CN103785470A - Preparation method of catalyst for synthesis of acrylic acid - Google Patents
Preparation method of catalyst for synthesis of acrylic acid Download PDFInfo
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- CN103785470A CN103785470A CN201210427731.5A CN201210427731A CN103785470A CN 103785470 A CN103785470 A CN 103785470A CN 201210427731 A CN201210427731 A CN 201210427731A CN 103785470 A CN103785470 A CN 103785470A
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Abstract
The invention discloses a preparation method of a catalyst for synthesis of acrylic acid. The method includes the following steps: loading a noble metal component by using SiO2 as a carrier through an impregnation method; drying, roasting and reducing; immersing ligands in an organic solvent; and conducting vacuum drying to obtain the catalyst for synthesis of acrylic acid. In the method, SiO2 carrier can be commercially available product or also can be made according to the existing technology. The SiO2 carrier is subjected to roasting treatment at 200-600 DEG C for 1-6 h before usage. The catalyst prepared by the method can be used in direct synthesis of acrylic acid from CO2 and ethylene, and has the advantages of low reaction temperature and high yield of acrylic acid.
Description
Technical field
The present invention relates to a kind of preparation method for the synthesis of acrylic acid catalyst, relate in particular to a kind of for CO
2with ethene be the preparation method of the support type organometallic complex catalyst of the direct acrylic acid synthesizing of raw material.
Background technology
Along with the day by day dependence of modern society to petrochemical industry resource, ever-increasing CO
2emission problem has been not only an environmental problem, has risen to especially international relations and the height that concerns human survival and development.CO
2the greenhouse effects that increase severely and cause are by the serious threat mankind's existence.Global energy shortage and CO
2caused day by day serious environmental problem forces people to go to find the approach addressing these problems, thereby is devoted to CO
2processing and utilizing.The most direct CO
2processing method is how to consume more CO
2, realize CO
2recycle, to solve CO at all
2problem.CO
2chemistry utilization be to realize CO
2one of important means recycling, utilizes CO in a large number in especially larger Chemical Manufacture
2its reduction of discharging is played the important and pivotal role.
Acrylic acid is a kind of bulk chemical, is mainly used to produce esters of acrylic acid (resin).Within 2010, domestic acrylic acid demand reaches 1,160,000 tons.Acrylic acid main production method is Carbonylation of Acetylene method and oxidation of propylene at present.Oxidation of propylene is main flow, but due to rise in oil price, it is more lucrative that Carbonylation of Acetylene method is just becoming.Oxidation of propylene is divided into two steps, and first propylene is oxidized to methacrylaldehyde, and then methacrylaldehyde is oxidized to acrylic acid.But this reaction has the strong heat release of reaction, and reaction is worked within the scope of the explosion limit of propylene, the shortcoming such as easily blast.
Ethene and CO
2the method of acrylic acid synthesizing, the obvious advantage that has more economic advantages and green chemical industry than propylene oxidation.This route is atom economy at present, and reaction condition is very gentle, does not have refuse to produce.The method is also greenhouse gases CO simultaneously
2the efficient a kind of cost-effective approach that provides that utilizes of resource.CN101745428A discloses catalyst and the application that a kind of catalysis transform of carbon dioxide is methacrylic acid, adopts cerium oxide support type polyoxometallate catalyst, take carbon dioxide, propylene as raw material, and the direct synthesize methyl acrylic acid of catalysis.Wherein cerium oxide support type polyoxometallate catalyst is made up of polyoxometallate and cerium oxide.Used catalyst activity is high, and to target product selectivity, high and catalytic performance is stable.Catalyst preparation process is simple and safe, nontoxic, pollution-free, and is convenient to recycle.But the application of temperature of this catalyst is 300 ℃, and reaction temperature is higher.Cheng Qingyan etc. have reported Ni in " catalysis journal " the 24th volume the 7th phase 558-562 page
2(Et)
2/ SiO
2catalysis carbon dioxide and Direct Synthesis of Methacrylic Acid from Propylene, with Ni
2(Et)
2/ SiO
2for catalyst, in fixed bed, carbon dioxide and propylene are that raw material has directly synthesized methacrylic acid, are 2 at carbon dioxide and ethylene molar ratio, air speed 1500h
-1, reaction pressure 0.5MPa, under the condition that reaction temperature is 120 ℃, propylene conversion is only 1.58%.Propylene conversion and methacrylate yield are low.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of load type metal composition catalyst of acrylic acid synthesizing.Catalyst prepared by the method is for CO
2in the process of the direct acrylic acid synthesizing of ethene, there is reaction temperature low, acrylic acid yield advantages of higher.
For the synthesis of a preparation method for acrylic acid catalyst, comprise following content: with SiO
2for carrier, adopt infusion process carried noble metal component, after dry, roasting, reduction, in organic solvent, flood part, obtain synthesizing propylene acid catalyst through vacuum drying.
In the inventive method, SiO
2carrier can adopt commercially available commodity, also can make by oneself according to prior art.SiO
2carrier use before at 200-600 ℃ calcination process 1～6h.
In the inventive method, described noble metal component is generally selected from the one in platinum, palladium, rhodium or ruthenium, is preferably rhodium.The consumption of noble metal component is counted 0.5%～10% of vehicle weight with simple substance, is preferably 1.0%～9%.Dipping noble metal component after at 300～700 ℃ roasting 2～7h, be preferably roasting 3～7h at 400～600 ℃.
In the inventive method, described reducing condition is 200～600 ℃ of reduction temperatures, the volume space velocity 500～5000h of hydrogen
-1, recovery time 2～10h; Preferably at 250～500 ℃, hydrogen volume air speed 1000～4000h
-1condition under reduce 3～8h.
In the inventive method, described organic solvent is toluene, oxolane, acetonitrile or N, and N-, to the one in dimethyl formamide, is preferably oxolane.Selected part is the one in two (diphenylphosphine) propane of 1,3-, two (diphenylphosphine) methane, trimethyl phosphorus or triphenyl phosphorus, is preferably two (diphenylphosphine) propane of 1,3-.The mol ratio of part and metal is 1～5, is preferably 1.5～4.In dipping part process, can, to the one that adds citric acid or butanedioic acid in organic solvent, be preferably butanedioic acid.
Catalyst prepared by the said method application in acrylic acid synthesizing, adopts fixed bed, and reaction condition is as follows: carbon dioxide and ethylene molar ratio 1～7, be preferably 2～6; 50～250 ℃ of reaction temperatures, are preferably 70～200 ℃; Reaction pressure 0.1～5MPa, is preferably 0.3～4.5MPa; Carbon dioxide and volume of ethylene air speed 500～6000 h
-1, be preferably 1000～5000 h
-1.
Load type metal composition catalyst prepared by the inventive method can be used for CO
2in the reaction of the direct acrylic acid synthesizing of ethene, can prepare at a lower temperature the acrylic acid of high yield.
The specific embodiment
Further illustrate effect and the effect of the inventive method below by embodiment.
Example 1
The dipping of metal component and reduction.1.6g radium chloride is configured to the aqueous solution of 60ml, to the SiO of roasting at 300 ℃
2flood, after dipping 2h, at 60 ℃, rotate evaporate to dryness, flooded cool putting at normal temperatures, then under 120 ℃ of conditions, dry 3 hours roasting 4h at 500 ℃.Material after roasting is reduced in hydrogen atmosphere, and wherein hydrogen volume air speed is 1500h
-1, reduction temperature is 400 ℃, and the recovery time is 4h, and the material after reduction adopts inert gas shielding sealing to preserve stand-by.
The dipping of part.By 12.4g1, two (diphenylphosphine) propane of 3-is dissolved in 70ml toluene, and add 1.1g butanedioic acid in the toluene solution of two (diphenylphosphine) propane, the material of the solution obtaining after to above-mentioned reduction floods, after dipping 4h, at 80 ℃, rotate evaporate to dryness toluene, the rhodium base organometallic complex catalyst components that material obtains after vacuum drying is: rhodium 2wt%, the mol ratio 3:1 of two (diphenylphosphine) propane and rhodium.Adopt inert gas seal to preserve the catalyst obtaining stand-by.
CO
2adopt fixed bed reactors with the reaction of ethene acrylic acid synthesizing, reaction condition is as follows: carbon dioxide and ethylene molar ratio 3, rhodium base organometallic complex catalyst 10ml, 180 ℃ of reaction temperatures, reaction pressure 1.0MPa, volume space velocity 2000 h
-1, obtaining acrylic acid yield is 1.83%, is selectively 98.3%.
Example 2
The dipping of metal component and reduction.2.1g radium chloride is configured to the aqueous solution of 70ml, to the SiO of roasting at 350 ℃
2flood, after dipping 3h, at 60 ℃, rotate evaporate to dryness, flooded cool putting at normal temperatures, then under 120 ℃ of conditions, dry 3 hours roasting 6h at 450 ℃.Material after roasting is reduced in hydrogen atmosphere, and wherein hydrogen volume air speed is 3000h
-1, reduction temperature is 300 ℃, and the recovery time is 5h, and the material after reduction adopts inert gas shielding sealing to preserve stand-by.
The dipping of part.By 10.9g1, two (diphenylphosphine) propane of 3-is dissolved in 70ml toluene, and add 0.9g butanedioic acid in the toluene solution of two (diphenylphosphine) propane, the material of the solution obtaining after to above-mentioned reduction floods, after dipping 4h, at 80 ℃, rotate evaporate to dryness toluene, the rhodium base organometallic complex catalyst components that material obtains after vacuum drying is: rhodium 3.5wt%, the mol ratio 2:1 of two (diphenylphosphine) propane and rhodium.Adopt inert gas seal to preserve the catalyst obtaining stand-by.
CO
2adopt fixed bed reactors with the reaction of ethene acrylic acid synthesizing, reaction condition is as follows: carbon dioxide and ethylene molar ratio 2, rhodium base organometallic complex catalyst 10ml, 120 ℃ of reaction temperatures, reaction pressure 1.5MPa, volume space velocity 2500 h
-1, obtaining acrylic acid yield is 2.10%, is selectively 99.2%.
Example 3
The dipping of metal component and reduction.1.6g radium chloride is configured to the aqueous solution of 40ml, to the SiO of roasting at 300 ℃
2flood, after dipping 2h, at 60 ℃, rotate evaporate to dryness, flooded cool putting at normal temperatures, then under 120 ℃ of conditions, dry 3 hours roasting 6h at 450 ℃.Material after roasting is reduced in hydrogen atmosphere, and wherein hydrogen volume air speed is 2000h
-1, reduction temperature is 350 ℃, and the recovery time is 4h, and the material after reduction adopts inert gas shielding sealing to preserve stand-by.
The dipping of part.By 5.12g1, two (diphenylphosphine) propane of 3-is dissolved in 50ml toluene, and add 0.4g butanedioic acid in the toluene solution of two (diphenylphosphine) propane, the material of the solution obtaining after to above-mentioned reduction floods, after dipping 4h, at 80 ℃, rotate evaporate to dryness toluene, the rhodium base organometallic complex catalyst components that material obtains after vacuum drying is: rhodium 4wt%, the mol ratio 2.5:1 of two (diphenylphosphine) propane and rhodium.Adopt inert gas seal to preserve the catalyst obtaining stand-by.
CO
2adopt fixed bed reactors with the reaction of ethene acrylic acid synthesizing, reaction condition is as follows: carbon dioxide and ethylene molar ratio 4, rhodium base organometallic complex catalyst 8ml, 150 ℃ of reaction temperatures, reaction pressure 2.0MPa, volume space velocity 3000 h
-1, obtaining acrylic acid yield is 2.23%, is selectively 98.1%.
Example 4
The dipping of metal component and reduction.2.4g radium chloride is configured to the aqueous solution of 50ml, to the SiO of roasting at 300 ℃
2flood, after dipping 2h, at 60 ℃, rotate evaporate to dryness, flooded cool putting at normal temperatures, then under 120 ℃ of conditions, dry 3 hours roasting 3h at 550 ℃.Material after roasting is reduced in hydrogen atmosphere, and wherein hydrogen volume air speed is 3000h
-1, reduction temperature is 400 ℃, and the recovery time is 6h, and the material after reduction adopts inert gas shielding sealing to preserve stand-by.
The dipping of part.By 21.7g1, two (diphenylphosphine) propane of 3-is dissolved in 100ml toluene, and add 1.7g butanedioic acid in the toluene solution of two (diphenylphosphine) propane, the material of the solution obtaining after to above-mentioned reduction floods, after dipping 4h, at 80 ℃, rotate evaporate to dryness toluene, the rhodium base organometallic complex catalyst components that material obtains after vacuum drying is: rhodium 6wt%, the mol ratio 3.5:1 of two (diphenylphosphine) propane and rhodium.Adopt inert gas seal to preserve the catalyst obtaining stand-by.
CO
2adopt fixed bed reactors with the reaction of ethene acrylic acid synthesizing, reaction condition is as follows: carbon dioxide and ethylene molar ratio 5, rhodium base organometallic complex catalyst 8ml, 95 ℃ of reaction temperatures, reaction pressure 3.0MPa, volume space velocity 5000 h
-1, obtaining acrylic acid yield is 2.16%, is selectively 99.1%.
Example 5
The dipping of metal component and reduction.3.4g radium chloride is configured to the aqueous solution of 60ml, to the SiO of roasting at 300 ℃
2flood, after dipping 3h, at 65 ℃, rotate evaporate to dryness, flooded cool putting at normal temperatures, then under 120 ℃ of conditions, dry 4 hours roasting 7h at 400 ℃.Material after roasting is reduced in hydrogen atmosphere, and wherein hydrogen volume air speed is 3500h
-1, reduction temperature is 450 ℃, and the recovery time is 7h, and the material after reduction adopts inert gas shielding sealing to preserve stand-by.
The dipping of part.By 13.2g1, two (diphenylphosphine) propane of 3-is dissolved in 70ml toluene, and add 1.1g butanedioic acid in the toluene solution of two (diphenylphosphine) propane, the material of the solution obtaining after to above-mentioned reduction floods, after dipping 4h, at 80 ℃, rotate evaporate to dryness toluene, the rhodium base organometallic complex catalyst components that material obtains after vacuum drying is: rhodium 8.5wt%, the mol ratio 1.5:1 of two (diphenylphosphine) propane and rhodium.Adopt inert gas seal to preserve the catalyst obtaining stand-by.
CO
2adopt fixed bed reactors with the reaction of ethene acrylic acid synthesizing, reaction condition is as follows: carbon dioxide and ethylene molar ratio 3, rhodium base organometallic complex catalyst 8ml, 100 ℃ of reaction temperatures, reaction pressure 1.5MPa, volume space velocity 4000 h
-1, obtaining acrylic acid yield is 2.05%, is selectively 99.3%.
Example 6
The dipping of metal component and reduction.1.2g ruthenic chloride is configured to the aqueous solution of 50ml, to the SiO of roasting at 350 ℃
2flood, after dipping 3h, at 70 ℃, rotate evaporate to dryness, flooded cool putting at normal temperatures, then under 120 ℃ of conditions, dry 3 hours roasting 5h at 500 ℃.Material after roasting is reduced in hydrogen atmosphere, and wherein hydrogen volume air speed is 2000h
-1, reduction temperature is 400 ℃, and the recovery time is 4h, and the material after reduction adopts inert gas shielding sealing to preserve stand-by.
The dipping of part.5.2g triphenyl phosphorus is dissolved in to 50ml toluene, and add 0.4g butanedioic acid in the toluene solution of triphenyl phosphorus, the material of the solution obtaining after to above-mentioned reduction floods, after dipping 4h, at 80 ℃, rotate evaporate to dryness toluene, the rhodium base organometallic complex catalyst components that material obtains after vacuum drying is: ruthenium 3wt%, the mol ratio 3:1 of triphenyl phosphorus and ruthenium.Adopt inert gas seal to preserve the catalyst obtaining stand-by.
CO
2adopt fixed bed reactors with the reaction of ethene acrylic acid synthesizing, reaction condition is as follows: carbon dioxide and ethylene molar ratio 3, ruthenium base organometallic complex catalyst 6ml, 130 ℃ of reaction temperatures, reaction pressure 0.7MPa, volume space velocity 4500 h
-1, obtaining acrylic acid yield is 1.73%, is selectively 98.2%.
Example 7
The dipping of metal component and reduction.3.1g ruthenic chloride is configured to the aqueous solution of 80ml, to the SiO of roasting at 350 ℃
2flood, after dipping 3h, at 70 ℃, rotate evaporate to dryness, flooded cool putting at normal temperatures, then under 120 ℃ of conditions, dry 3 hours roasting 5h at 450 ℃.Material after roasting is reduced in hydrogen atmosphere, and wherein hydrogen volume air speed is 3000h
-1, reduction temperature is 450 ℃, and the recovery time is 5h, and the material after reduction adopts inert gas shielding sealing to preserve stand-by.
The dipping of part.6.8g triphenyl phosphorus is dissolved in to 60ml toluene, and add 0.6g butanedioic acid in the toluene solution of triphenyl phosphorus, the material of the solution obtaining after to above-mentioned reduction floods, after dipping 4h, at 80 ℃, rotate evaporate to dryness toluene, the rhodium base organometallic complex catalyst components that material obtains after vacuum drying is: ruthenium 5wt%, the mol ratio 1.5:1 of triphenyl phosphorus and ruthenium.Adopt inert gas seal to preserve the catalyst obtaining stand-by.
CO
2adopt fixed bed reactors with the reaction of ethene acrylic acid synthesizing, reaction condition is as follows: carbon dioxide and ethylene molar ratio 2, ruthenium base organometallic complex catalyst 7ml, 80 ℃ of reaction temperatures, reaction pressure 4.0MPa, volume space velocity 3500 h
-1, obtaining acrylic acid yield is 1.68%, is selectively 98.8%.
Comparative example 1
With Ni
2(Et)
2/ SiO
2for catalyst, CO
2with ethene be that raw material adopts fixed bed reactors acrylic acid synthesizings, reaction condition is identical with example 2, acrylic acid yield is 1.63%, is selectively 97.2%.
Comparative example 2
With Ni
2(Et)
2/ SiO
2for catalyst, CO
2with ethene be that raw material adopts fixed bed reactors acrylic acid synthesizings, reaction condition is identical with example 7, acrylic acid yield is 1.35%, is selectively 98.2%.
Claims (10)
1. for the synthesis of a preparation method for acrylic acid catalyst, it is characterized in that: comprise following content: with SiO
2for carrier, adopt infusion process carried noble metal component, after dry, roasting, reduction, in organic solvent, flood part, obtain synthesizing propylene acid catalyst through vacuum drying.
2. method according to claim 1, is characterized in that: SiO
2carrier use before at 200-600 ℃ calcination process 1～6h.
3. method according to claim 1, it is characterized in that: described noble metal component is selected from the one in platinum, palladium, rhodium or ruthenium, the consumption of noble metal component is counted 0.5%～10% of vehicle weight with simple substance, dipping noble metal component after at 300～700 ℃ roasting 2～7h.
4. method according to claim 2, is characterized in that: the consumption of noble metal component is counted 1.0%～9% of vehicle weight with simple substance, dipping noble metal component after at 400～600 ℃ roasting 3～7h.
5. method according to claim 1, is characterized in that: described reducing condition is 200～600 ℃ of reduction temperatures, the volume space velocity 500～5000h of hydrogen
-1, recovery time 2～10h.
6. method according to claim 5, is characterized in that: described reducing condition is at 250～500 ℃ of reduction temperatures, hydrogen volume air speed 1000～4000h
-1condition under reduce 3～8h.
7. method according to claim 1, is characterized in that: described organic solvent is toluene, oxolane, acetonitrile or N, and N-is to the one in dimethyl formamide.
8. method according to claim 1, is characterized in that: selected part is the one in two (diphenylphosphine) propane of 1,3-, two (diphenylphosphine) methane, trimethyl phosphorus or triphenyl phosphorus, and the mol ratio of part and metal is 1～5.
9. the application of the catalyst that prepared by the arbitrary described method of claim 1 to 8 in acrylic acid synthesizing, is characterized in that: adopt fixed bed, reaction condition is as follows: carbon dioxide and ethylene molar ratio 1～7; 50～250 ℃ of reaction temperatures; Reaction pressure 0.1～5MPa; Carbon dioxide and volume of ethylene air speed 500～6000 h
-1.
10. application according to claim 9, is characterized in that: reaction condition is as follows: carbon dioxide and ethylene molar ratio 2～6; Reaction temperature is 70～200 ℃; Reaction pressure is 0.3～4.5MPa; Carbon dioxide and volume of ethylene air speed are 1000～5000 h
-1.
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| CN105622400A (en) * | 2014-10-28 | 2016-06-01 | 中国石油化工股份有限公司 | Acrylate synthesis method |
| CN108884010A (en) * | 2016-04-11 | 2018-11-23 | 巴斯夫欧洲公司 | The method for preparing salt unsaturated carboxylic acid |
| CN109071398A (en) * | 2016-04-06 | 2018-12-21 | 切弗朗菲利浦化学公司 | The method for generating alpha, beta-unsaturated carboxylic acid and its salt |
| US20190062250A1 (en) * | 2014-10-08 | 2019-02-28 | Chevron Phillips Chemical Company Lp | Methods for the Production of alpha,beta-Unsaturated Carboxylic Acids and Salts Thereof |
| US10544080B2 (en) | 2017-06-14 | 2020-01-28 | Chevron Phillips Chemical Company Lp | Continuous process for the conversion of olefins and carbon dioxide to acrylates via solution phase reactor |
| US10550061B2 (en) | 2017-06-14 | 2020-02-04 | Chevron Phillips Chemical Company Lp | Sulfur oxoacid-substituted and phosphorus oxoacid-substituted polyaromatic resins and salts thereof as promoters in acrylate production from coupling reactions of olefins and carbon dioxide |
| US10941101B2 (en) | 2015-12-15 | 2021-03-09 | Chevron Phillips Chemical Company, Lp | Formation of alpha,beta-unsaturated carboxylic acids and salts thereof from metalalactones and anionic polyelectrolytes |
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| US10584088B2 (en) * | 2014-10-08 | 2020-03-10 | Chevron Phillips Chemical Company Lp | Methods for the production of α,β-unsaturated carboxylic acids and salts thereof |
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| US10941101B2 (en) | 2015-12-15 | 2021-03-09 | Chevron Phillips Chemical Company, Lp | Formation of alpha,beta-unsaturated carboxylic acids and salts thereof from metalalactones and anionic polyelectrolytes |
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| US10550061B2 (en) | 2017-06-14 | 2020-02-04 | Chevron Phillips Chemical Company Lp | Sulfur oxoacid-substituted and phosphorus oxoacid-substituted polyaromatic resins and salts thereof as promoters in acrylate production from coupling reactions of olefins and carbon dioxide |
| US10926247B2 (en) | 2017-06-14 | 2021-02-23 | Chevron Phillips Chemical Company Lp | Sulfur oxoacid-substituted and phosphorus oxoacid-substituted polyaromatic resins and salts thereof as promoters in acrylate production from coupling reactions of olefins and carbon dioxide |
| US10544080B2 (en) | 2017-06-14 | 2020-01-28 | Chevron Phillips Chemical Company Lp | Continuous process for the conversion of olefins and carbon dioxide to acrylates via solution phase reactor |
| US10988430B2 (en) | 2017-06-14 | 2021-04-27 | Chevron Phillips Chemical Company Lp | Continuous process for the conversion of olefins and carbon dioxide to acrylates via solution phase reactor |
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