CN103657715A - Catalyst for methanol or dimethyl ether carbonylation synthesis of methyl acetate, preparation method and application thereof - Google Patents
Catalyst for methanol or dimethyl ether carbonylation synthesis of methyl acetate, preparation method and application thereof Download PDFInfo
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- CN103657715A CN103657715A CN201310646236.8A CN201310646236A CN103657715A CN 103657715 A CN103657715 A CN 103657715A CN 201310646236 A CN201310646236 A CN 201310646236A CN 103657715 A CN103657715 A CN 103657715A
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Abstract
A catalyst for methanol or dimethyl ether carbonylation synthesis of methyl acetate is composed of copper oxide, titanium silicalite molecular sieves and transition metal oxides. The copper oxide accounts for 5-30 wt% calculated by pure copper, transition metal oxides account for 0.2-5.0 wt% calculated by elementary transition metal, and the titanium silicalite molecular sieves account for 94.8-65 wt%. The invention has the advantages of mild reaction conditions, high selectivity of methyl acetate, and good stability and long service life of the catalyst.
Description
Technical field
The present invention relates to a kind of synthetic method of methyl acetate, relate in particular to a kind of Catalysts and its preparation method and application for methyl alcohol or dimethyl ether carbonylation acetic acid methyl esters.
Technical background
Methyl acetate is a kind of important chemical products, is widely used in a plurality of industries such as weaving, spices and medicine, and has suitable potential value in leather, PET industry.Simultaneously, as a kind of important hardware and software platform compound, the existing methyl acetate synthesis technique of main development direction that methyl acetate is widely used in technology path that the rare products, particularly methyl acetate such as synthesizing vinyl acetate ester, methyl acrylate produce aceticanhydride through carbonylation and has become aceticanhydride synthetic technology is mainly acetic acid-methanol esterification method and methyl alcohol liquid phase carbonylation method.Acetic acid-methanol esterification method is to take liquid acid as catalyst, acetic acid and the acetic acid synthesized methyl esters of methyl alcohol generation esterification, and this explained hereafter cost is high, flow process is loaded down with trivial details, equipment corrosion is serious.Methyl alcohol liquid phase carbonylation method is that to take methyl alcohol and CO be raw material, take noble metal Rh as catalyst, adding Cl, I etc. be the acetic acid synthesized methyl esters of auxiliary agent, there is product and catalyst separation difficulty, rhodium resource scarcity, catalyst loss seriously and iodide to problems such as equipment corrosions.Methanol/dimethyl ether vapor phase carbonylation method is not add under any promoter condition, reactant and CO be the direct acetic acid synthesized methyl esters of normal pressure (low pressure) on solid catalyst, this technological process is simple, process is green, easy to operate, equipment investment and feed purification cost all lower.Therefore,, from Atom economy, process green and technical feasibility, this technique has industrial value and academic significance.Catalyst about the acetic acid synthesized methyl esters of methanol/dimethyl ether vapor phase carbonylation has relevant report at present, the transition-metal catalyst that typically has the Si-Al zeolite load of reporting in EP2072125A1 and EP2198963A1, the transition metal sulfide catalyst of Alvaro Calafat and Peng Feng report.The transition-metal catalyst acidity of Si-Al zeolite load is too strong, generates dehydration/hydrolysate in a large number; Transition metal sulfuration acidity of catalyst too a little less than, catalyst activity is lower, catalyst stability is poor simultaneously.
Summary of the invention
The object of this invention is to provide a kind of good stability, life-span length, selective high catalyst and the preparation method and application for the acetic acid synthesized methyl esters of methanol/dimethyl ether vapor phase carbonylation of methyl acetate.
Catalyst of the present invention is comprised of cupric oxide, HTS and transition metal oxide, wherein cupric oxide content is counted 5～30wt% with elemental copper, transition metal oxide content is counted 0.2～5.0wt% with its simple substance transition metal, and HTS content is 94.8～65wt%.
In HTS as above, titanium silicon mol ratio is 1:20～200, and micropore size is 0.5～2nm, and proportion is 10～30%, and mesoporous aperture is 2.1～10nm, and proportion is 90～70%.
Transition metal as above is one or more in ruthenium, rhodium, palladium, platinum, silver, molybdenum, iron, zinc, nickel, manganese, tin.
The preparation method of catalyst of the present invention is as follows
(1) preparation of HTS presoma:
By ethyl orthosilicate (TEOS), tetrapropyl oxyammonia (TPAOH) is dissolved in distilled water, and stirring at room 0.5～2.5h obtains solution A.Butyl titanate (TBOT) is dissolved in isopropyl alcohol (IPA), then adds TPAOH and distilled water, stirring at room 10～40min obtains the yellow solution B of clarification.Solution A and solution B are mixed, stir and obtain solution C, reaction mass mole consist of n(SiO
2): n(TiO
2); N(TPAOH): n(IPA): n(H
2o)=1.0:0.04～0.005:0.6～0.07:2.0～0.25:20～50.This reaction mass stirs 2～3h with the alcohol in the system of removing at 40～60 ℃, supplements distilled water simultaneously and maintains glue constant volume, then fills still, in 80～140 ℃ of ageing 4～31h, obtains colloidal sol 1;
(2) preparation of HTS:
Lauryl amine (DDA) in molar ratio: absolute ethyl alcohol: water=1:20～35:100 forms mixed solution, after stirring, obtain solution D, solution D and colloidal sol obtained above 1 are mixed, and wherein solution D and colloidal sol 1 mass ratio are 1:2～3, by the pH value of hydrochloric acid regulation system, are 9～11, gained mixture is in stirring at room 9～24h, suction filtration, washing, 80～120 ℃ of oven dry, 350～650 ℃ of roasting 3～7h, obtain HTS;
(3) the catalyst based preparation of copper/HTS
Adopt vacuum impregnation technology to prepare required catalyst: HTS obtained above is placed in to vacuum plant, when system vacuum degree reaches 0.05～0.1MPa, keep 0.5～1h, then the aqueous solution that adds soluble metal mantoquita and soluble metal builder salts, the vacuum of keeping system, continue to stir 1～3h, then recover normal pressure, at 40～60 ℃, be stirred to water volatilization dry.Products therefrom is at 80～100 ℃ of dry 10～24h, and then the speed with 0.5～1.0 ℃/min is warmed up to 350～500 ℃, and keeps 5～8h, obtains required catalyst.
The application operating condition of catalyst of the present invention is:
(1) the acetic acid synthesized methyl esters of methanol vapor phase carbonylation: catalyst is activated to 1～5h in 300～600 ℃ in hydrogen atmosphere, pass into and be preheated to the methanol steam of 130～150 ℃ and the hybrid reaction gas of CO, methanol steam proportion in reaction gas is 10～40v%, reaction temperature is 220～350 ℃,, reaction gas air speed is 1000～4000ml/g
cat.h, reaction pressure is 0～2.0MPa.
(2) dimethyl ether vapor phase carbonylation reacts acetic acid synthesized methyl esters: catalyst is activated to 1～5h in 300～600 ℃ in hydrogen atmosphere, pass into the hybrid reaction gas of dimethyl ether and CO, dimethyl ether shared volume in reaction gas is 10～40v%, reaction temperature is 180～300 ℃, and reaction velocity is 1000～4000ml/g
cat.h, reaction pressure is 0～2.0MPa.
Advantage of the present invention:
1) the present invention can realize the synthetic of methyl acetate under need not any additive, and process green, atom economy, technological process is simple, production cost is low.
2) gentle, the methyl acetate of reaction condition selective high, catalyst stability is good, the life-span is long.
The specific embodiment
Embodiment 1
By 33.6ml TEOS, 46.2ml TPAOH(0.68M) aqueous solution and the mixing of 3.9ml deionized water, stirring at room 2h, to complete hydrolysis, obtains solution A.1.02g TBOT is dissolved in 11.4ml IPA, adds 19.3ml TPAOH(0.68M) aqueous solution and 16.6ml deionized water, stirring at room 40min obtains the faint yellow hydrolyzate B of clarification.To after A and two kinds of hydrolysate mixing and stirring of B, at 50 ℃, stir 3h with the alcohol in the system of removing, supplement deionized water simultaneously and maintain glue constant volume, then pack into in teflon-lined stainless steel crystallizing kettle, in 80 ℃ of ageing 27h, obtain colloidal sol 1.Get 6.0g DDA and be dissolved in the mixed solution that 60ml absolute ethyl alcohol and 60ml deionized water form, the colloidal sol 1 that adds the first step to prepare, is 10 by the pH value of hydrochloric acid regulation system.Gained mixture continues to stir 20h in room temperature, suction filtration, and washing, 100 ℃ of oven dry, 550 ℃ of roasting 4h, obtain Si(mol)/Ti(mol)=50, the HTS of micropore/mesoporous=10/90.
Adopt vacuum impregnation technology to prepare required catalyst, 6g HTS obtained above is placed in to vacuum plant, when system vacuum degree reaches 0.06MPa, keep 1h, then drip 10ml and contain 10.5gCu(NO
3)
2.3H
2o and 0.2gAgNO
3solution, dropwise the vacuum of rear keeping system, continue to stir 2h, then recover normal pressure, at 40 ℃, be stirred to water volatilization dry.Products therefrom is at 100 ℃ of dry 12h, and then the speed with 0.5 ℃/min is warmed up to 400 ℃, and keeps 6h, and obtaining Cu content is 28.8wt%, the catalyst that Ag content is 1.2wt%.
By catalyst in H
2the lower 450 ℃ of reduction 5h of atmosphere, drop to 290 ℃, pass into the methanol steam of 140 ℃ of preheatings and the gaseous mixture of CO, and unstrpped gas consists of 10v/90v, and reaction gas air speed is 3000ml/g
cat.h, reaction pressure is 1.0MPa, and the reactivity worth of catalyst is in Table 1.
Embodiment 2
By 20ml TEOS, 25.2ml TPAOH(0.68M) aqueous solution and the mixing of 3.5ml deionized water, stirring at room 1h, to complete hydrolysis, obtains solution A.1.25g TBOT is dissolved in 9.8ml IPA, adds 17ml TPAOH(0.68M) aqueous solution and 9.5ml deionized water, stirring at room 30min obtains the faint yellow hydrolyzate B of clarification.To after A and two kinds of hydrolysate mixing and stirring of B, at 40 ℃, stir 3h with the alcohol in the system of removing, supplement deionized water simultaneously and maintain glue constant volume, then pack into in teflon-lined stainless steel crystallizing kettle, in 80 ℃ of ageing 30h, obtain colloidal sol 1.
Get 3.3g DDA and be dissolved in the mixed solution that 30ml absolute ethyl alcohol and 32ml deionized water form, the colloidal sol 1 that adds the first step to prepare, is 11 by the pH value of hydrochloric acid regulation system.Gained mixture at room temperature continues to stir 18h, suction filtration, and washing, dries 18h for 100 ℃, 500 ℃ of roasting 4h, obtain Si(mol)/Ti(mol)=24, the HTS of micropore/mesoporous=20/80.
Adopt vacuum impregnation technology to prepare required catalyst: 6g HTS obtained above to be placed in to vacuum plant, when system vacuum degree reaches 0.06MPa, to keep 1h, then drip 10ml and contain 6.04gCu(NO
3)
2.3H
2o and 0.2ml palladium bichloride (Pd content: solution 10wt Pd/v), dropwise the vacuum of rear keeping system, continue to stir 2h, then recover normal pressure, at 60 ℃, be stirred to water volatilization dry.Products therefrom is at 110 ℃ of dry 12h, and then the speed with 0.8 ℃/min is warmed up to 500 ℃, and keeps 5h, and obtaining Cu content is 19.8wt%, the catalyst that Pd content is 0.25wt%.
By catalyst in H
2the lower 400 ℃ of reduction 3h of atmosphere, drop to 240 ℃ of gaseous mixtures that pass into dimethyl ether and CO, and unstrpped gas consists of DME/CO=20v/80v, and reaction gas air speed is 1000ml/g
cat.h, reaction pressure is 1.5MPa, and the reactivity worth of catalyst is in Table 1.
Embodiment 3
By 20ml TEOS, 25.2ml TPAOH(0.68M) aqueous solution and the mixing of 9ml deionized water, stirring at room 1h, to complete hydrolysis, obtains solution A.0.5g TBOT is dissolved in 5.6ml IPA, adds 9.5ml TPAOH(0.68M) aqueous solution and 8.5ml deionized water, stirring at room 30min obtains the faint yellow hydrolyzate B of clarification.To after A and two kinds of hydrolysate mixing and stirring of B, at 45 ℃, stir 2h with the alcohol in the system of removing, supplement deionized water simultaneously and maintain glue constant volume, then pack into in teflon-lined stainless steel crystallizing kettle, in 140 ℃ of ageing 6h, obtain colloidal sol 1.
Get 3.5g DDA and be dissolved in the mixed solution that 35ml absolute ethyl alcohol and 34ml deionized water form, the colloidal sol 1 that adds the first step to prepare, is 9.5 by the pH value of hydrochloric acid regulation system.Gained mixture at room temperature continues to stir 22h, suction filtration, and washing, 100 ℃ of oven dry, 500 ℃ of roasting 4h, obtain Si(mol)/Ti(mol)=61, the HTS of micropore/mesoporous=25/75.
Adopt vacuum impregnation technology to prepare required catalyst: 5g HTS obtained above is placed in to vacuum plant, when system vacuum degree reaches 0.06MPa, keep 1h, then drip the solution that 10ml contains 4.2g copper nitrate and 0.6g zinc nitrate and 1.4g ferric nitrate, dropwise the vacuum of rear keeping system, continue to stir 2h, then recover normal pressure, at 50 ℃, be stirred to water volatilization dry.Products therefrom is at 90 ℃ of dry 24h, and then the speed with 0.5 ℃/min is warmed up to 400 ℃, and keeps 8h, and obtaining Cu content is 16.2wt%, and Zn content is 1.9wt%, the catalyst that Fe content is 2.8wt%.
By catalyst in H
2the lower 450 ℃ of reduction 5h of atmosphere, drop to 290 ℃, pass into the methanol steam of 140 ℃ of preheatings and the gaseous mixture of CO, and unstrpped gas consists of CH3OH/CO=20v/80v, and reaction gas air speed is 2000ml/g
cat.h, reaction pressure is 0.5MPa, and the reactivity worth of catalyst is in Table 1.
Embodiment 4
By 20ml TEOS, 25.2ml TPAOH(0.68M) aqueous solution and the mixing of 8.6ml deionized water, stirring at room 1.5h, to complete hydrolysis, obtains solution A.0.4g TBOT is dissolved in 4.6ml IPA, adds 7.6ml TPAOH(0.68M) aqueous solution and 9.5ml deionized water, stirring at room 30min obtains the faint yellow hydrolyzate B of clarification.To after A and two kinds of hydrolysate mixing and stirring of B, at 50 ℃, stir 2h with the alcohol in the system of removing, supplement deionized water simultaneously and maintain glue constant volume, then pack into in teflon-lined stainless steel crystallizing kettle, in 90 ℃ of ageing 30h, obtain colloidal sol 1.
Get 3.5g DDA and be dissolved in the mixed solution that 35ml absolute ethyl alcohol and 34ml deionized water form, the colloidal sol 1 that adds the first step to prepare, is 10 by the pH value of hydrochloric acid regulation system.Gained mixture at room temperature continues to stir 18h, suction filtration, and washing, 100 ℃ of oven dry, 450 ℃ of roasting 4h, obtain Si(mol)/Ti(mol)=76, the HTS of micropore/mesoporous=30/70.
Adopt vacuum impregnation technology to prepare required catalyst: 6g HTS obtained above to be placed in to vacuum plant, when system vacuum degree reaches 0.06MPa, to keep 1h, then drip 10ml and contain 3.2g Cu(NO
3)
2.3H
2o and 0.4g SnCl
4solution, dropwise the vacuum of rear keeping system, continue to stir 2h, then recover normal pressure, at 50 ℃, be stirred to water volatilization dry.Products therefrom is at 100 ℃ of dry 12h, and then the speed with 0.5 ℃/min is warmed up to 450 ℃, and keeps 5h, and obtaining Cu content is 11.2wt%, the catalyst that Sn content is 2.4wt%.
By catalyst in H
2the lower 400 ℃ of reduction 3h of atmosphere, drop to 280 ℃, pass into the methanol steam of 140 ℃ of preheatings and the gaseous mixture of CO, and unstrpped gas consists of CH
3oH/CO=30v/70v, reaction gas air speed is 2000ml/g
cat.h, reaction pressure is 1.5MPa, and the reactivity worth of catalyst is in Table 1.
Embodiment 5
By 25ml TEOS, 31.5ml TPAOH(0.68M) aqueous solution and the mixing of 8.5ml deionized water, stirring at room 1.5h, to complete hydrolysis, obtains solution A.0.3g TBOT is dissolved in 3.5ml IPA, adds 5.7ml TPAOH(0.68M) aqueous solution and 10.5ml deionized water, stirring at room 20min obtains the faint yellow hydrolyzate B of clarification.To after A and two kinds of hydrolysate mixing and stirring of B, at 40 ℃, stir 2.5h with the alcohol in the system of removing, supplement deionized water simultaneously and maintain glue constant volume, then pack into in teflon-lined stainless steel crystallizing kettle, in 140 ℃ of ageing 6h, obtain colloidal sol 1.
Get 4g DDA and be dissolved in the mixed solution that 30ml absolute ethyl alcohol and 39ml deionized water form, the colloidal sol 1 that adds the first step to prepare, is 11 by the pH value of hydrochloric acid regulation system.Gained mixture continues to stir 22h in room temperature, suction filtration, and washing, 110 ℃ of oven dry, 550 ℃ of roasting 4h, obtain Si(mol)/Ti(mol)=127, the HTS of micropore/mesoporous=15/85.
Adopt vacuum impregnation technology to prepare required catalyst: 6g HTS obtained above to be placed in to vacuum plant, when system vacuum degree reaches 0.06MPa, to keep 1h, then drip 10ml and contain 4.5gCu(NO
3)
2.3H
2o, 0.3g AgNO
3with 0.6g Zn (NO
3)
2.6H
2the solution of O, dropwises the vacuum of rear keeping system, continues to stir 2h, then recovers normal pressure, is stirred to water volatilization dry at 50 ℃.Products therefrom is at 100 ℃ of dry 12h, and then the speed with 0.5 ℃/min is warmed up to 500 ℃, and keeps 5h, and obtaining Cu content is 15.3wt%, and Ag content is 2.4wt%, the catalyst that Zn content is 1.7wt%.
By catalyst in H
2the lower 400 ℃ of reduction 3h of atmosphere, drop to 240 ℃, pass into the gaseous mixture of dimethyl ether and CO, and unstrpped gas consists of DME/CO=30v/70v, and reaction gas air speed is 1000ml/g
cat.h, reaction pressure is 1.MPa, and the reactivity worth of catalyst is in Table 1.
Embodiment 6
By 20ml TEOS, 25.2ml TPAOH(0.68M) aqueous solution and the mixing of 7.5ml deionized water, stirring at room 2.5h, to complete hydrolysis, obtains solution A.0.3g TBOT is dissolved in 3.4ml IPA, adds 5.7ml TPAOH(0.68M) aqueous solution and 12.5ml deionized water, stirring at room 30min obtains the faint yellow hydrolyzate B of clarification.To after A and two kinds of hydrolysate mixing and stirring of B, at 50 ℃, stir 2h with the alcohol in the system of removing, supplement deionized water simultaneously and maintain glue constant volume, then pack into in teflon-lined stainless steel crystallizing kettle, in 100 ℃ of ageing 20h, obtain colloidal sol 1.
Get that 3.5g DDA is dissolved in that 33ml absolute ethyl alcohol and 34ml deionized water form mix molten in, the colloidal sol 1 that adds the first step to prepare, is 11 by the pH value of hydrochloric acid regulation system.Gained mixture continues to stir 20h in room temperature, suction filtration, and washing, 100 ℃ of oven dry, 450 ℃ of roasting 5h, obtain Si(mol)/Ti(mol)=102, the HTS of micropore/mesoporous=18/82.
Adopt vacuum impregnation technology to prepare required catalyst: 6g HTS obtained above to be placed in to vacuum plant, when system vacuum degree reaches 0.06MPa, to keep 1h, then drip 10ml and contain 1.36g Cu(NO
3)
2.3H
2o and 0.3g AgNO
3solution, dropwise the vacuum of rear keeping system, continue to stir 2h, then recover normal pressure, at 50 ℃, be stirred to water volatilization dry.Products therefrom is at 100 ℃ of dry 12h, and then the speed with 0.5 ℃/min is warmed up to 500 ℃, and keeps 5h, and obtaining Cu content is 5.4wt%, the catalyst that Ag content is 2.8wt%.
By catalyst in H
2the lower 500 ℃ of reduction 4h of atmosphere, drop to 280 ℃, pass into the methanol steam of 130 ℃ of preheatings and the gaseous mixture of CO, and unstrpped gas consists of CH
3oH/CO=40v/60v, reaction gas air speed is 2500ml/g
cat.h, reaction pressure is 1.2Mpa, and the reactivity worth of catalyst is in Table 1.
Embodiment 7
By 20ml TEOS, 25.2ml TPAOH(0.68M) aqueous solution and the mixing of 9ml deionized water, stirring at room 2h, to complete hydrolysis, obtains solution A.0.2g TBOT is dissolved in 2.3ml IPA, adds 3.8ml TPAOH(0.68M) aqueous solution and 9.5ml deionized water, stirring at room 20min obtains the faint yellow hydrolyzate B of clarification.To after A and two kinds of hydrolysate mixing and stirring of B, at 45 ℃, stir 2.5h with the alcohol in the system of removing, supplement deionized water simultaneously and maintain glue constant volume, then pack into in teflon-lined stainless steel crystallizing kettle, in 90 ℃ of ageing 25h, obtain colloidal sol 1.
Get 3.4g DDA and be dissolved in the mixed solution that 35ml absolute ethyl alcohol and 33ml deionized water form, the colloidal sol 1 that adds the first step to prepare, is 10 by the pH value of hydrochloric acid regulation system.Gained mixture continues to stir 20h in room temperature, suction filtration, and washing, 100 ℃ of oven dry, 600 ℃ of roasting 4h, obtain Si(mol)/Ti(mol)=153, the HTS of micropore/mesoporous=22/78.
Adopt vacuum impregnation technology to prepare required catalyst: 6g HTS obtained above to be placed in to vacuum plant, when system vacuum degree reaches 0.06MPa, to keep 1h, then drip 10ml and contain 5.0g Cu(NO
3)
2.3H
2the solution of O and 1.5ml nitric acid ruthenium (Ru:1wt%/v), dropwises the vacuum of rear keeping system, continues to stir 2h, then recovers normal pressure, is stirred to water volatilization dry at 50 ℃.Products therefrom is at 100 ℃ of dry 12h, and then the speed with 0.5 ℃/min is warmed up to 500 ℃, and keeps 4h, and obtaining Cu content is 17.2wt%, the catalyst that Ru content is 0.2wt%.
By catalyst in H
2the lower 450 ℃ of reduction 3h of atmosphere, drop to 220 ℃, pass into the gaseous mixture of dimethyl ether and CO, and unstrpped gas consists of DME/CO=10v/90v, and reaction gas air speed is 1000ml/g
cat.h, reaction pressure is 1.5Mpa, and the reactivity worth of catalyst is in Table 1.
Embodiment 8
By 20ml TEOS, 25.2ml TPAOH(0.68M) aqueous solution and the mixing of 9ml deionized water, stirring at room 2h, to complete hydrolysis, obtains solution A.0.16g TBOT is dissolved in 1.8ml IPA, adds 3ml TPAOH(0.68M) aqueous solution and 10.5ml deionized water, stirring at room 20min obtains the faint yellow hydrolyzate B of clarification.To after A and two kinds of hydrolysate mixing and stirring of B, at 50 ℃, stir 3h with the alcohol in the system of removing, supplement deionized water simultaneously and maintain glue constant volume, then pack into in teflon-lined stainless steel crystallizing kettle, in 80 ℃ of ageing 31h, obtain colloidal sol 1.
Get 2g DDA and be dissolved in the mixed solution that 20ml absolute ethyl alcohol and 19.5ml deionized water form, the colloidal sol 1 that adds the first step to prepare, is 10 by the pH value of hydrochloric acid regulation system.Gained mixture continues to stir 20h in room temperature, suction filtration, and washing, 100 ℃ of oven dry, 500 ℃ of roasting 4h, obtain Si(mol)/Ti(mol)=191, the HTS of micropore/mesoporous=28/72.
Adopt vacuum impregnation technology to prepare required catalyst: 5g HTS obtained above to be placed in to vacuum plant, when system vacuum degree reaches 0.06MPa, to keep 1h, then drip 10ml and contain 1.67gCu(NO
3)
2.3H
2o and 1ml Mn (NO
3)
2(Mn content: solution 15wt%/v), dropwise the vacuum of rear keeping system, continue to stir 2h, then recover normal pressure, at 50 ℃, be stirred to water volatilization dry.Products therefrom is at 100 ℃ of dry 12h, and then the speed with 0.5 ℃/min is warmed up to 400 ℃, and keeps 5h, and obtaining Cu content is 7.7wt%, the catalyst that Mn content is 2.6wt%.
By catalyst in H
2the lower 450 ℃ of reduction 5h of atmosphere, drop to 290 ℃, pass into the methanol steam of 140 ℃ of preheatings and the gaseous mixture of CO, and unstrpped gas consists of CH
3oH/CO=40v/60v, reaction gas air speed is 3000ml/g
cat.h, reaction pressure is 1.4MPa, and the reactivity worth of catalyst is in Table 1.
The catalyst based upper methanol/dimethyl ether carbonylation performance of table 1Cu/ HTS
Claims (6)
1. the catalyst of a methyl alcohol or dimethyl ether carbonylation acetic acid methyl esters, it is characterized in that catalyst is comprised of cupric oxide, HTS and transition metal oxide, wherein cupric oxide content is counted 5～30wt% with elemental copper, transition metal oxide content is counted 0.2～5.0wt% with its simple substance transition metal, and HTS content is 94.8～65wt%.
2. the catalyst of a kind of methyl alcohol as claimed in claim 1 or dimethyl ether carbonylation acetic acid methyl esters, it is characterized in that in described HTS, titanium silicon mol ratio is 1:20～200, micropore size is 0.5～2nm, proportion is 10～30%, mesoporous aperture is 2.1～10nm, and proportion is 90～70%.
3. the catalyst of a kind of methyl alcohol as claimed in claim 1 or dimethyl ether carbonylation acetic acid methyl esters, is characterized in that described transition metal is one or more in ruthenium, rhodium, palladium, platinum, silver, molybdenum, iron, zinc, nickel, manganese, tin.
4. the preparation method of the catalyst of a kind of methyl alcohol as described in claim 1-3 any one or dimethyl ether carbonylation acetic acid methyl esters, is characterized in that comprising the steps:
(1) preparation of HTS presoma:
By ethyl orthosilicate, tetrapropyl oxyammonia is dissolved in distilled water, and stirring at room 0.5～2.5h obtains solution A; Butyl titanate is dissolved in isopropyl alcohol, then adds TPAOH and distilled water, stirring at room 10～40min obtains the yellow solution B of clarification; Solution A and solution B are mixed, stir and obtain solution C, reaction mass mole consist of SiO
2: TiO
2; Tetrapropyl oxyammonia: isopropyl alcohol: H
2o=1.0:0.04～0.005:0.6～0.07:2.0～0.25:20～50, this reaction mass stirs 2～3h with the alcohol in the system of removing at 40～60 ℃, supplements distilled water simultaneously and maintains glue constant volume, then fills still, in 80～140 ℃ of ageing 4～31h, obtain colloidal sol 1;
(2) preparation of HTS:
Lauryl amine in molar ratio: absolute ethyl alcohol: water=1:20～35:100 forms mixed solution, after stirring, obtain solution D, solution D and colloidal sol obtained above 1 are mixed, and wherein solution D and colloidal sol 1 mass ratio are 1:2～3, by the pH value of hydrochloric acid regulation system, are 9～11, gained mixture is in stirring at room 9～24h, suction filtration, washing, 80～120 ℃ of oven dry, 350～650 ℃ of roasting 3～7h, obtain HTS;
(3) the catalyst based preparation of copper/HTS
Adopt vacuum impregnation technology to prepare required catalyst: HTS obtained above is placed in to vacuum plant, when system vacuum degree reaches 0.05～0.1MPa, keep 0.5～1h, then the aqueous solution that adds soluble metal mantoquita and soluble metal builder salts, the vacuum of keeping system, continue to stir 1～3h, then recover normal pressure, at 40～60 ℃, be stirred to water volatilization dry, products therefrom is at 80～100 ℃ of dry 10～24h, then the speed with 0.5～1.0 ℃/min is warmed up to 350～500 ℃, and keeps 5～8h, obtains required catalyst.
5. the application of the catalyst of a kind of methyl alcohol as described in claim 1-3 any one or dimethyl ether carbonylation acetic acid methyl esters, the application operating condition it is characterized in that is:
The acetic acid synthesized methyl esters of methanol vapor phase carbonylation: catalyst is activated to 1～5h in 300～600 ℃ in hydrogen atmosphere, pass into and be preheated to the methanol steam of 130～150 ℃ and the hybrid reaction gas of CO, methanol steam proportion in reaction gas is 10～40v%, reaction temperature is 220～350 ℃,, reaction gas air speed is 1000～4000ml/g
cat.h, reaction pressure is 0～2.0MPa.
6. the application of the catalyst of a kind of methyl alcohol as described in claim 1-3 any one or dimethyl ether carbonylation acetic acid methyl esters, the application operating condition it is characterized in that is:
Dimethyl ether vapor phase carbonylation reacts acetic acid synthesized methyl esters: catalyst is activated to 1～5h in 300～600 ℃ in hydrogen atmosphere, pass into the hybrid reaction gas of dimethyl ether and CO, dimethyl ether shared volume in reaction gas is 10～40v%, reaction temperature is 180～300 ℃, and reaction velocity is 1000～4000ml/g
cat.h, reaction pressure is 0～2.0MPa.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310646236.8A CN103657715B (en) | 2013-12-04 | 2013-12-04 | The catalyst of methyl alcohol or the acetic acid synthesized methyl esters of Dimethyl ether carbonylation and method for making and application |
Applications Claiming Priority (1)
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|---|---|---|---|
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| CN106966913A (en) * | 2017-04-06 | 2017-07-21 | 青岛科技大学 | A kind of preparation method of improved methacrylic acid dialkylamino ethyl ester |
| CN108855209A (en) * | 2018-07-13 | 2018-11-23 | 武汉理工大学 | A kind of ormolu support type grade hole titanium molecular sieve catalysis material and preparation method thereof |
| CN109503326A (en) * | 2018-11-30 | 2019-03-22 | 西南化工研究设计院有限公司 | A kind of technique that dimethyl ether produces ethyl alcohol indirectly |
| CN110746301A (en) * | 2019-11-28 | 2020-02-04 | 上海华谊（集团）公司 | Method for synthesizing methyl glycolate by dimethyl oxalate hydrogenation |
| CN113797966A (en) * | 2021-01-20 | 2021-12-17 | 济宁学院 | Preparation method of core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst and method for preparing N, N-diethylhydroxylamine by using core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst |
| CN114210360A (en) * | 2021-12-29 | 2022-03-22 | 延长中科（大连）能源科技股份有限公司 | Preparation method of catalyst and application of catalyst in direct synthesis of ethanol from dimethyl ether |
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| CN104399517B (en) * | 2014-10-15 | 2016-06-15 | 中国科学院山西煤炭化学研究所 | The catalyst of acetic acid synthesis from methanol carbonylation methyl ester and method for making and application |
| CN104399517A (en) * | 2014-10-15 | 2015-03-11 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing methyl acetate through methanol carbonylation, preparation method and application thereof |
| CN106365995A (en) * | 2015-07-20 | 2017-02-01 | 中国科学院大连化学物理研究所 | Methyl acetate production method |
| 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 |
| CN106000430B (en) * | 2016-05-27 | 2019-06-25 | 中国科学院山西煤炭化学研究所 | A kind of catalyst synthesizing methyl acetate and preparation method and application |
| CN106000430A (en) * | 2016-05-27 | 2016-10-12 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing methyl acetate as well as preparation method and application |
| CN106966913A (en) * | 2017-04-06 | 2017-07-21 | 青岛科技大学 | A kind of preparation method of improved methacrylic acid dialkylamino ethyl ester |
| CN108855209A (en) * | 2018-07-13 | 2018-11-23 | 武汉理工大学 | A kind of ormolu support type grade hole titanium molecular sieve catalysis material and preparation method thereof |
| CN109503326A (en) * | 2018-11-30 | 2019-03-22 | 西南化工研究设计院有限公司 | A kind of technique that dimethyl ether produces ethyl alcohol indirectly |
| CN109503326B (en) * | 2018-11-30 | 2020-10-09 | 西南化工研究设计院有限公司 | Process for indirectly producing ethanol by dimethyl ether |
| CN110746301A (en) * | 2019-11-28 | 2020-02-04 | 上海华谊（集团）公司 | Method for synthesizing methyl glycolate by dimethyl oxalate hydrogenation |
| CN110746301B (en) * | 2019-11-28 | 2022-09-27 | 上海华谊（集团）公司 | Method for synthesizing methyl glycolate by hydrogenating dimethyl oxalate |
| CN113797966A (en) * | 2021-01-20 | 2021-12-17 | 济宁学院 | Preparation method of core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst and method for preparing N, N-diethylhydroxylamine by using core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst |
| CN113797966B (en) * | 2021-01-20 | 2024-02-27 | 济宁学院 | Preparation method of core-shell titanium-silicon molecular sieve coated zinc-cadmium alloy particle catalyst and method for preparing N, N-diethyl hydroxylamine by using same |
| CN114210360A (en) * | 2021-12-29 | 2022-03-22 | 延长中科（大连）能源科技股份有限公司 | Preparation method of catalyst and application of catalyst in direct synthesis of ethanol from dimethyl ether |
| CN114210360B (en) * | 2021-12-29 | 2024-02-27 | 延长中科（大连）能源科技股份有限公司 | Preparation method of catalyst and application of catalyst in direct synthesis of ethanol from dimethyl ether |
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