CN103464216B - The method for making of acetic acid and the acetic acid synthesized secondary butyl ester heteropolyacid catalyst silica-gel carrier of butylene - Google Patents
The method for making of acetic acid and the acetic acid synthesized secondary butyl ester heteropolyacid catalyst silica-gel carrier of butylene Download PDFInfo
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Abstract
The present invention is the preparation method of the acetic acid synthesized secondary butyl ester heteropolyacid catalyst silica-gel carrier of a kind of acetic acid and butylene, it is characterized in that, comprising: 1) preparation is in the sodium silicate solution of silica 18-20%wt, and prepares the aqueous sulfuric acid of 30-35%wt; 2) then aqueous sulfuric acid is added reactor, at 10-15 DEG C, add the sodium silicate solution of preparation with the speed of 300-500g/min, stop when being 3-4 to pH adding sodium metasilicate, leave standstill 20-24h at normal temperatures to gel; 3) gel is smashed, after adding complexing agent, be warming up to 70-80 DEG C, insulation 1-5h; 4) by step 3) gained material filtering, washing, be washed till below sodium ions content 0.1%wt, again filter cake is carried out making beating to add ammoniacal liquor to be adjusted to pH be 7-8, be warming up to 80-90 DEG C, insulation 1-2 hour, 5) press spray drying and dehydrating drying adjustment granularity is finally utilized to be 1-2mm, obtained silica-gel carrier.The carrier pore volume that the inventive method obtains is 1.4-2.0ml/g, and specific area is 400-600m
2/ g, silica purity is greater than 99.5%, particle mean size 1-2mm, has higher reactivity.
Description
Technical field
The present invention relates to a kind of preparation method of heteropolyacid catalyst silica-gel carrier, particularly relate to the method for making of a kind of acetic acid and the acetic acid synthesized secondary butyl ester heteropolyacid catalyst silica-gel carrier of butylene.
Background technology
Increasingly strict to the requirement of environmental protection in current world wide.2-butyl acetate due to toxicity comparatively I replace the organic solvent such as toluene, dimethylbenzene, ketone, be widely used in the every field such as coating, ink, medicine, essence and flavoring agent, metal cleaning, adhesive.
Current acetic acid and butene esters are combined to the catalyst that 2-butyl acetate uses and comprise: 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 have impact on the life-span of catalyst owing to there being swelling phenomenon in HTHP.Heteropoly acid is the emphasis of research at present as a kind of novel effective catalyst, but is used alone the difficulty that heteropoly acid also can cause separation and recovery.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 to be catalyst activity component, porous carrier is dispersant, the weight ratio of heteropoly acid and porous carrier is 0.01:1-10:1, wherein porous carrier uses white carbon, kaolin etc., but uses white carbon silica in embodiment.Because white carbon is a kind of open-celled structure, its heteropoly acid in esterification process has stripping phenomenon, the activity of catalyst is reduced very fast.
Summary of the invention
The object of the present invention is to provide one to have suitable pore property, there is again the preparation method that the acetic acid of good catalytic performance and butene esters are combined to the heteropolyacid catalyst silica-gel carrier of 2-butyl acetate.
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) be mixed with by sodium silicate solution in the solution of silica 18-20%wt, sulfuric acid adds water and is mixed with the aqueous solution of 30-35%wt;
2) aqueous sulfuric acid is added reactor, then at 10-15 DEG C, adds step 1 with the speed of 300-500g/min) sodium silicate solution prepared, be that 3-4 stops adding sodium silicate solution to pH value, leave standstill 20-24 at normal temperatures little of formation gel;
3) by step 2) gel that obtains smashes, and add EDTA, sodium tartrate and sodium oxalate one or more complexing agents wherein, complexing agent addition is the 7%-13% of silica total amount, is warming up to 70-80 DEG C, insulation 1-5 hour;
4) by step 3) obtain that product filters, washing, be washed till filter cake below sodium ions content 0.1%wt, filter cake carried out making beating and add ammoniacal liquor to be adjusted to pH value be 7-8, be warming up to 80-90 DEG C, insulation 1-2 hour;
5) press spray drying steps 4 is finally utilized) product that obtains, 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.
Be combined to the method for making of the heteropolyacid catalyst silica-gel carrier of 2-butyl acetate according to acetic acid of the present invention and butene esters, be characterised in that, comprise the following steps:
1) be mixed with by sodium silicate solution in the solution of silica 18-20%wt, sulfuric acid adds water and is mixed with the aqueous solution of 30-35%wt;
2) aqueous sulfuric acid is added reactor, then at 10-15 DEG C, adds step 1 with the speed of 300-500g/min) sodium silicate solution prepared, be that 3-4 stops adding sodium silicate solution to pH value, leave standstill 20-24 at normal temperatures little of formation gel;
3) by step 2) gel that obtains smashes, and add EDTA, sodium tartrate and sodium oxalate one or more complexing agents wherein, complexing agent addition is the 8-12% of silica total amount, is warming up to 70-80 DEG C, insulation 1-5 hour;
4) by step 3) obtain that product filters, washing, be washed till below sodium ions content 0.1%wt in filter cake, filter cake carried out making beating and add ammoniacal liquor to be adjusted to pH value be 7-8, be warming up to 80-90 DEG C, insulation 1-2 hour;
5) press spray drying steps 4 is finally utilized) product that obtains, 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 good catalytic performance; And due to this carrier pore volume and specific area comparatively large, avoid the spatial obstacle of course of reaction, and there is higher activity; In addition, larger particle mean size is more conducive to the reaction efficiency improving fixed bed.
Detailed description of the invention
More being convenient to make content of the present invention understand, below in conjunction with detailed description of the invention, technical solutions according to the invention are described further, but the present invention being not limited only to this.
The preparation of heteropolyacid catalyst silica-gel carrier
Embodiment 1:
(1) will add water in sodium silicate raw material and be mixed with the solution 1000g of 18wt%, sulfuric acid adds water and is mixed with the aqueous solution 320g of 30wt%;
(2) first 320g aqueous sulfuric acid is added reactor, at 10 DEG C, add sodium silicate solution with the speed of 500g/min, stop adding sodium silicate solution to reaction end pH=3.At normal temperatures, leave standstill 20 little of gel.
(3) above-mentioned gel high shear is smashed, add 18 grams of EDTA.Be warming up to 70 DEG C, be incubated 2 hours.
(4) by 3) material filtering that obtains, washing, be washed till below sodium ions content 0.1%wt in filter cake, filter cake carried out making beating and add ammoniacal liquor to be adjusted to pH value be after 7, be warming up to 90 DEG C, be incubated 1 hour.
(5) press spray drying steps 4 is utilized) product that obtains, adjustment particle mean size is 1mm.
Embodiment 2
(1) the solution 1000g that water is mixed with 19% will be added in sodium silicate raw material, sulfuric acid add water be mixed with 35% aqueous solution 380g,
(2) first 380g aqueous sulfuric acid is added reactor, at 12 DEG C, add sodium silicate solution with the speed of 300g/min, stop adding sodium silicate solution to reaction end pH=3.At normal temperatures, leave standstill 22 little of gel.
(3) above-mentioned gel high shear is smashed, add 19 grams of EDTA.Be warming up to 80 DEG C, be incubated 2 hours.
(4) by 3) material filtering that obtains, washing, be washed till below sodium ions content 0.1%wt in filter cake, filter cake carried out making beating and add ammoniacal liquor to be adjusted to pH value be after 8, be warming up to 80 DEG C, be incubated 1 hour.
(5) press spray drying steps 4 is utilized) product that obtains; Adjustment granularity is 1mm.
Embodiment 3:
(1) the solution 1000g that water is mixed with 20% will be added in sodium silicate raw material, sulfuric acid add water be mixed with 30% aqueous solution 467g,
(2) first 467g aqueous sulfuric acid being added reactor, at 15 DEG C, add sodium silicate solution with the speed of 300g/min, is that 4 stoppings add sodium silicate solution to reaction end pH value.At normal temperatures, leave standstill 24 little of gel.
(3) above-mentioned gel high shear is smashed, add 20 grams of EDTA.Be warming up to 80 DEG C, be incubated 3 hours.
(4) by 3) material filtering that obtains, washing, be washed till filter cake below sodium ions content 0.1%wt, filter cake carried out making beating and add ammoniacal liquor to be adjusted to pH value be after 8, be warming up to 90 DEG C, be incubated 2 hours.
(5) press spray drying 4 is utilized) product that obtains; Adjustment granularity is 2mm.
Performance test
Adopt the heteropolyacid catalyst silica-gel carrier that the acetic acid prepared embodiment 1-3 with the following method and butene esters be combined to 2-butyl acetate below from several aspect below and carry out performance measurement:
(1) mensuration of pore volume, specific area
Classical BET nitrogen adsorption is adopted to carry out single point assay.
(2) silicon dioxide content test
Measure according to food-grade silica standard Q/THY 224-95.
(3) average grain diameter measures
The laser particle analyzer of Malvern is adopted to measure.
(4) mensuration-2-butyl acetate selective of catalyst activity
(1) preparation of catalyst
First should configure catalyst to measure catalyst activity, catalyst activity component adopts phosphomolybdic acid.Phosphomolybdic acid and silica-gel carrier weight ratio are 1:10, and preparation method is as follows, take 10g carrier, take 1 gram of phosphomolybdic acid to add 100 grams of stirrings phosphomolybdic acid is dissolved, dry at 150 DEG C after adding silica-gel carrier mixing, by dried material at 400 DEG C, calcine 6 hours, obtained catalyst.
(2) catalyst activity examination
Take the industrial acetic 40g of 98%, 1-butylene (98% content) 40 grams, 10 grams of catalyst.Load 200mL autoclave.Reaction temperature 120 DEG C, 2 hours reaction time.After reaction terminates, cooling, gets liquid phase material gas-chromatography and carries out analyzing the selective of mensuration 2-butyl acetate.
The pore volume of the heteropolyacid catalyst silica-gel carrier that embodiment 1-3 obtains, specific area, dioxide-containing silica, average grain diameter and 2-butyl acetate optionally measurement result, all list 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. a method for making for acetic acid and the acetic acid synthesized secondary butyl ester heteropolyacid catalyst silica-gel carrier of butylene, is characterized in that, comprise the following steps:
1) be mixed with by sodium silicate solution in the solution of silica 18-20%wt, sulfuric acid adds water and is mixed with the aqueous solution of 30-35%wt;
2) aqueous sulfuric acid is added reactor, then at 10-15 DEG C, adds step 1 with the speed of 300-500g/min) sodium silicate solution prepared, be that 3-4 stops adding sodium silicate solution to pH value, leave standstill 20-24 at normal temperatures little of formation gel;
3) by step 2) gel that obtains smashes, and add EDTA, sodium tartrate and sodium oxalate one or more complexing agents wherein, complexing agent addition is the 7%-13% of silica total amount, is warming up to 70-80 DEG C, insulation 1-5 hour;
4) by step 3) obtain that product filters, washing, be washed till filter cake below sodium ions content 0.1%wt, filter cake carried out making beating and add ammoniacal liquor to be adjusted to pH value be 7-8, be warming up to 80-90 DEG C, insulation 1-2 hour;
5) press spray drying steps 4 is finally utilized) product that obtains, 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, comprise the following steps:
1) be mixed with by sodium silicate solution in the solution of silica 18-20%wt, sulfuric acid adds water and is mixed with the aqueous solution of 30-35%wt;
2) aqueous sulfuric acid is added reactor, then at 10-15 DEG C, adds step 1 with the speed of 300-500g/min) sodium silicate solution prepared, be that 3-4 stops adding sodium silicate solution to pH value, leave standstill 20-24 at normal temperatures little of formation gel;
3) by step 2) gel that obtains smashes, and add EDTA, sodium tartrate and sodium oxalate one or more complexing agents wherein, complexing agent addition is the 8-12% of silica total amount, is warming up to 70-80 DEG C, insulation 1-5 hour;
4) by step 3) obtain that product filters, washing, be washed till below sodium ions content 0.1%wt in filter cake, filter cake carried out making beating and add ammoniacal liquor to be adjusted to pH value be 7-8, be warming up to 80-90 DEG C, insulation 1-2 hour;
5) press spray drying steps 4 is finally utilized) product that obtains, 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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| 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 |
| 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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| 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 |
| WO2010105941A1 (en) * | 2009-03-16 | 2010-09-23 | 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 |
| CN102382216B (en) * | 2011-05-26 | 2013-01-16 | 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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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. |