together, the silica alumina ratio of h-mordenite is changed to 6: 1, and on catalyzer, adsorption of aniline changes 2 into for experimental procedure and embodiment 1,6-dichlor-4-trifluoromethyl aniline, in unstripped gas, aniline changes 4-fluoroaniline into, and all the other experimental procedures are consistent with embodiment 1, and reaction result is in table 1.
Embodiment 3:
Experimental procedure and embodiment 1 are together, the silica alumina ratio of h-mordenite is changed to 60: 1, on catalyzer, adsorption of aniline changes N into, N-methyl open-chain crown ether, in unstripped gas, aniline changes 2-bromaniline and the 3-chloroaniline that mol ratio is 1: 1 into, all the other experimental procedures are consistent with embodiment 1, and reaction result is in table 1.
Embodiment 4:
Change the unstripped gas in embodiment 1 into carbon monoxide: dme: 4-monomethylaniline=15: 1: 0.0001, reaction pressure is 0.1MPa, reaction velocity GHSV=500h -1, all the other experimental procedures are consistent with embodiment 1, and reaction result is in table 1.
Embodiment 5:
Change adsorption of aniline on catalyzer in embodiment 1 into 2-ethylaniline, unstripped gas changes carbon monoxide into: hydrogen: dme: aniline=1: 10: 1: 0.01, and temperature of reaction is 320 DEG C, and reaction pressure is 8MPa, reaction velocity GHSV=10000h -1, all the other experimental procedures are consistent with embodiment 1, and reaction result is in table 1.
Embodiment 6
Preadsorption aromatic amine in embodiment 1 is changed to 4-monomethylaniline, and unstripped gas changes carbon monoxide into: hydrogen: dme: 2-chloroaniline=45: 20: 1: 0.2, and temperature of reaction is 150 DEG C, and all the other experimental procedures are consistent with embodiment 1, and reaction result is in table 1.
Table 1 is catalyzed reaction result in comparative example and embodiment 1 ~ 6

Claims (9)

1. prepare the method for methyl acetate for one kind, it is characterized in that: by the unstripped gas containing aromatic amine, dme, carbon monoxide and optional hydrogen by being loaded with the reactor of h-mordenite molecular sieve catalyst, at temperature of reaction 150 ~ 320 DEG C, reaction pressure 0.1 ~ 8MPa, gas volume air speed 500 ~ 10000h -1lower reaction, prepares methyl acetate;
Wherein said h-mordenite molecular sieve catalyst is the h-mordenite molecular sieve catalyst of aromatic amine absorption, described aromatic amine is any one or mixtures several arbitrarily in aniline or aniline substituent, and described aniline substituent is that in totally seven H one, two, three, four, five, six or seven of two H on phenyl ring in five H and amino are selected from F, Cl, Br, I, CH independently 3, CF 3or CH 3cH 2in substituting group replaced;
In described unstripped gas, the mol ratio of carbon monoxide and dme is 1:1 ~ 45:1, and the mol ratio of aromatic amine and dme is 0.00001:1 ~ 0.2:1, and the mol ratio of hydrogen and dme is 0:1 ~ 20:1.
2. method according to claim 1, is characterized in that: in described unstripped gas, the mol ratio of aromatic amine and dme is 0.0001:1 ~ 0.01:1.
3. method according to claim 1, is characterized in that: the h-mordenite molecular sieve catalyst of described aromatic amine absorption is prepared by following steps:
H-mordenite is filled in reactor, aromatic amine and carbon monoxide, hydrogen, air, nitrogen, helium or argon gas or they two or more gas mixture is passed under the adsorption temp of 90 ~ 420 DEG C, adsorb 0.5 ~ 48 hour, then purge 0.5 ~ 6 hour with carbon monoxide, hydrogen, air, nitrogen, helium or argon gas or they two or more gas mixture at such a temperature, namely obtain the h-mordenite of aromatic amine absorption.
4. method according to claim 3, is characterized in that: described adsorption temp is 160 ~ 320 DEG C.
5. method according to claim 1, is characterized in that: the sial atomic ratio of described h-mordenite molecular sieve catalyst is 4:1 ~ 60:1.
6. method according to claim 1, is characterized in that: the aromatic amine adsorbed in described catalyzer is identical with the aromatic amine in described unstripped gas, or different.
7. method according to claim 1, the aromatic amine adsorbed in described catalyzer is aniline or 4-monomethylaniline; Aromatic amine in described unstripped gas is aniline or 4-monomethylaniline.
8. method according to claim 1, the aromatic amine in described unstripped gas is the fresh aromatic amine added, or the recycle of gained aromatic amine in product separation process.
9. method according to claim 1, is characterized in that: described reactor is the fixed-bed reactor of continuous flow, moving-burden bed reactor or fluidized-bed reactor.
CN201210571440.3A 2012-12-25 2012-12-25 A kind of method of producing methyl acetate Active CN103896770B (en)

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Application Number Priority Date Filing Date Title
CN201210571440.3A CN103896770B (en) 2012-12-25 2012-12-25 A kind of method of producing methyl acetate
US14/650,589 US9440226B2 (en) 2012-12-25 2014-01-28 Method for preparing methyl acetate
SG11201504630QA SG11201504630QA (en) 2012-12-25 2014-01-28 Method For Preparing Methyl Acetate
PCT/CN2014/000124 WO2014101897A1 (en) 2012-12-25 2014-01-28 Process for preparing methyl acetate
BR112015014700-3A BR112015014700B1 (en) 2012-12-25 2014-01-28 METHOD FOR PREPARING METHYL ACETATE
EA201591207A EA027396B1 (en) 2012-12-25 2014-01-28 Process for preparing methyl acetate
AU2014203724A AU2014203724B2 (en) 2012-12-25 2014-01-28 Process for preparing methyl acetate
MYPI2015702092A MY172224A (en) 2012-12-25 2014-01-28 Process for preparing methyl acetate
PL14733065T PL2940000T3 (en) 2012-12-25 2014-01-28 Process for preparing methyl acetate
EP14733065.8A EP2940000B1 (en) 2012-12-25 2014-01-28 Process for preparing methyl acetate
ZA2015/04517A ZA201504517B (en) 2012-12-25 2015-06-23 Method for preparing methyl acetate

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CN106365995B (en) * 2015-07-20 2018-06-05 中国科学院大连化学物理研究所 A kind of production method of methyl acetate
WO2023160805A1 (en) 2022-02-25 2023-08-31 Symrise Ag Fragrances with methoxy acetate structure

Citations (4)

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Publication number Priority date Publication date Assignee Title
CN101613274A (en) * 2008-06-25 2009-12-30 中国科学院大连化学物理研究所 A kind of method of preparing methyl acetate by carbonylating dimethyl ether
CN102227401A (en) * 2008-11-27 2011-10-26 英国石油化学品有限公司 Carbonylation process for production of methyl acetate
CN102421524A (en) * 2009-05-14 2012-04-18 英国石油化学品有限公司 Carbonylation process
WO2012101403A1 (en) * 2011-01-27 2012-08-02 Bp Chemicals Limited Process for the production of methyl acetate/acetic acid

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101613274A (en) * 2008-06-25 2009-12-30 中国科学院大连化学物理研究所 A kind of method of preparing methyl acetate by carbonylating dimethyl ether
CN102227401A (en) * 2008-11-27 2011-10-26 英国石油化学品有限公司 Carbonylation process for production of methyl acetate
CN102421524A (en) * 2009-05-14 2012-04-18 英国石油化学品有限公司 Carbonylation process
WO2012101403A1 (en) * 2011-01-27 2012-08-02 Bp Chemicals Limited Process for the production of methyl acetate/acetic acid

Non-Patent Citations (1)

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Stability Enhancement of H-Mordenite in Dimethyl Ether Carbonylation to Methyl Acetate by Pre-adsorption of Pyridine;LIU Junlong et al;《CHINESE JOURNAL OF CATALYSIS》;20101231;第31卷(第7期);729-738 *

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