CN103464153A - Method for preparing hydrogenation catalyst for producing dimethyl succinate - Google Patents
Method for preparing hydrogenation catalyst for producing dimethyl succinate Download PDFInfo
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- CN103464153A CN103464153A CN2013104517718A CN201310451771A CN103464153A CN 103464153 A CN103464153 A CN 103464153A CN 2013104517718 A CN2013104517718 A CN 2013104517718A CN 201310451771 A CN201310451771 A CN 201310451771A CN 103464153 A CN103464153 A CN 103464153A
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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 who produces the dimethyl succinate spent hydroprocessing catalyst.
Technical background
Dimethyl succinate (also claiming dimethyl succinate) is important synthetic perfume and food additives, can be used as food antiseptics.Simultaneously, it or a kind of important chemical intermediate, adopt excessive dimethyl succinate to make solvent, and methyl alcohol is made cosolvent, makes dimethyl succinate react and prepare DMSS with sodium methoxide.DMSS (DMSS) is the important intermediate of synthetic quinacridone class pigment (Quiacridone).At present industrial is all to adopt dimethyl succinate (DMS) to produce by the synthetic route of self condensation reaction for raw material.Dimethyl succinate is mainly that succinic acid and methyl alcohol are raw material, make catalyst with the concentrated sulfuric acid and obtain by esterification at present, but the technique side reaction of this employing sulphuric acid catalysis esterification is many, yield is low, the post processing complexity, and equipment corrosion is serious, the dimethyl suflfate of by-product severe toxicity, serious environment pollution.The dimethyl succinate most up-to-date techniques take dimethyl maleate and hydrogen as raw material, make catalyst with palladium-carbon catalyst and obtain by hydrogenation reaction, existing process catalyst is short service life, production capacity is low, cost is higher.
CN102070448A method for preparing 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, the active component total amount is 0.2-10%(wt), carrier is one or more of metal oxide and active carbon.
Above patented technology all exists catalyst shorter service life, accumulate coke on catalyst surface after, the shortcoming of the very fast inactivation of catalyst, often more catalyst changeout can affect production efficiency, improve production cost, so how to increase the service life, become problem in the urgent need to address.
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.
It is carrier that the resin based sphere active carbon with high-specific surface area and microcellular structure is take in the present invention, by liquid phase sedimentation load palladium nitrate, and then it is carried out to WO
3load, then through washing, drying, roasting, generate the dimethyl succinate spent hydroprocessing catalyst.WO
3for catalyst provides suitable weakly acidic active sites, thereby 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 to 2～5h(and be optimized for 4h), add and account for the palladium nitrate that the resin based sphere active carbon mass percent is 0.5～5%, 0～30 ℃ (being optimized for 15 ℃) reacted 10～20h(and is optimized for 15h), with ethanol, clean, dry, obtain the resin carbon catalyst of load palladium nitrate, intermediate products 1;
2). liquid phase sedimentation 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 to reactor, add the sodium tungstate oxalic acid solution that accounts for intermediate products 1 mass percentage content 1～5%, 100～120 ℃ of temperature (being optimized for 110 ℃), stir most of water in lower slow evaporate to dryness system, repeatedly be washed till neutrality by deionized water, put into the Muffle furnace roasting, 200～400 ℃ (being optimized for 250 ℃) are processed 2～5h(and are optimized for 3h), obtain final products.
Resin based sphere active carbon is commercially available prod, by macropore phenylethylene resin series polymer, through roasting, made, and as Shanxi Cui Hong Science and Technology Ltd., the resin based sphere active carbon that the enterprises such as Langfang Ai Er blood purification equipment factory produce.
This product has following beneficial effect:
The shape selective that catalyst of the present invention has and restriction aperture are very effective to suppressing side reaction, the WO of load
3for catalyst provides weakly acidic active sites, thereby 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 longest use 102 days.
The specific embodiment
Following instance is only to further illustrate the present invention, is not the 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 is 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 in alcohol solvent to 4h, add and account for the palladium nitrate that the resin based sphere active carbon mass percent is 2%, 15 ℃ of reaction 15h, clean with ethanol, dries, and obtains the resin carbon catalyst of load palladium nitrate, and intermediate products 1.
2). liquid phase sedimentation 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 to reactor, add the sodium tungstate oxalic acid solution that accounts for intermediate products 1 mass percentage content 3%, 110 ℃ of temperature, stir most of water in lower slow evaporate to dryness system, repeatedly be washed till neutrality by deionized water, put into the Muffle furnace roasting, process 3h for 250 ℃, obtain final products, be numbered KRB-1.
Embodiment 2
Add in step 1 and account for the palladium nitrate that the 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 the 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
Add the sodium tungstate oxalic acid solution that accounts for intermediate products 1 mass percentage content 1% in step 2, the other the same as in Example 1.Products obtained therefrom is numbered KRB-4.
Embodiment 5
Add the sodium tungstate oxalic acid solution that accounts for intermediate products 1 mass percentage content 1% in step 2, the other the same as in Example 2.Products obtained therefrom is numbered KRB-5.
Embodiment 6
Add the sodium tungstate oxalic acid solution that accounts for intermediate products 1 mass percentage content 1% in step 2, the other the same as in Example 3.Products obtained therefrom is numbered KRB-6.
Embodiment 7
Add the sodium tungstate oxalic acid solution that accounts for intermediate products 1 mass percentage content 5% in step 2, the other the same as in Example 1.Products obtained therefrom is numbered KRB-7.
Embodiment 8
Add the sodium tungstate oxalic acid solution that accounts for intermediate products 1 mass percentage content 5% in step 2, the other the same as in Example 2.Products obtained therefrom is numbered KRB-8.
Embodiment 9
Add the sodium tungstate oxalic acid solution that accounts for intermediate products 1 mass percentage content 5% in step 2, the other the same as in Example 3.Products obtained therefrom is numbered KRB-9.
Comparative example:
Palladium carbon catalyst: Shanghai Yi Xing catalyst Co., Ltd produces.
Embodiment 10. catalyst are for the evaluation of the standby dimethyl succinate reaction of Hydrogenation
The embodiment evaluating catalyst:
Evaluation experiment 1L reactor is divided into four sections, every section production dimethyl succinate spent hydroprocessing catalyst sample 100mL loaded in embodiment, dimethyl maleate and hydrogen feed are passed through four sections beds from below to up, from the bed of every section catalyst, four sections of parts enter, and under the effect of catalyst, reaction generates dimethyl succinate.100 ℃ of reaction temperatures, dimethyl maleate air speed 0.5/h, reaction pressure is for being 0.5MPa, and the dimethyl maleate conversion ratio contrasts in Table 1, and low conversion rate is inactivation in 50%.
The comparative example evaluating catalyst:
Evaluation experiment 1L reactor is divided into four sections, every section filling palladium carbon catalyst sample 100mL, dimethyl maleate and hydrogen feed are passed through four sections beds from below to up, and from the bed of every section catalyst, four sections of parts enter, and under the effect of catalyst, reaction generates dimethyl succinate.100 ℃ of reaction temperatures, dimethyl maleate air speed 0.5/h, reaction pressure is 0.5MPa, and low conversion rate is inactivation in 50%, and service life is relatively 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 Examples | 29 |
Visible gained catalyst of the present invention has catalytic effect preferably, and the service life of the effective extending catalyst of energy, extend service life more than 3 times, illustrate that shape selective and restriction aperture that catalyst of the present invention has are very effective to suppressing side reaction, the WO of load simultaneously
3for catalyst provides suitable weakly acidic active sites, thereby hydrogenation catalyst still can keep higher activity after long period of operation.
Claims (5)
1. a preparation method who produces the dimethyl succinate spent hydroprocessing catalyst comprises the following steps:
1). the load operation of palladium nitrate
Resin based sphere active carbon is soaked in alcohol solvent to 2～5h, add and account for the palladium nitrate that the resin based sphere active carbon mass percent is 0.5～5%, 0～30 ℃ of reaction 10～20h, with ethanol, clean, dry, obtain the resin carbon catalyst of load palladium nitrate, intermediate products 1;
2). liquid phase sedimentation 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 to reactor, add the sodium tungstate oxalic acid solution that accounts for intermediate products 1 mass percentage content 1～5%, 100～120 ℃ of temperature, stir most of water in lower slow evaporate to dryness system, repeatedly be washed till neutrality by deionized water, put into the Muffle furnace roasting, process 2～5h, obtain the dimethyl succinate spent hydroprocessing catalyst for 200～400 ℃.
2. preparation method according to claim 1, is characterized in that: in step 1), resin based sphere active carbon is soaked in alcohol solvent to 4h, add and account for the palladium nitrate that the resin based sphere active carbon mass percent is 0.5～5%, 15 ℃ of reaction 15h.
3. preparation method according to claim 1, it is characterized in that: step 2) in sodium tungstate is dissolved in to oxalic acid solution, be made into mass percent concentration 30% solution, intermediate products 1 are put into to reactor, add the sodium tungstate oxalic acid solution that accounts for intermediate products 1 mass percentage content 1～5%, 110 ℃ of temperature, stir most of water in lower slow evaporate to dryness system, by deionized water, repeatedly be washed till neutrality, put into the Muffle furnace roasting, process 3h, obtain the dimethyl succinate spent hydroprocessing catalyst for 250 ℃.
4. the production dimethyl succinate spent hydroprocessing catalyst obtained according to the described preparation method of one of claim 1-3.
5. the application of catalyst in producing dimethyl succinate according to claim 4.
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| Application Number | Priority Date | Filing Date | Title |
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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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| 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 |
-
2013
- 2013-09-27 CN CN201310451771.8A patent/CN103464153B/en not_active Expired - Fee Related
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 |
|---|
| 努尔买买提·阿布都克力木等: "液相催化加氢合成丁二酸二甲酯的研究", 《应用化工》 * |
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