CN103464153B - Hydrogenation catalyst for producing dimethyl succinate and method for preparing hydrogenation catalyst for producing dimethyl succinate - Google Patents
Hydrogenation catalyst for producing dimethyl succinate and method for preparing hydrogenation catalyst for producing dimethyl succinate Download PDFInfo
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- CN103464153B CN103464153B CN201310451771.8A CN201310451771A CN103464153B CN 103464153 B CN103464153 B CN 103464153B CN 201310451771 A CN201310451771 A CN 201310451771A CN 103464153 B CN103464153 B CN 103464153B
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Abstract
The invention provides a method for preparing hydrogenation catalyst for producing dimethyl succinate. According to the method, Resin ribbon ball-shaped active carbon having high specific surface area and a micro-hole structure serves as the carrier, palladium nitrate loading is carried out according to a liquid phase deposition method, WO3 loading is then carried out, washing, drying and roasting are then carried out, and the hydrogenation catalyst is generated. WO3 provides proper weakly acidic active sites for the catalyst, and therefore high activity and high selectivity of the catalyst can still be kept after long-period operation and the service life of the hydrocarbon catalyst can be prolonged.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst and preparation method thereof, particularly a kind of preparation method producing dimethyl succinate spent hydroprocessing catalyst.
Technical background
Dimethyl succinate (also known as dimethyl succinate) is important synthetic perfume and food additives, can be used as food antiseptics.Meanwhile, it or a kind of important chemical intermediate, adopt excessive dimethyl succinate to make solvent, methyl alcohol makees cosolvent, dimethyl succinate and sodium methoxide is reacted and prepares DMSS.DMSS (DMSS) is the important intermediate of synthesis quinacridone class pigment (Quiacridone).Industrial is at present all that the synthetic route adopting dimethyl succinate (DMS) to be reacted by self-condensation for raw material is produced.At present mainly succinic acid and methyl alcohol are raw material, make catalyst obtained by esterification with the concentrated sulfuric acid dimethyl succinate, but the technique side reaction of this employing sulphuric acid catalysis esterification is many, yield is low, post processing is complicated, and equipment corrosion is serious, the dimethyl suflfate of by-product severe toxicity, serious environment pollution.Dimethyl succinate most up-to-date techniques are raw material with dimethyl maleate and hydrogen, make catalyst obtained by hydrogenation reaction with palladium-carbon catalyst, and existing process catalyst is short for service life, and production capacity is low, and cost is higher.
CN102070448A mono-kind prepares the method for dimethyl succinate, under hydrogenation catalyst and reaction condition, dimethyl maleate and hydrogen hydrogenation reaction in fixed bed reactors generates dimethyl succinate, the active component of catalyst is one or more in group VIII metal, active component total amount is 0.2-10%(wt), carrier is one or more of metal oxide and active carbon.
It is shorter for service life all to there is catalyst in above patented technology, catalyst surface accumulates after coke, the shortcoming of the very fast inactivation of catalyst, often more catalyst changeout can affect production efficiency, improve production cost, become problem in the urgent need to address so how to increase the service life.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of production dimethyl succinate spent hydroprocessing catalyst and preparation method thereof.
The present invention, to have the resin based sphere active carbon of high-ratio surface sum microcellular structure for carrier, by liquid deposition method load palladium nitrate, and then carries out WO to it
3load, then through washing, dry, roasting, generates dimethyl succinate spent hydroprocessing catalyst.WO
3for catalyst provides suitable weakly acidic active sites, thus catalyst still can keep higher activity and selectivity after long period of operation.
The invention provides a kind of production dimethyl succinate spent hydroprocessing catalyst and preparation method thereof, comprise the following steps:
1). the load operation of palladium nitrate
Resin based sphere active carbon is soaked in alcohol solvent 2 ~ 5h(and be optimized for 4h), add and account for the palladium nitrate that resin based sphere active carbon mass percent is 0.5 ~ 5%, 0 ~ 30 DEG C (being optimized for 15 DEG C) reaction, 10 ~ 20h(is optimized for 15h), with ethanol purge, dry, obtain the resin carbon catalyst of load palladium nitrate, i.e. intermediate products 1;
2). liquid deposition method load WO
3:
Sodium tungstate is dissolved in oxalic acid solution, be made into mass percent concentration 10 ~ 50%(and be optimized for 30%) solution, intermediate products 1 are put into reactor, add the sodium tungstate oxalic acid solution accounting for intermediate products 1 mass percentage content 1 ~ 5%, temperature 100 ~ 120 DEG C (being optimized for 110 DEG C), stir most of water in lower slow evaporate to dryness system, repeatedly neutrality is washed till by deionized water, put into Muffle furnace roasting, 200 ~ 400 DEG C (being optimized for 250 DEG C) process, 2 ~ 5h(is optimized for 3h), obtain final products.
Resin based sphere active carbon is commercially available prod, is obtained through roasting by macropore phenylethylene resin series polymer, as Shanxi Cui Hong Science and Technology Ltd., and the resin based sphere active carbon that Langfang Ai Er blood purification equipment Chang Deng enterprise produces.
This product has following beneficial effect:
The shape selective that catalyst of the present invention has is very effective to suppression side reaction with restriction aperture, the WO of load
3for catalyst provides weakly acidic active sites, thus catalyst still can keep higher activity after long period of operation, can improve the service life of hydrogenation catalyst, is 3 times of common palladium-carbon catalyst, the longlyest uses 102 days.
Detailed description of the invention
Following instance is only further illustrate the present invention, is not restriction the scope of protection of the invention.
Embodiment 1:
Resin based sphere active carbon, Shanxi Cui Hong Science and Technology Ltd. produces
Sphere diameter at 0.3-1.2mm, specific area (BET) 950-1200 (m2/g), pore volume 0.6-0.75ml/g.
1). the load operation of palladium nitrate
Resin based sphere active carbon is soaked 4h in alcohol solvent, adds and account for the palladium nitrate that resin based sphere active carbon mass percent is 2%, 15 DEG C of reaction 15h, with ethanol purge, dry, obtain the resin carbon catalyst of load palladium nitrate, i.e. intermediate products 1.
2). liquid deposition method load WO
3:
Sodium tungstate is dissolved in oxalic acid solution, being made into mass percent concentration is 30% solution, intermediate products 1 are put into reactor, adds the sodium tungstate oxalic acid solution accounting for intermediate products 1 mass percentage content 3%, temperature 110 DEG C, stir most of water in lower slow evaporate to dryness system, repeatedly be washed till neutrality by deionized water, put into Muffle furnace roasting, 250 DEG C of process 3h, obtain final products, be numbered KRB-1.
Embodiment 2
Add in step 1 and account for the palladium nitrate that resin based sphere active carbon mass percent is 0.5%, the other the same as in Example 1.Products obtained therefrom is numbered KRB-2.
Embodiment 3
Add in step 1 and account for the palladium nitrate that resin based sphere active carbon mass percent is 5%, the other the same as in Example 1.Products obtained therefrom is numbered KRB-3.
Embodiment 4
The sodium tungstate oxalic acid solution accounting for intermediate products 1 mass percentage content 1% is added, the other the same as in Example 1 in step 2.Products obtained therefrom is numbered KRB-4.
Embodiment 5
The sodium tungstate oxalic acid solution accounting for intermediate products 1 mass percentage content 1% is added, the other the same as in Example 2 in step 2.Products obtained therefrom is numbered KRB-5.
Embodiment 6
The sodium tungstate oxalic acid solution accounting for intermediate products 1 mass percentage content 1% is added, the other the same as in Example 3 in step 2.Products obtained therefrom is numbered KRB-6.
Embodiment 7
The sodium tungstate oxalic acid solution accounting for intermediate products 1 mass percentage content 5% is added, the other the same as in Example 1 in step 2.Products obtained therefrom is numbered KRB-7.
Embodiment 8
The sodium tungstate oxalic acid solution accounting for intermediate products 1 mass percentage content 5% is added, the other the same as in Example 2 in step 2.Products obtained therefrom is numbered KRB-8.
Embodiment 9
The sodium tungstate oxalic acid solution accounting for intermediate products 1 mass percentage content 5% is added, the other the same as in Example 3 in step 2.Products obtained therefrom is numbered KRB-9.
Comparative example:
Palladium carbon catalyst: Shanghai Yi Xing catalyst Co., Ltd produces.
Embodiment 10. catalyst is used for the evaluation that Hydrogenation reacts for dimethyl succinate
Embodiment evaluating catalyst:
Evaluation experiment 1L reactor is divided into four sections, production dimethyl succinate spent hydroprocessing catalyst sample 100mL in every section of filling embodiment, dimethyl maleate and hydrogen feed pass through four sections of beds from below to up, enter from the bed lower part four sections of every section of catalyst, under the effect of catalyst, reaction generates dimethyl succinate.Reaction temperature 100 DEG C, dimethyl maleate air speed 0.5/h, reaction pressure is for being 0.5MPa, and the contrast of dimethyl maleate conversion ratio is in table 1, and low conversion rate is inactivation in 50%.
Comparative example evaluating catalyst:
Evaluation experiment 1L reactor is divided into four sections, every section of filling palladium carbon catalyst sample 100mL, dimethyl maleate and hydrogen feed pass through four sections of beds from below to up, enter from the bed lower part four sections of every section of catalyst, and under the effect of catalyst, reaction generates dimethyl succinate.Reaction temperature 100 DEG C, dimethyl maleate air speed 0.5/h, reaction pressure is 0.5MPa, and low conversion rate is inactivation in 50%, and service life compares in table 1.
Table 1: the comparison in test specimen service life that different process is made
| Numbering | Service life/sky |
| KRB－1 | 92 |
| KRB－2 | 88 |
| KRB－3 | 94 |
| KRB－4 | 102 |
| KRB－5 | 84 |
| KRB－6 | 76 |
| KRB－7 | 82 |
| KRB－8 | 78 |
| KRB－9 | 74 |
| KRB－10 | 84 |
| Comparative example | 29 |
Visible gained catalyst of the present invention has good catalytic effect, and the service life of the effective extending catalyst of energy, extend more than 3 times service life, the shape selective that catalyst of the present invention has is described and limits aperture very effective to suppression side reaction, the WO of load simultaneously
3for catalyst provides suitable weakly acidic active sites, thus hydrogenation catalyst still can keep higher activity after long period of operation.
Claims (5)
1. produce a preparation method for dimethyl succinate spent hydroprocessing catalyst, comprise the following steps:
1). the load operation of palladium nitrate
Resin based sphere active carbon is soaked 2 ~ 5h in alcohol solvent, adds and account for the palladium nitrate that resin based sphere active carbon mass percent is 0.5 ~ 5%, 0 ~ 30 DEG C of reaction 10 ~ 20h, with ethanol purge, dry, obtain the resin carbon catalyst of load palladium nitrate, i.e. intermediate products 1;
2). liquid deposition method load WO
3:
Sodium tungstate is dissolved in oxalic acid solution, be made into mass percent concentration 10 ~ 50% solution, intermediate products 1 are put into reactor, add the sodium tungstate oxalic acid solution accounting for intermediate products 1 mass percentage content 1 ~ 5%, temperature 100 ~ 120 DEG C, stir most of water in lower slow evaporate to dryness system, repeatedly neutrality is washed till by deionized water, put into Muffle furnace roasting, 200 ~ 400 DEG C of process 2 ~ 5h, obtain dimethyl succinate spent hydroprocessing catalyst.
2. preparation method according to claim 1, is characterized in that: in step 1), resin based sphere active carbon is soaked 4h in alcohol solvent, adds and accounts for the palladium nitrate that resin based sphere active carbon mass percent is 0.5 ~ 5%, 15 DEG C of reaction 15h.
3. preparation method according to claim 1, it is characterized in that: step 2) in sodium tungstate is dissolved in oxalic acid solution, be made into mass percent concentration 30% solution, intermediate products 1 are put into reactor, add the sodium tungstate oxalic acid solution accounting for intermediate products 1 mass percentage content 1 ~ 5%, temperature 110 DEG C, stir most of water in lower slow evaporate to dryness system, be repeatedly washed till neutrality by deionized water, put into Muffle furnace roasting, 250 DEG C of process 3h, obtain dimethyl succinate spent hydroprocessing catalyst.
4. according to the production dimethyl succinate spent hydroprocessing catalyst that the described preparation method of one of claim 1-3 obtains.
5. the application in dimethyl succinate produced by catalyst according to claim 4.
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| CN201310451771.8A CN103464153B (en) | 2013-09-27 | 2013-09-27 | Hydrogenation catalyst for producing dimethyl succinate and method for preparing hydrogenation catalyst for producing dimethyl succinate |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070448A (en) * | 2011-02-22 | 2011-05-25 | 湖南长岭石化科技开发有限公司 | Method for preparing dimethyl succinate |
| CN102228831A (en) * | 2011-04-25 | 2011-11-02 | 中国科学院大连化学物理研究所 | Catalyst for gas phase hydrogenation of acetic acid to prepare ethanol |
| CN102863335A (en) * | 2012-10-15 | 2013-01-09 | 中国科学院长春应用化学研究所 | Preparation method of diethyl succinate |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070448A (en) * | 2011-02-22 | 2011-05-25 | 湖南长岭石化科技开发有限公司 | Method for preparing dimethyl succinate |
| CN102228831A (en) * | 2011-04-25 | 2011-11-02 | 中国科学院大连化学物理研究所 | Catalyst for gas phase hydrogenation of acetic acid to prepare ethanol |
| CN102863335A (en) * | 2012-10-15 | 2013-01-09 | 中国科学院长春应用化学研究所 | Preparation method of diethyl succinate |
Non-Patent Citations (1)
| Title |
|---|
| 液相催化加氢合成丁二酸二甲酯的研究;努尔买买提·阿布都克力木等;《应用化工》;20110731;第40卷(第07期);1176-1179,1185 * |
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