CN102580754A - Catalyst for synthesizing methyl acetate as well as preparation method and application - Google Patents
Catalyst for synthesizing methyl acetate as well as preparation method and application Download PDFInfo
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- CN102580754A CN102580754A CN2011104315401A CN201110431540A CN102580754A CN 102580754 A CN102580754 A CN 102580754A CN 2011104315401 A CN2011104315401 A CN 2011104315401A CN 201110431540 A CN201110431540 A CN 201110431540A CN 102580754 A CN102580754 A CN 102580754A
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Abstract
A catalyst for synthesizing methyl acetate comprises the following components according to weight percent: 1 to 5wt% of active component nickel, 1 to 5wt% of second metal component and 90 to 98wt% of carrier; and the catalyst is used for preparing methyl acetate through methanol carbonylation. The catalyst provided by the invention has the advantages of good selectivity, high activity, low corrosion to equipment and low manufacturing cost.
Description
Technical field
The invention belongs to a kind of catalyst and preparation method and application, relate in particular to a kind of catalyst and preparation method and application of acetic acid synthesized methyl esters.
Background technology
As a kind of important basic Organic Chemicals, methyl acetate is widely used in fields such as synthesizing of medicine, synthetic fibers, agricultural chemicals, printing and dyeing, light textile, adhesive and Fine Organic Chemical article.It can with most of immiscible organic solvents, be widely used as industrial solvent.Methyl acetate is the important intermediate of producing multiple polyester product, also is simultaneously the important source material that carbonylation is produced acetic anhydride, can be used for products such as acetic acid synthesized, aceticanhydride, methyl acrylate, vinyl acetate and acetamide.
The production method of traditional methyl acetate is an esterification process, is that raw material obtains methyl acetate under the acidic catalyst effect with acetic acid and methyl alcohol.Because this reaction is a kind of reversible reaction, receives the restriction of the equilibrium constant, the conversion per pass of reaction is not high.In order to make the raw material recycle, a series of extractive distillation columns and relevant device must be set.Therefore loaded down with trivial details, energy consumption of traditional esterification technique flow process and investment are all very high.
And methanol carbonylation mainly is that the employing two-step method is an acetic acid synthesis from methanol carbonylation, and acetic acid reacts acetic acid synthesized methyl esters with methanol esterification again.The carbonylation of methanol industrial process adopts the homogeneous catalysis system that is the basis with rhodium or iridium of Mosanto and BP company.Because rhodium or iridium homogeneous catalyst system exist noble metal to cost an arm and a leg, the catalyst circulation of homogeneous phase solution method and with the product separation difficulty, and, make reactor corrosion serious because of containing acid solution in the product, must adopt shortcomings such as expensive alloy reactor.
People are devoted to adopt heterogeneous catalyst cheap and easy to get to replace present acetic acid industry production method always for many years.US 4,918, and 218 disclose in the methanol vapor phase carbonylation that is promoted by halide, and adding palladium and copper can improve activity of such catalysts in the Raney nickel on carrier.It is that the carbon molecular sieve of skeleton is a carrier with the pottery that CN1039884C has reported a kind of, combines with nickel to form the PTNi catalyst, and the yield of primary product acetic acid is 40%, and the yield of methyl acetate is 18%.CN1255213C discloses a kind of high polymer bead nickel-loaded and lanthanum bimetallic heterogeneous catalyst of carbonization, and under the effect of iodomethane auxiliary agent, product is mainly acetic acid, and the selectivity of methyl acetate is up to 39%.People such as Liu have reported that tin can improve the activity of activated carbon supported Raney nickel [Ind.Eng.Chem.Res., 1994 (33): 488], are 300 ℃ in reaction temperature, and pressure is 0.1MPa, CO/CH
3OH/CH
3The I mol ratio is 10/9/1, and the reaction time is that methanol conversion is 58.8% under 4 hours the condition, and the selectivity of methyl acetate is 70%.But because of in its Preparation of catalysts process without the inert atmosphere roasting, cause the yield of methyl acetate relatively low.People such as Shi Lei [Chemical Reaction Engineering and technology, 2002,18 (3): 206] find that second components such as lanthanum, tin, molybdenum have facilitation to the activity of Raney nickel, but the concentration of auxiliary agent iodomethane is higher in the reactant, and equipment corrosion is serious.
Summary of the invention
The catalyst and preparation method and the application that the object of the present invention is to provide good, active high being used to of a kind of selectivity to prepare methyl acetate.
Consisting of of catalyst of the present invention:
Catalyst is by active component nickel, and second metal component and carrier are formed, and each weight percentages of components of catalyst consists of: active component nickel 1%～5wt%; Second metal, 1%～5wt%; Carrier 90～98wt%.
Second metal component is a kind of among Sm, La, Ce, Nd or the Sn as stated.
Aforesaid carrier is active carbon, carbon molecular sieve or CNT.
Preparation of catalysts method of the present invention is following:
The soluble compound of the active component nickel and second metal component is dissolved in the solvent; Then carrier is joined the medium volume dipping of the solution that contains the active component nickel and second metal component; After ultrasonic oscillation 0.5-2 hour, left standstill 8～24 hours, in 80～120 ℃ of oven dry; In inert atmosphere, rise under 400～800 ℃ through 2～6 hours roasting, promptly get required catalyst.
The compound of active component Ni is nickel nitrate, nickel acetate or nickel chloride as stated.
The soluble compound of second metal component is samaric nitrate, acetic acid samarium, samarium trichloride, lanthanum nitrate, lanthanum acetate, lanthanum chloride, cerous nitrate, cerous acetate, cerium chloride, neodymium nitrate, acetic acid neodymium, neodymium chloride, butter of tin or stannous chloride as stated.Be preferably samaric nitrate, lanthanum nitrate, cerous nitrate, neodymium nitrate or butter of tin.
Aforesaid solvent is water, methyl alcohol, ethanol, ethylene glycol or propane diols, is preferably ethylene glycol or propane diols.
Aforesaid inert atmosphere is nitrogen or argon gas.
The present invention is used for the application process that carbonylation of methanol prepares the methyl acetate catalysis agent, it is characterized in that comprising the steps:
(1) reduction of catalyst
Catalyst is at hydrogen atmosphere, and gas space velocity is 1000～2000h
-1, 350～600 ℃ of reduction temperatures reduced under the condition of normal pressure 3～5 hours;
(2) carbonylation
On fixed bed or paste state bed reactor, react, reaction condition is: the mol ratio of reactant methanol and auxiliary agent iodomethane is 10～35: 1, is preferably 15～30: 1; The mol ratio of methyl alcohol and carbon monoxide is 1: 1～10, be preferably 1: 1～and 5; Gas space velocity is 100～5000h
-1, be preferably 500～2000h
-1The liquid air speed is 0.1～5.0h
-1, be preferably 0.3～2.0h
-1Reaction temperature is 200～300 ℃, is preferably 230～290 ℃, and reaction pressure is 0.1～5MPa, is preferably 1～3MPa.
Advantage of the present invention is following:
1, catalyst of the present invention can significantly improve the selectivity of acetic acid synthesis from methanol carbonylation methyl esters on the Raney nickel, and methanol conversion is greater than 70%, and the selectivity of methyl acetate reaches 80～87%.
2,, make metal active constituent on the catalyst be easy to disperse and active component distributes very evenly owing to adopted ultrasonic Treatment in the catalyst preparation process; Owing to use solvent, especially used ethylene glycol or propylene glycol solvent simultaneously, further improved the dispersion of metal active constituent on carrier, thereby improved activity of such catalysts and selectivity of product.
3, the concentration of used co-catalyst iodomethane is lower in the reaction system, has alleviated corrosion on Equipment.
4, the catalyst raw material is cheap and easy to get, greatly reduces catalyst production cost.Technology is simple, easy to operate.
The specific embodiment
Embodiment 1:
1. preparation catalyst: press the composition of nickel nitrate 3wt%, butter of tin 5wt%, active carbon 92wt%, nickel nitrate and butter of tin are dissolved in the ethylene glycol, form mixed solution; Then active carbon is added the medium volume dipping of mixed solution; Supersonic oscillations 0.5 hour left standstill 12 hours, in 110 ℃ of oven dry; In 800 ℃ of roastings 2 hours, can make required catalyst under the argon atmospher.
2. be reflected in the fixed bed reactors and carry out: the mol ratio of reactant methanol and auxiliary agent iodomethane is 20: 1, and the mol ratio of methyl alcohol and carbon monoxide is 1: 1, and the carbon monoxide air speed is 700h
-1, the liquid air speed of methyl alcohol and iodomethane is 0.5h
-1, reaction temperature is 280 ℃, reaction pressure 0.1MPa, the reaction time is 24 hours, get final product methyl acetate.Test result is that methanol conversion is 81.2%, and the selectivity of methyl acetate is 83.3%.
Embodiment 2:
1. preparation catalyst: press the composition of nickel nitrate 5wt%, lanthanum nitrate 2.5wt%, active carbon 92.5wt%, nickel nitrate and lanthanum nitrate are dissolved in the ethylene glycol, form mixed solution; Then active carbon is added the medium volume dipping of mixed solution; Supersonic oscillations 1 hour left standstill 24 hours, in 100 ℃ of oven dry; In 700 ℃ of roastings 3 hours, can make required catalyst under the blanket of nitrogen.
2. be reflected in the fixed bed reactors and carry out: the mol ratio of reactant methanol and auxiliary agent iodomethane is 10: 1, and the mol ratio of methyl alcohol and carbon monoxide is 1: 2, and the carbon monoxide air speed is 1000h
-1, the liquid air speed of methyl alcohol and iodomethane is 1.2h
-1, reaction temperature is 230 ℃, reaction pressure 1.5MPa.Reaction time is 24 hours, get final product methyl acetate.Test result is that methanol conversion is 81.8%, and the selectivity of methyl acetate is 87.4%.
Embodiment 3:
1. preparation catalyst: press the composition of nickel nitrate 2.5wt%, cerous nitrate 2.5wt%, CNT 95%wt, nickel nitrate and cerous nitrate are dissolved in the propane diols, form mixed solution; Then CNT is added the medium volume dipping of mixed solution; Supersonic oscillations 1.5 hours left standstill 24 hours, in 120 ℃ of oven dry; In 600 ℃ of roastings 4 hours, can make required catalyst under the blanket of nitrogen.
2. be reflected in the fixed bed reactors and carry out: the mol ratio of reactant methanol and auxiliary agent iodomethane is 10: 1, and the mol ratio of methyl alcohol and carbon monoxide is 1: 1, and the carbon monoxide air speed is 500h
-1, the liquid air speed of methyl alcohol and iodomethane is 0.1h
-1, reaction temperature is 240 ℃, reaction pressure 3.0MPa.Reaction time is 24 hours, and test result is that methanol conversion is 73.9%, and the selectivity of methyl acetate is 85.9%.
Embodiment 4:
1. preparation catalyst: press the composition of nickel chloride 1wt%, neodymium chloride 1.0wt%, active carbon 98wt%, nickel chloride and neodymium chloride is soluble in water, form mixed aqueous solution; Then active carbon is added the medium volume dipping of mixed aqueous solution; Supersonic oscillations 2 hours left standstill 8 hours, in 100 ℃ of oven dry; In 500 ℃ of roastings 5 hours, can make required catalyst under the argon atmospher.
2. be reflected in the paste state bed reactor and carry out: the mol ratio of reactant methanol and auxiliary agent iodomethane is 20: 1, and the mol ratio of methyl alcohol and carbon monoxide is 1: 10, and the carbon monoxide air speed is 5000h
-1, the liquid air speed of methyl alcohol and iodomethane is 1.0h
-1, reaction temperature is 260 ℃, reaction pressure 2MPa.Reaction time is 24 hours, and test result is that methanol conversion is 70.9%, and the selectivity of methyl acetate is 80.5%.
Embodiment 5:
1. preparation catalyst: press the composition of nickel nitrate 5.0wt%, stannous chloride 5.0%wt, active carbon 90wt%, nickel nitrate and stannous chloride are dissolved in the methyl alcohol, form mixed solution; Active carbon adds the medium volume dipping of mixed solution then; Supersonic oscillations 1 hour left standstill 24 hours, in 120 ℃ of oven dry; In 600 ℃ of roastings 4 hours, can make required catalyst under the argon atmospher.
2. be reflected in the fixed bed reactors and carry out: the mol ratio of reactant methanol and auxiliary agent iodomethane is 15: 1, and the mol ratio of methyl alcohol and carbon monoxide is 1: 1, and the carbon monoxide air speed is 600h
-1, the liquid air speed of methyl alcohol and iodomethane is 0.5h
-1, reaction temperature is 200 ℃, reaction pressure 1.5MPa.Reaction time is 24 hours, and test result is that methanol conversion is 71.2%, and the selectivity of methyl acetate is 80.3%.
Embodiment 6:
1. preparation catalyst: press the composition of nickel nitrate 4.0wt%, samaric nitrate 1.5wt%, carbon molecular sieve 94.5wt%, nickel nitrate and samaric nitrate are dissolved in the ethylene glycol, form mixed solution; Then carbon molecular sieve is added the medium volume dipping of mixed solution; Supersonic oscillations 1 hour left standstill 12 hours, in 110 ℃ of oven dry; In 700 ℃ of roastings 3 hours, can make required catalyst under the blanket of nitrogen.
2. be reflected in the fixed bed reactors and carry out: the mol ratio of reactant methanol and auxiliary agent iodomethane is 30: 1, and the mol ratio of methyl alcohol and carbon monoxide is 1: 5, and the carbon monoxide air speed is 2000h
-1, the liquid air speed of methyl alcohol and iodomethane is 0.5h
-1, reaction temperature is 280 ℃, reaction pressure 5MPa.Reaction time is 24 hours, and test result is that methanol conversion is 80.7%, and the selectivity of methyl acetate is 83.8%.
Embodiment 7:
1. preparation catalyst: press the composition of nickel acetate 2.5wt%, neodymium nitrate 1.0wt%, CNT 96.5wt%, nickel acetate and neodymium nitrate is soluble in water, form mixed aqueous solution; Then CNT is added the medium volume dipping of mixed aqueous solution; Supersonic oscillations 2 hours left standstill 12 hours, in 110 ℃ of oven dry; In 400 ℃ of roastings 6 hours, can make required catalyst under the argon atmospher.
2. be reflected in the paste state bed reactor and carry out: the mol ratio of reactant methanol and auxiliary agent iodomethane is 20: 1, and the mol ratio of methyl alcohol and carbon monoxide is 1: 3, and the carbon monoxide air speed is 1500h
-1, the liquid air speed of methyl alcohol and iodomethane is 5.0h
-1, reaction temperature is 250 ℃, reaction pressure 1.5MPa.Reaction time is 24 hours, and test result is that methanol conversion is 73.3%, and the selectivity of methyl acetate is 80.6%.
Embodiment 8:
1. preparation catalyst: press the composition of nickel nitrate 5.0wt%, acetic acid samarium 1.0wt%, active carbon 94wt%, nickel nitrate and acetic acid samarium are dissolved in the ethylene glycol, form mixed solution; Then active carbon is added the medium volume dipping of mixed solution; Supersonic oscillations 1 hour left standstill 12 hours, in 80 ℃ of oven dry; In 700 ℃ of roastings 3 hours, can make required catalyst under the blanket of nitrogen.
2. be reflected in the fixed bed reactors and carry out: the mol ratio of reactant methanol and auxiliary agent iodomethane is 25: 1, and the mol ratio of methyl alcohol and carbon monoxide is 1: 2, and the carbon monoxide air speed is 900h
-1, the liquid air speed of methyl alcohol and iodomethane is 1.0h
-1Reaction temperature is 260 ℃, reaction pressure 1.0MPa.Reaction time is 24 hours, and test result is that methanol conversion is 74.3%, and the selectivity of methyl acetate is 86.5%.
Embodiment 9:
1. preparation catalyst: press the composition of nickel acetate 3.0wt%, lanthanum chloride 3.0wt%, carbon molecular sieve 94wt%, nickel acetate and lanthanum chloride are dissolved in the ethanol, form mixed solution; Then carbon molecular sieve is added the medium volume dipping of mixed solution; Supersonic oscillations 1.5 hours left standstill 24 hours, in 120 ℃ of oven dry; In 500 ℃ of roastings 5 hours, can make required catalyst under the argon atmospher.
2. be reflected in the fixed bed reactors and carry out: the mol ratio of reactant methanol and auxiliary agent iodomethane is 20: 1, and the mol ratio of methyl alcohol and carbon monoxide is 1: 1, and the carbon monoxide air speed is 100h
-1, the liquid air speed of methyl alcohol and iodomethane is 0.3h
-1, reaction temperature is 260 ℃, reaction pressure 1.5MPa.Reaction time is 24 hours, and test result is that methanol conversion is 71.2%, and the selectivity of methyl acetate is 80.2%.
Embodiment 10:
1. preparation catalyst: press the composition of nickel nitrate 5.0wt%, samarium trichloride 1.5wt%, active carbon 93.5wt%, nickel nitrate and samarium trichloride are dissolved in the propane diols, form mixed solution; Then active carbon is added the medium volume dipping of mixed solution; Supersonic oscillations 2 hours left standstill 24 hours, in 120 ℃ of oven dry; In 700 ℃ of roastings 3 hours, can make required catalyst under the argon atmospher.
2. be reflected in the fixed bed reactors and carry out: the mol ratio of reactant methanol and auxiliary agent iodomethane is 35: 1, and the mol ratio of methyl alcohol and carbon monoxide is 1: 1, and the carbon monoxide air speed is 800h
-1, the liquid air speed of methyl alcohol and iodomethane is 0.6h
-1, reaction temperature is 300 ℃, reaction pressure 2MPa.Reaction time is 24 hours, and test result is that methanol conversion is 74.6%, and the selectivity of methyl acetate is 86.5%.
Claims (11)
1. the catalyst of an acetic acid synthesized methyl esters is characterized in that catalyst consists of: catalyst is by active component nickel, and second metal component and carrier are formed, and it is active component nickel 1%～5wt% that each weight percentages of components of catalyst is formed; Second metal component, 1%～5wt%; Carrier 90～98wt%;
2. the catalyst of a kind of acetic acid synthesized methyl esters as claimed in claim 1 is characterized in that said second metal component is a kind of among Sm, La, Ce, Nd or the Sn.
3. the catalyst of a kind of acetic acid synthesized methyl esters as claimed in claim 1 is characterized in that described carrier is active carbon, carbon molecular sieve or CNT.
4. like the Preparation of catalysts method of claim 1,2 or 3 described a kind of acetic acid synthesized methyl esters, it is characterized in that comprising the steps:
The soluble compound of the active component nickel and second metal component is dissolved in the solvent; Then carrier is joined the medium volume dipping of the solution that contains the active component nickel and second metal component; After ultrasonic oscillation 0.5-2 hour, left standstill 8～24 hours, in 80～120 ℃ of oven dry; Rise in the inert atmosphere under 400～800 ℃ through 2～6 hours roasting, promptly get required catalyst.
5. the Preparation of catalysts method of a kind of acetic acid synthesized methyl esters as claimed in claim 4, the compound that it is characterized in that described active component Ni is nickel nitrate, nickel acetate or nickel chloride.
6. the Preparation of catalysts method of a kind of acetic acid synthesized methyl esters as claimed in claim 4, the soluble compound that it is characterized in that described second metal component is samaric nitrate, acetic acid samarium, samarium trichloride, lanthanum nitrate, lanthanum acetate, lanthanum chloride, cerous nitrate, cerous acetate, cerium chloride, neodymium nitrate, acetic acid neodymium, neodymium chloride, butter of tin or stannous chloride.Be preferably samaric nitrate, lanthanum nitrate, cerous nitrate, neodymium nitrate or butter of tin.
7. the Preparation of catalysts method of a kind of acetic acid synthesized methyl esters as claimed in claim 4 is characterized in that described solvent is water, methyl alcohol, ethanol, ethylene glycol or propane diols.
8. the Preparation of catalysts method of a kind of acetic acid synthesized methyl esters as claimed in claim 7 is characterized in that described solvent is ethylene glycol or propane diols.
9. the Preparation of catalysts method of a kind of acetic acid synthesized methyl esters as claimed in claim 4 is characterized in that described inert atmosphere is nitrogen or argon gas.
10. like the Application of Catalyst of claim 1,2 or 3 described a kind of acetic acid synthesized methyl esters, it is characterized in that comprising the steps:
(1) reduction of catalyst
Catalyst is at hydrogen atmosphere, and gas space velocity is 1000～2000h
-1, 350～600 ℃ of reduction temperatures reduced under the condition of normal pressure 3～5 hours;
(2) carbonylation
On fixed bed or paste state bed reactor, react, reaction condition is: the mol ratio of reactant methanol and auxiliary agent iodomethane is 10～35: 1, and the mol ratio of methyl alcohol and carbon monoxide is 1: 1～10, and gas space velocity is 100～5000h
-1, the liquid air speed is 0.1～5.0h
-1, reaction temperature is 200～300 ℃, reaction pressure is 0.1～5MPa.
11. the Application of Catalyst of a kind of acetic acid synthesized methyl esters as claimed in claim 10; The mol ratio that it is characterized in that described reactant methanol and auxiliary agent iodomethane is 15～30: 1; The mol ratio of methyl alcohol and carbon monoxide is for being 1: 1～5, and gas space velocity is 500～2000h
-1, the liquid air speed is 0.3～2.0h
-1, reaction temperature is 230～290 ℃, reaction pressure is 1～3MPa.
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Cited By (7)
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| CN104549258A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Ethylidene diacetate catalyst and preparation method thereof |
| CN106316846A (en) * | 2016-08-26 | 2017-01-11 | 西南化工研究设计院有限公司 | Production method of methyl acetate |
| CN108067226A (en) * | 2016-11-15 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of activated carbon supported iridium based catalyst and its preparation and application |
| CN110013866A (en) * | 2019-04-19 | 2019-07-16 | 山东玉皇化工有限公司 | A kind of iridium based catalyst of high activity and high stability and its preparation method and application |
| CN110560150A (en) * | 2019-09-12 | 2019-12-13 | 厦门大学 | Catalyst for preparing methyl acetate by methanol carbonylation and application thereof |
| CN113877561A (en) * | 2020-07-03 | 2022-01-04 | 中国石油化工股份有限公司 | Solid base catalyst and preparation method and application thereof |
| CN113877562A (en) * | 2020-07-03 | 2022-01-04 | 中国石油化工股份有限公司 | Solid base catalyst for synthesizing methyl acrylate and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549258A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Ethylidene diacetate catalyst and preparation method thereof |
| CN104549258B (en) * | 2013-10-28 | 2017-02-15 | 中国石油化工股份有限公司 | Ethylidene diacetate catalyst and preparation method thereof |
| CN106316846A (en) * | 2016-08-26 | 2017-01-11 | 西南化工研究设计院有限公司 | Production method of methyl acetate |
| CN106316846B (en) * | 2016-08-26 | 2018-12-25 | 西南化工研究设计院有限公司 | A kind of production method of methyl acetate |
| CN108067226A (en) * | 2016-11-15 | 2018-05-25 | 中国科学院大连化学物理研究所 | A kind of activated carbon supported iridium based catalyst and its preparation and application |
| CN110013866A (en) * | 2019-04-19 | 2019-07-16 | 山东玉皇化工有限公司 | A kind of iridium based catalyst of high activity and high stability and its preparation method and application |
| CN110560150A (en) * | 2019-09-12 | 2019-12-13 | 厦门大学 | Catalyst for preparing methyl acetate by methanol carbonylation and application thereof |
| CN110560150B (en) * | 2019-09-12 | 2020-09-01 | 厦门大学 | Catalyst for preparing methyl acetate by methanol carbonylation and application thereof |
| CN113877561A (en) * | 2020-07-03 | 2022-01-04 | 中国石油化工股份有限公司 | Solid base catalyst and preparation method and application thereof |
| CN113877562A (en) * | 2020-07-03 | 2022-01-04 | 中国石油化工股份有限公司 | Solid base catalyst for synthesizing methyl acrylate and preparation method and application thereof |
| CN113877561B (en) * | 2020-07-03 | 2024-03-26 | 中国石油化工股份有限公司 | Solid base catalyst and preparation method and application thereof |
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Application publication date: 20120718 |