CN103464216A - Preparation method of silica gel carrier of heteropoly acid catalyst for synthesizing sec-butyl acetate from acetic acid and butylene - Google Patents
Preparation method of silica gel carrier of heteropoly acid catalyst for synthesizing sec-butyl acetate from acetic acid and butylene Download PDFInfo
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Abstract
The invention discloses a preparation method of a silica gel carrier of a heteropoly acid catalyst for synthesizing sec-butyl acetate from acetic acid and butylene. The preparation method is characterized by comprising the following steps of 1, preparing a sodium silicate solution having the content of 18-20wt% by silica weight, and preparing a sulfuric acid aqueous solution having the content of 30-35wt%, 2, adding the sulfuric acid aqueous solution into a reactor, adding the prepared sodium silicate solution into the sulfuric acid aqueous solution at a temperature of 10-15 DEG C at a rate of 300-500g/min until a pH value is in a range of 3-4, and carrying out standing at a normal temperature for 20-24h until gel is obtained, 3, smashing the gel, adding a complexing agent into the smashed gel, heating the mixture to a temperature of 70-80 DEG C, and carrying out heat preservation for 1-5h, 4, carrying out filtration and water washing on the material obtained by the step 3 until sodion content is below 0.1wt%, carrying out beating on the filter cake, adding ammonia water into the pulp to adjust a pH value to 7-8, carrying out heating to a temperature of 80-90 DEG C, and carrying out heat preservation for 1-2h, and 5, carrying out pressure-type spray drying dehydration to adjust particle sizes to 1-2mm so that the silica gel carrier is obtained. The silica gel carrier has a pore volume of 1.4-2.0ml/g, a specific surface area of 400-600m<2>/g, silica purity greater than 99.5%, average granularity of 1-2mm and higher reaction activity.
Description
Technical field
The present invention relates to a kind of preparation method of heteropolyacid catalyst silica-gel carrier, relate in particular to the method for making of the acetic acid synthesized secondary butyl ester heteropolyacid catalyst silica-gel carrier of a kind of acetic acid and butylene.
Background technology
Increasingly strict to the requirement of environmental protection in world wide at present.2-butyl acetate replaces the organic solvents such as toluene, dimethylbenzene, ketone than I due to toxicity, be widely used in the every field such as coating, printing ink, medicine, essence and flavoring agent, metal cleaning, adhesive.
The catalyst that current acetic acid and butene esters are combined to the 2-butyl acetate use comprises: solid catalyst and liquid catalyst.Liquid catalyst mainly comprises sulfuric acid, P-TOLUENE SULFO ACID 99 etc., and this catalyst is serious to equipment corrosion, and environmental pollution is serious.Solid catalyst mainly contains cationic ion-exchange resin, heteropoly acid etc., and cationic ion-exchange resin is owing to there being the swelling phenomenon to affect the life-span of catalyst in HTHP.Heteropoly acid is the emphasis of studying at present as a kind of novel effective catalyst, but uses separately heteropoly acid also can cause the difficulty of separating and reclaiming.Therefore, people have invented a kind of heteropolyacid catalyst of support type.Patent CN101293210A discloses the preparation method of the composite catalyst of a kind of ethyl ester and butylene preparing sec-butyl acetate with direct esterification, it adopts heteropoly acid is the catalyst activity component, porous carrier is dispersant, the weight ratio of heteropoly acid and porous carrier is 0.01:1-10:1, what wherein porous carrier was used is white carbon, kaolin etc., but what in embodiment, use is white carbon silica.Because white carbon is a kind of open-celled structure, its heteropoly acid in esterification process has the stripping phenomenon, makes the activity decreased of catalyst very fast.
Summary of the invention
The object of the present invention is to provide a kind of suitable pore property that has, there is again the acetic acid of catalytic performance and the preparation method of the heteropolyacid catalyst silica-gel carrier that butene esters is combined to 2-butyl acetate preferably.
The present invention is the method for making that acetic acid and butene esters are combined to the heteropolyacid catalyst silica-gel carrier of 2-butyl acetate, it is characterized in that, comprises the following steps:
1) sodium silicate solution is mixed with to the solution in silica 18-20%wt, sulfuric acid adds the aqueous solution that water is mixed with 30-35%wt;
2) aqueous sulfuric acid is added to reactor, then under 10-15 ℃, with the speed of 300-500g/min, adds step 1) sodium silicate solution of preparation, stop adding sodium silicate solution for 3-4 to the pH value, standing 20-24 hour at normal temperatures to forming gel;
3) by step 2) gel that obtains smashes, and adds EDTA, sodium tartrate and sodium oxalate one or more complexing agents wherein, and the 7%-13% that the complexing agent addition is the silica total amount, be warming up to 70-80 ℃, insulation 1-5 hour;
4) step 3) is obtained to product and filter, wash, be washed till below filter cake sodium ions content 0.1%wt, filter cake is pulled an oar and added ammoniacal liquor to be adjusted to the pH value for 7-8, be warming up to 80-90 ℃, insulation 1-2 hour;
5) finally utilize press spray drying and dehydrating drying that step 4) is obtained to product, the adjustment granularity is 1-2mm;
The pore volume of described heteropolyacid catalyst silica-gel carrier is 1.4-2.0ml/g, specific area: 400-600m
2/ g, silica purity is greater than 99.5%, particle mean size 1-2mm.
According to the present invention, acetic acid and butene esters are combined to the method for making of the heteropolyacid catalyst silica-gel carrier of 2-butyl acetate, are characterised in that, comprise the following steps:
1) sodium silicate solution is mixed with to the solution in silica 18-20%wt, sulfuric acid adds the aqueous solution that water is mixed with 30-35%wt;
2) aqueous sulfuric acid is added to reactor, then under 10-15 ℃, with the speed of 300-500g/min, adds step 1) sodium silicate solution of preparation, stop adding sodium silicate solution for 3-4 to the pH value, standing 20-24 hour at normal temperatures to forming gel;
3) by step 2) gel that obtains smashes, and adds EDTA, sodium tartrate and sodium oxalate one or more complexing agents wherein, and the 8-12% that the complexing agent addition is the silica total amount, be warming up to 70-80 ℃, insulation 1-5 hour;
4) step 3) is obtained to product filters, washing, be washed till in filter cake below sodium ions content 0.1%wt, filter cake pull an oar and added ammoniacal liquor to be adjusted to pH value to be 7-8, to be warming up to 80-90 ℃, be incubated 1-2 hour;
5) finally utilize press spray drying and dehydrating drying that step 4) is obtained to product, the adjustment granularity is 1-2mm;
The pore volume of described heteropolyacid catalyst silica-gel carrier is 1.8-2.0ml/g, specific area: 400-600m
2/ g, silica purity is greater than 99.5%, particle mean size 1-2mm.
The inventive method compared with prior art, the heteropolyacid catalyst silica-gel carrier prepared by the present invention, it has suitable pore property, suitable intensity and catalytic performance preferably; And due to this carrier pore volume and specific area larger, avoided the spatial obstacle of course of reaction, and there is higher activity; In addition, larger particle mean size is more conducive to improve the reaction efficiency of fixed bed.
The specific embodiment
In order to make content of the present invention more be convenient to understand, below in conjunction with the specific embodiment, technical solutions according to the invention are described further, but the present invention is not limited only to this.
The preparation of heteropolyacid catalyst silica-gel carrier
Embodiment 1:
(1) will in sodium silicate raw material, add water to be mixed with the solution 1000g of 18wt%, sulfuric acid adds the aqueous solution 320g that water is mixed with 30wt%;
(2) at first the 320g aqueous sulfuric acid is added to reactor, under 10 ℃, with the speed of 500g/min, add sodium silicate solution, stop adding sodium silicate solution to reaction end pH=3.At normal temperatures, standing 20 hours to gel.
(3) above-mentioned gel is smashed with high shear, added 18 gram EDTA.Be warming up to 70 ℃, be incubated 2 hours.
(4) by 3) material filtering, the washing that obtain, be washed till in filter cake below sodium ions content 0.1%wt, after filter cake is pulled an oar and added ammoniacal liquor to be adjusted to the pH value to be 7, be warming up to 90 ℃, be incubated 1 hour.
(5) utilize press spray drying and dehydrating drying steps 4) product that obtains, the adjustment particle mean size is 1mm.
Embodiment 2
(1) will in sodium silicate raw material, add water to be mixed with 19% solution 1000g, sulfuric acid adds water and is mixed with 35% aqueous solution 380g,
(2) at first the 380g aqueous sulfuric acid is added to reactor, under 12 ℃, with the speed of 300g/min, add sodium silicate solution, stop adding sodium silicate solution to reaction end pH=3.At normal temperatures, standing 22 hours to gel.
(3) above-mentioned gel is smashed with high shear, added 19 gram EDTA.Be warming up to 80 ℃, be incubated 2 hours.
(4) by 3) material filtering, the washing that obtain, be washed till in filter cake below sodium ions content 0.1%wt, after filter cake is pulled an oar and added ammoniacal liquor to be adjusted to the pH value to be 8, be warming up to 80 ℃, be incubated 1 hour.
(5) utilize press spray drying and dehydrating drying steps 4) product that obtains; The adjustment granularity is 1mm.
Embodiment 3:
(1) will in sodium silicate raw material, add water to be mixed with 20% solution 1000g, sulfuric acid adds water and is mixed with 30% aqueous solution 467g,
(2) at first the 467g aqueous sulfuric acid being added to reactor, under 15 ℃, with the speed of 300g/min, add sodium silicate solution, is 4 to stop adding sodium silicate solution to reaction end pH value.At normal temperatures, standing 24 hours to gel.
(3) above-mentioned gel is smashed with high shear, added 20 gram EDTA.Be warming up to 80 ℃, be incubated 3 hours.
(4) by 3) material filtering, the washing that obtain, be washed till below filter cake sodium ions content 0.1%wt, after filter cake is pulled an oar and added ammoniacal liquor to be adjusted to the pH value to be 8, be warming up to 90 ℃, be incubated 2 hours.
(5) utilize press spray drying and dehydrating drying 3) product that obtains; The adjustment granularity is 2mm.
Performance test
The heteropolyacid catalyst silica-gel carrier that the acetic acid that below from following several aspects, adopts following method to prepare embodiment 1-3 and butene esters are combined to 2-butyl acetate carries out performance measurement:
(1) mensuration of pore volume, specific area
Adopt classical BET nitrogen adsorption to carry out single point assay.
(2) silicon dioxide content test
According to food stage silica standard, Q/THY224-95 is measured.
(3) average grain diameter is measured
Adopt the laser particle analyzer of Ma Erwen to be measured.
(4) mensuration-2-butyl acetate of catalyst activity is selective
(1) preparation of catalyst
Should at first configure catalyst in order to measure catalyst activity, the catalyst activity component adopts phosphomolybdic acid.Phosphomolybdic acid and silica-gel carrier weight ratio are 1:10, and the preparation method is as follows, take the 10g carrier, take 1 gram phosphomolybdic acid and add 100 grams to stir phosphomolybdic acid is dissolved, dry under 150 ℃ after adding silica-gel carrier to mix, by dried material under 400 ℃, calcine 6 hours, make catalyst.
(2) catalyst activity examination
Take 98% industrial acetic 40g, 1-butylene (98% content) 40 grams, 10 gram catalyst.The 200ml autoclave of packing into.120 ℃ of reaction temperatures, 2 hours reaction time.After reaction finishes, cooling, get liquid phase material and analyze and measure the selective of 2-butyl acetate by gas-chromatography.
Pore volume, specific area, dioxide-containing silica, average grain diameter and the 2-butyl acetate of the heteropolyacid catalyst silica-gel carrier that embodiment 1-3 makes be measurement result optionally, all lists in table 1.
Table 1 acetic acid and butene esters are combined to the heteropolyacid catalyst silica-gel carrier performance measurement result of 2-butyl acetate
Claims (2)
1. the method for making of an acetic acid and the acetic acid synthesized secondary butyl ester heteropolyacid catalyst silica-gel carrier of butylene, is characterized in that, comprises the following steps:
1) sodium silicate solution is mixed with to the solution in silica 18-20%wt, sulfuric acid adds the aqueous solution that water is mixed with 30-35%wt;
2) aqueous sulfuric acid is added to reactor, then under 10-15 ℃, with the speed of 300-500g/min, adds step 1) sodium silicate solution of preparation, stop adding sodium silicate solution for 3-4 to the pH value, standing 20-24 hour at normal temperatures to forming gel;
3) by step 2) gel that obtains smashes, and adds EDTA, sodium tartrate and sodium oxalate one or more complexing agents wherein, and the 7%-13% that the complexing agent addition is the silica total amount, be warming up to 70-80 ℃, insulation 1-5 hour;
4) step 3) is obtained to product and filter, wash, be washed till below filter cake sodium ions content 0.1%wt, filter cake is pulled an oar and added ammoniacal liquor to be adjusted to the pH value for 7-8, be warming up to 80-90 ℃, insulation 1-2 hour;
5) finally utilize press spray drying and dehydrating drying that step 4) is obtained to product, the adjustment granularity is 1-2mm;
The pore volume of described heteropolyacid catalyst silica-gel carrier is 1.4-2.0ml/g, specific area: 400-600m
2/ g, silica purity is greater than 99.5%, particle mean size 1-2mm.
2. the method for making of heteropolyacid catalyst silica-gel carrier according to claim 1, is characterized in that, comprises the following steps:
1) sodium silicate solution is mixed with to the solution in silica 18-20%wt, sulfuric acid adds the aqueous solution that water is mixed with 30-35%wt;
2) aqueous sulfuric acid is added to reactor, then under 10-15 ℃, with the speed of 300-500g/min, adds step 1) sodium silicate solution of preparation, stop adding sodium silicate solution for 3-4 to the pH value, standing 20-24 hour at normal temperatures to forming gel;
3) by step 2) gel that obtains smashes, and adds EDTA, sodium tartrate and sodium oxalate one or more complexing agents wherein, and the 8-12% that the complexing agent addition is the silica total amount, be warming up to 70-80 ℃, insulation 1-5 hour;
4) step 3) is obtained to product filters, washing, be washed till in filter cake below sodium ions content 0.1%wt, filter cake pull an oar and added ammoniacal liquor to be adjusted to pH value to be 7-8, to be warming up to 80-90 ℃, be incubated 1-2 hour;
5) finally utilize press spray drying and dehydrating drying that step 4) is obtained to product, the adjustment granularity is 1-2mm;
The pore volume of described heteropolyacid catalyst silica-gel carrier is 1.8-2.0ml/g, specific area: 400-600m
2/ g, silica purity is greater than 99.5%, particle mean size 1-2mm.
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Cited By (3)
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| CN106111097A (en) * | 2016-06-27 | 2016-11-16 | 中国海洋石油总公司 | A kind of preparation method of high-purity column chromatography silica gel |
| CN108623836A (en) * | 2018-05-15 | 2018-10-09 | 东华大学 | A kind of heteropolyacid salt carrying fiber element porous material and preparation method thereof |
| CN108620094A (en) * | 2017-03-21 | 2018-10-09 | 广州凌玮科技股份有限公司 | A kind of preparation method of four esterification catalyst sulfonation silica gel of carbon |
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| CN101293210A (en) * | 2007-04-25 | 2008-10-29 | 中国科学院大连化学物理研究所 | Composite catalyst for preparing sec-butyl acetate with direct esterification of ethyl ester and butylene |
| CN102002120A (en) * | 2010-09-20 | 2011-04-06 | 中国海洋石油总公司 | Method for preparing special silica gel carrier with large pore volume and large specific surface area |
| US20120010379A1 (en) * | 2009-03-16 | 2012-01-12 | Basf Se | Catalyst carrier based on silica gel |
| CN102382216A (en) * | 2011-05-26 | 2012-03-21 | 中国海洋石油总公司 | Preparation method of silica gel carrier for ethylene polymerization catalyst |
| CN103043670A (en) * | 2012-12-26 | 2013-04-17 | 青岛中能集团有限公司 | Process flow of novel water-absorbent silica gel |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101293210A (en) * | 2007-04-25 | 2008-10-29 | 中国科学院大连化学物理研究所 | Composite catalyst for preparing sec-butyl acetate with direct esterification of ethyl ester and butylene |
| US20120010379A1 (en) * | 2009-03-16 | 2012-01-12 | Basf Se | Catalyst carrier based on silica gel |
| CN102002120A (en) * | 2010-09-20 | 2011-04-06 | 中国海洋石油总公司 | Method for preparing special silica gel carrier with large pore volume and large specific surface area |
| CN102382216A (en) * | 2011-05-26 | 2012-03-21 | 中国海洋石油总公司 | Preparation method of silica gel carrier for ethylene polymerization catalyst |
| CN103043670A (en) * | 2012-12-26 | 2013-04-17 | 青岛中能集团有限公司 | Process flow of novel water-absorbent silica gel |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106111097A (en) * | 2016-06-27 | 2016-11-16 | 中国海洋石油总公司 | A kind of preparation method of high-purity column chromatography silica gel |
| CN108620094A (en) * | 2017-03-21 | 2018-10-09 | 广州凌玮科技股份有限公司 | A kind of preparation method of four esterification catalyst sulfonation silica gel of carbon |
| CN108620094B (en) * | 2017-03-21 | 2021-01-05 | 广州凌玮科技股份有限公司 | Preparation method of carbon tetra-esterification catalyst sulfonated silica gel |
| CN108623836A (en) * | 2018-05-15 | 2018-10-09 | 东华大学 | A kind of heteropolyacid salt carrying fiber element porous material and preparation method thereof |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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Effective date of registration: 20161012 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |