CN105327701A - Preparation method of dibasic ester aromatic ring saturation catalyst containing benzene ring - Google Patents
Preparation method of dibasic ester aromatic ring saturation catalyst containing benzene ring Download PDFInfo
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- CN105327701A CN105327701A CN201510866966.8A CN201510866966A CN105327701A CN 105327701 A CN105327701 A CN 105327701A CN 201510866966 A CN201510866966 A CN 201510866966A CN 105327701 A CN105327701 A CN 105327701A
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Abstract
The invention discloses a preparation method of a dibasic ester aromatic ring saturation catalyst containing a benzene ring. According to the preparation method, a carrier with a specific macroporous structure and a halogen-free noble metal precursor are adopted, a Ru-containing catalyst is prepared through a special impregnation method, and the catalyst with the total pore volume ranging from 0.7 mg/g to 2.5 ml/g is prepared after low-temperature drying and calcination are conducted, wherein the proportion of pores with the pore volume larger than 15 nm is not lower than 55%, and the specific surface area ranges from 90 cm<2>/g to 240 cm<2>/g; the active component is the noble metal Ru, and the content of the simple substance Ru ranges from 0.02 wt% to 1.3 wt%; the chlorine content of the catalyst is smaller than or equal to 0.05 wt% of the total weight of the catalyst, the active component is distributed on the catalyst in an eggshell or egg white mode, and the content of the active component in the carrier is not larger than 0.01 wt%. According to the preparation method, the use ratio of the noble metal and the activity of the catalyst can be increased; meanwhile, the intoxicating phenomenon of the active component is restrained, the catalyst can be applied to the hydrogenation process of terephthalic acid dibasic ester or isophthalic acid dibasic ester and the hydrogenation process of o-benzene dibasic ester or p-benzene dibasic ester or m-benzene dibasic ester, and the conversion rate of reactants and the selectivity both reach 99 percent or above.
Description
Technical field
The invention belongs to chemical catalyst technical field, be specifically related to a kind of preparation method of the dibasic ester class aromatic ring saturation catalyst containing phenyl ring.
Background technology
In plastics industry, the negative effect of adjacent benzene class plasticizer to human body and environment more and more receives the concern of people, and a lot of country is all at the nontoxic green plasticization agent product of research and development, and cyclohexane cyclohexanedimethanodibasic dibasic ester is exactly a kind of novel environmental friendliness plasticizer product.Its preparation technology is simple, can react a step obtain by adjacent benzene class dioctyl phthalate dicarboxylic ester by benzene ring hydrogenation.
US Patent No. 6284917 and US6248924 disclose the preparation method that hydrogenation method produces cyclohexane cyclohexanedimethanodibasic ester, to adopt in load regulation group VIII metal the-catalyst of macropore carrier, adopt batch reactor; US Patent No. 7361714 reports on support type Ru, Pt, Rh, Pa, Co or Ni catalyst that aromatics dicarboxylic acid dimethyl ester is at 100 ~ 200 DEG C, and under 5-20MPa condition, hydro-conversion is the course of reaction of corresponding fats dicarboxylic acid dimethyl ester.Domestic CN101927166B patent describes a kind of coprecipitation to be prepared high activity and supports Raney nickel for phthalic acid dibasic ester class Hydrogenation cyclohexane cyclohexanedimethanodibasic dibasic ester, but reaction conversion ratio is not high and catalyst preparation process is not easy to industrialization amplifies.CN101406941A discloses a kind of Al
2o
3, ZrO
2, TiO
2the hydrogenation catalyst of load regulation group VIII metal on macropore carrier.
The important topic that higher reaction-ure conversion-age (being greater than 99%) and target product selectivity (being greater than 98%) are researchers can be reached at present.In addition, existing of well-known halogen element as easy as rolling off a logly causes active component deactivation phenomenom.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of preparation method of the dibasic ester class aromatic ring saturation catalyst containing phenyl ring, this preparation method selects the form of suitable active component presoma to coordinate the post processor optimized, active component can be obtained in eggshell or the catalyst of protein type distribution on carrier, and the migration of inhibit activities component and grain growth effectively.Not halogen-containing noble metal precursor body is selected to it also avoid the inactivation of the catalyst that halogen causes in long period reaction.
For solving the problems of the technologies described above, the present invention is achieved by the following technical solutions,
The preparation method of a kind of dibasic ester class aromatic ring saturation catalyst containing phenyl ring of the present invention, the carrier of wherein said catalyst is SiO
2-Al
2o
3, SiO
2, Al
2o
3in one or both mixture; Total pore volume 0.7-2.5ml/g, wherein more than 15nm pore volume proportion is not less than 55%, and specific surface is 90-240cm
2/ g; Active component is noble metal Ru, and simple substance Ru content is 0.02-1.3wt%; The chlorinity of catalyst accounts for total catalyst weight≤0.05wt%; Active component is eggshell or protein type distribution on a catalyst, and carrier center active component content is not higher than 0.01wt%;
The preparation method of described catalyst comprises:
A) by the solid salt powder containing Ru, the mixture of one or more dripped in appropriate glacial acetic acid, ethanol, ethylene glycol, acetone, methyl alcohol dissolves;
B) slowly drip ammoniacal liquor to containing in ruthenium solution, adjustment pH value of solution is 7.0-12.0, is preferably 8.5-11.5;
C) step b is used) solution impregnating carrier that obtains, immediately at 30-100 DEG C of freeze-day with constant temperature 10-24h after saturated adsorption;
D) by step c) product roasting under the sintering temperature of 250-350 DEG C of obtaining obtains catalyst;
The solid salt wherein containing Ru is the mixture of one or more of nitric acid ruthenium (III), acetic acid ruthenium (III), nitrosyl nitrate ruthenium (III).
According to preparation method of the present invention, wherein step c) in freeze-day with constant temperature temperature be 40-80 DEG C, drying time is 12-20h.
Present invention also offers catalyst that above-mentioned preparation method obtains adjacent (to or) application in the technique of the producing cyclohexane by adding hydrogen class dibasic ester of benzene dibasic acid ester class, it is characterized in that, described catalyst needs to carry out H before using
2reduction activation.
Preparation method of the present invention adopts has specific macroporous structure carrier and not halogen-containing noble metal precursor body, with the catalyst of special infusion process technique preparation containing Ru, through low temperature drying and roasting, obtain a kind of highly active loaded noble metal catalyst, its active component is Ru, in catalyst, halogen element content is lower than 0.05%wt, and carrier has suitable specific area and pore structure.Particularly utilize the obtained catalyst activity component of the inventive method to be albumen or eggshell type distribution, have followed the feature that this reaction external diffusion controls, more contribute to improving reaction efficiency and noble metal utilisation.Activity evaluation display reaction-ure conversion-age and selectively all reach more than 99%.The catalyst that the inventive method obtains also can be used for the hydrogenation of () phthalic acid dibasic ester and adjacent (to or) hydrogenation process of benzene class dibasic ester.
Specific embodiment
Below in conjunction with specific embodiment, preparation method of the present invention is further described.
Embodiment 1
Get amorphous silicon aluminium powder and macro porous silica gel mixes appropriate alumina binder extruded moulding, carrier specific area 105cm after drying roasting
2/ g, total pore volume 2.0ml/g.Get proper amount of acetic acid ruthenium powder, be dissolved in proper amount of acetic acid solution, slowly drip dilute ammonia solution until pH value of solution reaches 9.5, by appropriate carrier impregnation wherein, after saturated adsorption, put into baking oven 80 DEG C of dry 18h immediately, 300 DEG C of roasting 3h.X-ray fluorescence analysis result shows: simple substance Ru content accounts for the 0.3%wt of catalyst, and Cl constituent content is less than 0.02%wt.
Embodiment 2
Get appropriate macroporous aluminium oxide dry powder (butt accounts for 90%) and tie agent (butt accounts for 10%) extruded moulding with aluminium oxide, carrier specific area 193cm after drying roasting
2/ g, total pore volume 1.31ml/g.Get proper amount of acetic acid ruthenium powder, be dissolved in ethanol in proper amount solution, slowly drip dilute ammonia solution until pH value of solution reaches 8.5, by appropriate carrier impregnation wherein, after saturated adsorption, put into the dry 18h of baking oven 60 immediately, 300 roasting 3h.X-ray fluorescence analysis result shows: simple substance Ru content accounts for the 0.8%wt of catalyst, and Cl constituent content is less than 0.02%wt.
Embodiment 3
Get macroporous aluminium oxide powder (butt accounts for 30%) and aluminium oxide A101 powder (butt 70%) extruded moulding, carrier specific area 218cm after drying roasting
2/ g, total pore volume 0.79ml/g.Get proper amount of acetic acid ruthenium powder, be dissolved in ethanol in proper amount solution, slowly drip dilute ammonia solution until pH value of solution reaches 8.0, by appropriate carrier impregnation wherein, after saturated adsorption, put into the dry 18h of baking oven 60 immediately, 300 roasting 3h.X-ray fluorescence analysis result shows: simple substance Ru content accounts for the 0.8%wt of catalyst, and Cl constituent content is less than 0.02%wt.
Embodiment 4
Get appropriate nitrosyl nitrate ruthenium ruthenium powder, be dissolved in proper amount of acetone solution, slowly drip dilute ammonia solution until pH value of solution reaches 10.5, by appropriate macroporous silicon dioxide carrier (pore volume 2.33ml/g, specific surface 220cm
2/ g) flood wherein, after saturated adsorption, put into the dry 12h of baking oven 60 immediately, 350 roasting 3h.X-ray fluorescence analysis result shows: simple substance Ru content accounts for the 0.5%wt of catalyst, and Cl constituent content is less than 0.02%wt.
Comparative example:
The Ru/Al that Ru load capacity is 0.8wt% is prepared according to the preparation method of CN101406840A
2o
3.
The evaluation of above-mentioned catalyst is carried out at fixed bed evaluating apparatus, and hydrogenating materials is diisooctyl phthalate.First temperature programmed reduction is carried out to catalyst before charging.Reaction condition: pressure 15MPa, reaction temperature 300 DEG C, hydrogen-oil ratio 1000:1, air speed 0.5h
-1.Reaction raw materials is separated with each product gas-chromatography, calculates the percentage composition of each material of mixture with area normalization method.
Evaluation result:
Evaluating catalyst the results are shown in Table 1
Table 1
Claims (4)
1., containing a preparation method for the dibasic ester class aromatic ring saturation catalyst of phenyl ring, it is characterized in that:
The carrier of described catalyst is SiO
2-Al
2o
3, SiO
2and Al
2o
3in the mixture of one or more; Total pore volume 0.7-2.5ml/g, wherein more than 15nm pore volume proportion is not less than 55%, and specific surface is 90-240cm
2/ g; Active component is noble metal Ru, and simple substance Ru content is 0.02-1.3wt%; The chlorinity of catalyst accounts for total catalyst weight≤0.05wt%; Active component is eggshell or protein type distribution on a catalyst, and carrier center active component content is not higher than 0.01wt%;
The preparation method of described catalyst comprises:
A) by the solid salt powder containing Ru, the mixture of one or more dripped in appropriate glacial acetic acid, ethanol, ethylene glycol, acetone, methyl alcohol dissolves;
B) slowly drip ammoniacal liquor to containing in ruthenium solution, adjustment pH value of solution is 7.0-12.0;
C) step b is used) solution impregnating carrier that obtains, immediately at 30-100 DEG C of freeze-day with constant temperature 10-24h after saturated adsorption;
D) by step c) product roasting under the sintering temperature of 250-350 DEG C of obtaining obtains catalyst;
The solid salt wherein containing Ru is the mixture of one or more of nitric acid ruthenium, acetic acid ruthenium, nitrosyl nitrate ruthenium.
2. preparation method according to claim 1, is characterized in that, the described pH containing ruthenium solution is 8.5-11.5.
3. preparation method according to claim 1, is characterized in that, step c) in freeze-day with constant temperature temperature be 40-80 DEG C, drying time is 12-20h.
4. the catalyst that obtains of preparation method according to claim 1 adjacent (to or) application in the technique of the producing cyclohexane by adding hydrogen class dibasic ester of benzene dibasic acid ester class, it is characterized in that, described catalyst needs to carry out H before using
2reduction activation.
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Cited By (6)
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| CN108187675A (en) * | 2017-12-01 | 2018-06-22 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of noble metal catalyst for benzene ring hydrogenation saturation |
| CN109896958A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of synthetic method of 1,2,4,5- cyclohexanetetracarboxylic acid tetra-ethyl ester |
| CN110624537A (en) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | Preparation method of phthalate hydrogenation catalyst |
| CN111318278A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Preparation method of catalyst for preparing cyclohexane-1, 2-dioctyl phthalate |
| JP2021501680A (en) * | 2017-11-06 | 2021-01-21 | ハンファ ケミカル コーポレーションＨａｎｗｈａ Ｃｈｅｍｉｃａｌ Ｃｏｒｐｏｒａｔｉｏｎ | A catalyst for hydrogenation reaction of aromatic compounds and its production method |
| CN115709064A (en) * | 2021-08-23 | 2023-02-24 | 中国石油化工股份有限公司 | Eggshell type catalyst, preparation method and application thereof, and method for preparing cyclohexane-1,2-dicarboxylic acid diester through selective hydrogenation |
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| JP2021501680A (en) * | 2017-11-06 | 2021-01-21 | ハンファ ケミカル コーポレーションＨａｎｗｈａ Ｃｈｅｍｉｃａｌ Ｃｏｒｐｏｒａｔｉｏｎ | A catalyst for hydrogenation reaction of aromatic compounds and its production method |
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| CN109896958A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of synthetic method of 1,2,4,5- cyclohexanetetracarboxylic acid tetra-ethyl ester |
| CN109896958B (en) * | 2017-12-07 | 2021-06-01 | 中国科学院大连化学物理研究所 | Synthesis method of 1,2,4, 5-cyclohexane tetracarboxylate |
| CN110624537A (en) * | 2018-06-25 | 2019-12-31 | 中国石油化工股份有限公司 | Preparation method of phthalate hydrogenation catalyst |
| CN110624537B (en) * | 2018-06-25 | 2022-08-23 | 中国石油化工股份有限公司 | Preparation method of phthalate hydrogenation catalyst |
| CN111318278A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Preparation method of catalyst for preparing cyclohexane-1, 2-dioctyl phthalate |
| CN115709064A (en) * | 2021-08-23 | 2023-02-24 | 中国石油化工股份有限公司 | Eggshell type catalyst, preparation method and application thereof, and method for preparing cyclohexane-1,2-dicarboxylic acid diester through selective hydrogenation |
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Application publication date: 20160217 |