CN104689814A - Method for preparing phthalate hydrogenation catalyst - Google Patents
Method for preparing phthalate hydrogenation catalyst Download PDFInfo
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- CN104689814A CN104689814A CN201510083129.8A CN201510083129A CN104689814A CN 104689814 A CN104689814 A CN 104689814A CN 201510083129 A CN201510083129 A CN 201510083129A CN 104689814 A CN104689814 A CN 104689814A
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Abstract
The invention discloses a method for preparing a phthalate hydrogenation catalyst. The method is characterized in that a carrier is the combination of one or more than one of amorphous silica-alumina or silicon dioxide; the BET specific surface area of the carrier is 80-400m<2>/g; the pore capacity is 0.2-3.0ml/g, and the pore diameter is 5-20nm; the active component is precious metal Ru, and the content of the elementary substance Ru is 0.02-1.3%wt; the chlorinity content of the catalyst is less than or equal to 0.05%wt of the total weight of the catalyst. The preparation method comprises the following steps: dropwise adding dilute ammonia water slowly into a Ru-contained solution, and adjusting the pH of the solution to be 7.0-12.0; dipping the carrier by the solution, and drying instantly after saturation and adsorption at the temperature of 60-150 DEG C for 1-8 hours; and roasting at the temperature of 150-300 DEG C for 1-6 hours. Solid salt containing Ru, prepared from the catalyst, is selected from one or a mixture of multiple of acetic acid (III) and nitroso acyl nitrate ruthenium (III). The prepared catalyst is used for evaluating the previous H2 reduction activation. The application field of the catalyst comprises the hydrogenation reaction of hydrogenation production of 1, 2-cyclohexane dioctyl phthalate esters of phthalate esters.
Description
Technical field
The present invention relates to catalyst technical field, be specially a kind of preparation method of phthalic acid ester hydrogenation catalyst, application is that the hydrogenation of adjacent benzene dicarboxylic acid esters class produces the reaction of 1,2-cyclohexanedicarboxyester ester.
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. 7,361,714 report at support type Ru, and on Pt, Rh, Pa, Co or Ni catalyst, 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 the hydrogenation catalyst of the load regulation group VIII metal on a kind of Al2O3, ZrO2, TiO2 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.
The invention provides a kind of highly active loaded noble metal catalyst, active component is Ru, carrier is silica or silica-alumina mixed oxide, this carrier has suitable specific area and pore structure, in catalyst, halogen element content is lower than 0.05%wt, and the life-span effectively can improving catalyst improves the anti-deactivation of catalyst.Activity evaluation display reaction-ure conversion-age and selectively all reach more than 99%.
Summary of the invention
The invention provides a kind of preparation method of phthalic acid ester hydrogenation catalyst, the catalyst that this invention relates to has suitable specific surface and pore structure, is conducive to the adsorption desorption of reactant and product, and in catalyst, halogen content is lower than 0.05%wt.The catalyst that this invention relates to carries out hydrogenation reaction in fixed bed reactors, selective all more than 99% with the conversion ratio of diisooctyl phthalate and 1,2-cyclohexane cyclohexanedimethanodibasic di-isooctyl.
The present invention is a kind of preparation method of phthalic acid ester hydrogenation catalyst, it is characterized in that:
The carrier of described catalyst is a kind of or several combination of amorphous aluminum silicide or silica, and the BET specific surface area of carrier is 80-400m
2/ g, pore volume 0.2-3.0ml/g, aperture 5-20nm; Active component is noble metal Ru, and simple substance Ru content is 0.02 ~ 1.3%wt; The chlorinity of catalyst accounts for total catalyst weight≤0.05%wt,
The preparation of catalyst adopts following steps:
A) slowly drip weak aqua ammonia to containing in ruthenium solution, adjustment pH value of solution is 7.0-12.0;
B) use a) solution impregnating carrier, dry immediately after saturated adsorption, baking temperature 60-150 DEG C, dry 1-8h;
C) sintering temperature 150-300 DEG C, roasting 1-6h.
According to preparation method of the present invention, it is characterized in that; The catalyst wherein related to, the solid salt containing Ru is selected from as acetic acid ruthenium (III), the mixture of one or more of nitrosyl nitrate ruthenium (III).
According to preparation method of the present invention, it is characterized in that; The catalyst wherein related to, containing ruthenium solution
PH is 8.5-11.5.
According to preparation method of the present invention, it is characterized in that; The catalyst wherein related to, for evaluating it
Front need carry out H
2reduction activation.
According to preparation method of the present invention, it is characterized in that; The catalyst wherein related to, the field of application comprises: the hydrogenation of phthalate produces the hydrogenation reaction of 1,2-cyclohexane cyclohexanedimethanodibasic ester class.
Detailed description of the invention
Embodiment 1
Get amorphous silicon aluminium powder and Ludox extruded moulding, through super-dry, roasting, shaping after, carrier pore volume 0.6ml/g, specific area 209cm
2/ g, gets 100g carrier stand-by.Get acetic acid ruthenium (laboratory synthesis) solution appropriate (acetic acid ruthenium quality is 2.75g), slowly drip weak aqua ammonia, regulate pH value of solution to 9.0, the carrier after dip forming.Dry immediately after dipping is even, 100 DEG C of 5h, then 220 DEG C of roasting 3h.Obtained Ru simple substance content is the Ru/SiO of 1.0%wt
2-Al
2o
3hydrogenation catalyst.
Embodiment 2
Get amorphous silicon aluminium powder and Ludox extruded moulding, through super-dry, roasting, shaping after, carrier pore volume 0.9ml/g, specific area 243cm
2/ g, gets 100g carrier stand-by.Get nitrosyl nitrate ruthenium (laboratory synthesis) solution appropriate (nitrosyl nitrate ruthenium quality is 2.51g), slowly drip weak aqua ammonia, regulate pH value of solution to 9.0, the carrier after dip forming.Dry immediately after dipping is even, 100 DEG C of 5h, 220 DEG C of roasting 3h.Obtained Ru simple substance content is the Ru/SiO of 1.0%wt
2-Al
2o
3hydrogenation catalyst.
Embodiment 3
Get amorphous silicon aluminium powder and Ludox extruded moulding, through super-dry, roasting, shaping after, carrier pore volume 1.3ml/g, specific area 161cm
2/ g, gets 100g carrier stand-by.Get acetic acid ruthenium (laboratory synthesis) solution appropriate (acetic acid ruthenium quality is 2.75g), slowly drip weak aqua ammonia, regulate pH value of solution to 9.0, the carrier after dip forming.Dry immediately after dipping is even, 100 DEG C of 5h, 220 DEG C of roasting 3h.Obtained Ru simple substance content is the Ru/SiO of 1.0%wt
2-Al
2o
3hydrogenation catalyst.
Embodiment 4
Laboratory self-control silica-gel carrier 100g, pore volume 2.2ml/g, specific surface 249cm
2/ g, goes 100g stand-by.Get acetic acid ruthenium (laboratory synthesis) solution appropriate (acetic acid ruthenium quality is 2.75g), slowly drip weak aqua ammonia, regulate pH value of solution to 10.2, the carrier after dip forming.Dry immediately after dipping is even, 100 DEG C of 5h, 220 DEG C of roasting 3h.Obtained Ru simple substance content is the Ru/SiO of 1.0%wt
2hydrogenation catalyst.
Embodiment 5
Laboratory self-control silica-gel carrier 100g, pore volume 2.2ml/g, specific surface 249cm
2/ g, goes 100g stand-by.Get nitrosyl nitrate ruthenium (III) (laboratory synthesis) solution appropriate (Solute mass is 2.51g), slowly drip weak aqua ammonia, regulate pH value of solution to 10.2, the carrier after dip forming.Dry immediately after dipping is even, 100 DEG C of 5h, 220 DEG C of roasting 3h.Obtained Ru simple substance content is the Ru/SiO of 0.8%wt
2hydrogenation catalyst.
Comparative example:
The Pd-Ru-Co/Al of identical load amount is prepared according to the preparation method of the embodiment 4 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.
Evaluation result:
Evaluating catalyst the results are shown in Table 1
Claims (5)
1. a preparation method for phthalic acid ester hydrogenation catalyst, is characterized in that:
The carrier of described catalyst is a kind of or several combination of amorphous aluminum silicide or silica, and the BET specific surface area of carrier is 80-400m
2/ g, pore volume 0.2-3.0ml/g, aperture 5-20nm; Active component is noble metal Ru, and simple substance Ru content is 0.02 ~ 1.3%wt; The chlorinity of catalyst accounts for total catalyst weight≤0.05%wt,
The preparation of catalyst adopts following steps:
A) slowly drip weak aqua ammonia to containing in ruthenium solution, adjustment pH value of solution is 7.0-12.0;
B) use a) solution impregnating carrier, dry immediately after saturated adsorption, baking temperature 60-150 DEG C, dry 1-8h;
C) sintering temperature 150-300 DEG C, roasting 1-6h.
2., according to preparation method according to claim 1, it is characterized in that; The catalyst wherein related to, the solid salt containing Ru is selected from as acetic acid ruthenium (III), the mixture of one or more of nitrosyl nitrate ruthenium (III).
3., according to preparation method according to claim 1, it is characterized in that; The catalyst wherein related to, the pH containing ruthenium solution is 8.5-11.5.
4., according to preparation method according to claim 1, it is characterized in that; The catalyst wherein related to, needed to carry out H before evaluating
2reduction activation.
5., according to preparation method according to claim 1, it is characterized in that; The catalyst wherein related to, the field of application comprises: the hydrogenation of phthalate produces the hydrogenation reaction of 1,2-cyclohexane cyclohexanedimethanodibasic ester class.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105327701A (en) * | 2015-12-01 | 2016-02-17 | 中国海洋石油总公司 | Preparation method of dibasic ester aromatic ring saturation catalyst containing benzene ring |
| WO2018046306A1 (en) * | 2016-09-09 | 2018-03-15 | Exxonmobil Chemical Patents Inc. | Processes for the hydrogenation of phthalate esters |
| 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 |
| CN110052266A (en) * | 2019-04-30 | 2019-07-26 | 天津大学 | A kind of phthalic acid ester hydrogenation catalyst and the preparation method and application thereof |
| CN111036194A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Preparation method of catalyst for hydrogenation of phthalate |
| 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 |
| CN112174818A (en) * | 2019-07-01 | 2021-01-05 | 中石化南京化工研究院有限公司 | Phthalate hydrogenation process |
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| CN101559377A (en) * | 2009-05-21 | 2009-10-21 | 浙江师范大学 | Supported catalyst for eliminating formaldehyde, preparation method and application thereof |
| CN102921409A (en) * | 2012-10-26 | 2013-02-13 | 中国海洋石油总公司 | Preparation method of catalyst for producing 1,2-cyclohexane dicarboxylic ester through hydrogenation |
| CN103304418A (en) * | 2013-06-09 | 2013-09-18 | 中国海洋石油总公司 | Method for preparing environment-friendly plasticizer cyclohexane dicarboxylic acid ester |
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Patent Citations (4)
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| JPH06116182A (en) * | 1992-10-09 | 1994-04-26 | Mitsubishi Kasei Corp | Hydrogenation of organic carboxylic acid and/or organic carboxylic acid ester |
| CN101559377A (en) * | 2009-05-21 | 2009-10-21 | 浙江师范大学 | Supported catalyst for eliminating formaldehyde, preparation method and application thereof |
| CN102921409A (en) * | 2012-10-26 | 2013-02-13 | 中国海洋石油总公司 | Preparation method of catalyst for producing 1,2-cyclohexane dicarboxylic ester through hydrogenation |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105327701A (en) * | 2015-12-01 | 2016-02-17 | 中国海洋石油总公司 | Preparation method of dibasic ester aromatic ring saturation catalyst containing benzene ring |
| WO2018046306A1 (en) * | 2016-09-09 | 2018-03-15 | Exxonmobil Chemical Patents Inc. | Processes for the hydrogenation of phthalate esters |
| CN109790101A (en) * | 2016-09-09 | 2019-05-21 | 埃克森美孚化学专利公司 | The method for hydrogenation of phthalic acid ester |
| US20190185404A1 (en) * | 2016-09-09 | 2019-06-20 | Nicolaas A. de Munck | Processes for the hydrogenation of phthalate esters |
| 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 |
| CN111036194A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Preparation method of catalyst for hydrogenation of phthalate |
| 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 |
| CN110052266A (en) * | 2019-04-30 | 2019-07-26 | 天津大学 | A kind of phthalic acid ester hydrogenation catalyst and the preparation method and application thereof |
| CN112174818A (en) * | 2019-07-01 | 2021-01-05 | 中石化南京化工研究院有限公司 | Phthalate hydrogenation process |
| CN112174818B (en) * | 2019-07-01 | 2023-03-31 | 中石化南京化工研究院有限公司 | Phthalate hydrogenation process |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: CHINA NATIONAL OFFSHORE OIL Corp. Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Applicant after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: CHINA NATIONAL OFFSHORE OIL Corp. Applicant before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Applicant before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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Effective date of registration: 20161013 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Applicant after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: CHINA NATIONAL OFFSHORE OIL Corp. Applicant before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Applicant before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
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