CN100465145C - Process of preparing 1,4-cyclohexane dimethand - Google Patents
Process of preparing 1,4-cyclohexane dimethand Download PDFInfo
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- CN100465145C CN100465145C CNB2007100415921A CN200710041592A CN100465145C CN 100465145 C CN100465145 C CN 100465145C CN B2007100415921 A CNB2007100415921 A CN B2007100415921A CN 200710041592 A CN200710041592 A CN 200710041592A CN 100465145 C CN100465145 C CN 100465145C
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- terephthalic acid
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Abstract
The present invention relates to process of preparing 1, 4-cyclohexane dimethanol. The preparation process includes the following main step: the reaction between terephthalic acid as the initial material and hydrogen are reacted in the presence of supported catalyst with active components metal Ru, metal Sn and non-metal B, so as to obtain the target product. The present invention has lowered 1, 4-cyclohexane dimethanol preparing cost and mild reaction condition.
Description
Technical field
The present invention relates to a kind of preparation method of 1,4 cyclohexane dimethanol, specifically, relating to a kind of is starting raw material with the terephthalic acid, makes the method for 1,4 cyclohexane dimethanol through a step catalytic hydrogenation reaction.
Background technology
So far, the existing multiple method for preparing 1,4 cyclohexane dimethanol is in the news, and wherein is starting raw material with the terephthalic acid, and the method that makes 1,4 cyclohexane dimethanol through a step catalytic hydrogenation reaction has:
US 6,495,730 disclose a kind of terephthalic acid liquid phase one-step method hydrogenation preparing 1, the method of 4-cyclohexanedimethanol, select the 5.0%Ru-3.5%Sn-5.6%Re/C catalyzer of loading type for use, reacted 5 hours in 250 ℃ of temperature and hydrogen pressure 15Mpa, the yield of terephthalic acid transformation efficiency and 1,4 cyclohexane dimethanol reaches 97% and 42% respectively.
It is starting raw material with the terephthalic acid that JP 2000007596 has described a kind of, make 1 through a step hydrogenation reaction, the method of 4-cyclohexanedimethanol, the used catalyzer of this method is: be that carrier, Ru-Sn-Pt are the loaded catalyst of active ingredient with the gac, reaction is 4 hours under 150 ℃ of temperature and hydrogen pressure 15MPa, the yield of 1,4 cyclohexane dimethanol is 28.3%.
US 6,284, and 932 also disclose a kind of method that adopts a step hydrogenation reaction legal system to be equipped with 1,4 cyclohexane dimethanol.The selected catalyzer of this method is expensive precious metal [as Pd, Pt or Re] or its oxide compound, and Ag, Mg or Au's is a kind of.Reaction is 2 hours under 150 ℃ of temperature and hydrogen pressure 10Mpa condition, and the intermediate product 1,4 cyclohexanedicarboxylic acid transforms fully, and the yield of purpose product 1,4 cyclohexane dimethanol is 83%.
CN 1911885 provides a kind of preparation method of 1,4 cyclohexane dimethanol, is about to two kinds of different catalyzer Ru/Al
2O
3And Ru-Sn/Al
2O
3Be mixed in proportion use, reaction divides two sections to be carried out, and adopts differential responses temperature and hydrogen pressure respectively.The result shows that the raw material terephthalic acid transforms fully, and product 1,4 cyclohexane dimethanol yield reaches 87%.
To sum up, existing is in the step hydrogen addition technology of starting raw material with the terephthalic acid, and that adopts single catalyst all exists the defective of need with expensive precious metal, and the catalyzer cost is than higher, and, can not all reach high purpose product yield.If adopt the combination of different catalysts, then the Preparation of catalysts process is more loaded down with trivial details, has also increased catalyst consumption.Therefore, provide a kind of succinct relatively, economic and method for preparing 1,4 cyclohexane dimethanol high yield to become purpose of the present invention.
Summary of the invention
The said preparation 1 of the present invention, the method of 4-cyclohexanedimethanol, its key step is: in water-bearing media, with the terephthalic acid is starting raw material, there being active ingredient to comprise under the loaded catalyst existence condition of metal Ru (Ru), metallic tin (Sn) and nonmetal boron (B), behind single step reaction, obtain target product with hydrogen;
In the active ingredient of the said loaded catalyst of the present invention, ruthenium (Ru) is preferably 0.5～2.5 with the molar ratio of tin (Sn), boron (B) is preferably 1～15[Mol (B)/Mol (Ru+Sn)=1～15 with the molar ratio of ruthenium and tin mole number sum], in the weight of carrier, the charge capacity of Ru is preferably 1wt%～20wt%;
The carrier of said loaded catalyst can be: gac, SiO
2, Al
2O
3Or TiO
2, or their mixture.Preferred carrier is Al
2O
3, gac or TiO
2
The used catalyzer of the present invention can prepare with the method that following contriver recommended:
Said catalyzer is to adopt the step impregnation method preparation, and key step is: at first, the compound that will contain metal Ru and Sn respectively (is generally selected its water-soluble salt for use, as RuCl
33H
2O or SnCl
22H
2O) be mixed with the aqueous solution of desired concn, support of the catalyst added contain in the aqueous solution of Sn then, leave standstill aging, drying after, the gained solid is added contain in the aqueous solution of Ru again, add NaBH after leaving standstill aging 10 hours～20 hours, drying and roasting
4Aqueous solution reduction more after filtration, washing and dry catalyst precursor, obtains required catalyzer to gained complex catalyst precursor body and function hydrogen treat 0.5 hour～5 hours (preferred 1 hour～3 hours) at last.
Wherein, the method of said hydrogen treat is: catalyst precursor is placed tubular reactor, under 150 ℃～650 ℃ (preferred 200 ℃～450 ℃) conditions, in this reactor, feed hydrogen, hydrogen flowing quantity is controlled to be 80ml/min～250ml/min (preferred 100ml/min～200ml/min), and keeping 0.5 hour～5 hours under this state.
Embodiment
The said method for preparing 1,4 cyclohexane dimethanol of the present invention, its key step is: with terephthalic acid and water-bearing media by weight being 1:(5～20) mixed, feeding hydrogen carries out hydrogenation reaction in the presence of catalyzer.Temperature of reaction is 100 ℃～300 ℃ (preferable reaction temperature is 150 ℃～250 ℃), and hydrogen pressure is that (preferred hydrogen pressure is that 6MPa～10MPa), the reaction times is 3 hours～6 hours to 4.0MPa～10.0MPa.
Wherein, said catalyzer is a loaded catalyst, its active ingredient comprises Ru, Sn and B, and the content of Ru is that the molar ratio of 3wt%～10wt% (in the weight of used carrier), Ru and Sn is 0.8～2.0, and the molar ratio of B and Ru and Sn mole number sum is 3～10; The carrier of said catalyzer is Al
2O
3, its mean particle size is preferably 80～200 orders; In the reaction system gross weight, the weight consumption of said catalyzer is 1%～10% (being preferably 2%～10%).
The present invention selects for use boron (B) part to substitute the existing precious metal (as Pt or Re) that is used for reducing simultaneously aromatic ring and carboxylic carbonylic catalyst, and so replacement is not a cost to reduce selectivity of catalyst.Antithesis, its selectivity is higher than existing catalyzer.In addition, use the said catalyzer of the present invention can make reaction (hydrogenation reaction) condition milder.
Below will the invention will be further described by embodiment, its purpose only is better to understand content of the present invention, and unrestricted protection scope of the present invention:
In an embodiment, the definition of transformation efficiency and yield is respectively:
Embodiment 1～10
The terephthalic acid of 150g aqueous solvent and aequum is placed the autoclave of 300ml, add the catalyzer of aequum in proportion.Extract air in the still behind the airtight autoclave out, feed hydrogen exchange again.Stirring heating feeds hydrogen then, reacts by preset condition, keeps hydrogen pressure to finish until reaction.The pressure release discharging of cooling back, filtration catalizer.Reaction solution calculates production concentration through gas chromatographic analysis by marker method.Adopt the determination of acid value method, calculate unreacted raw material P-phthalic acid at concentration.
Catalyzer composition and consumption, reaction conditions and reaction result that each embodiment uses see Table 1.
Claims (4)
1, a kind of preparation 1, the method of 4-cyclohexanedimethanol, it is characterized in that, said preparation method's key step is: in water medium, with the terephthalic acid is starting raw material, be under the loaded catalyst existence condition of active ingredient by the mixture of forming by metal Ru, metallic tin and nonmetal boron, behind single step reaction, getting target compound with hydrogen;
Wherein: in the active ingredient of said loaded catalyst, the molar ratio of ruthenium and tin is 0.5～2.5, and the molar ratio of boron and ruthenium and tin mole number sum is 1～15, and in the weight of used carrier, the content of ruthenium is 1wt%～20wt%.
As the said preparation method of claim 1, it is characterized in that 2, wherein the carrier of said loaded catalyst is Al
2O
3, TiO
2Or gac.
As the said preparation method of claim 1, it is characterized in that 3, wherein the temperature of reaction of terephthalic acid and hydrogen is 100 ℃～300 ℃, hydrogen pressure is 4.0MPa～10.0MPa, and the reaction times is 3 hours～6 hours.
As the said preparation method of claim 1, it is characterized in that 4, wherein terephthalic acid and water medium are the mixed of 1:5～20 by weight.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100415921A CN100465145C (en) | 2007-06-01 | 2007-06-01 | Process of preparing 1,4-cyclohexane dimethand |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100415921A CN100465145C (en) | 2007-06-01 | 2007-06-01 | Process of preparing 1,4-cyclohexane dimethand |
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|---|---|
| CN101066910A CN101066910A (en) | 2007-11-07 |
| CN100465145C true CN100465145C (en) | 2009-03-04 |
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| CNB2007100415921A Expired - Fee Related CN100465145C (en) | 2007-06-01 | 2007-06-01 | Process of preparing 1,4-cyclohexane dimethand |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795965A (en) * | 2011-05-24 | 2012-11-28 | 江苏恒祥化工有限责任公司 | Method for synthesizing 1,4-cyclohexanedimethanol |
| CN103877998B (en) * | 2012-12-19 | 2016-04-13 | 中国石油化工股份有限公司 | Produce the Catalysts and its preparation method of 1,4-CHDM |
| CN104549251A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for synthesizing 1, 4-cyclohexanedimethanol and preparation method of catalyst |
| KR102238548B1 (en) | 2017-12-29 | 2021-04-08 | 한화솔루션 주식회사 | Noble metal-transition metal complex catalyst of carbon coated silica-alumina and preparation method of thereof |
| CN108993500B (en) * | 2018-07-02 | 2021-06-15 | 中国科学院兰州化学物理研究所苏州研究院 | Catalyst for synthesizing chiral cyclohexane dimethanol compounds, preparation method and application thereof |
| CN113429549B (en) * | 2021-07-29 | 2023-03-21 | 天津斯坦利新型材料有限公司 | Composite catalyst, preparation method and polycyclohexylene dimethylene terephthalate prepared by using composite catalyst |
Citations (7)
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|---|---|---|---|---|
| JP2000007596A (en) * | 1998-06-22 | 2000-01-11 | Mitsubishi Chemicals Corp | Production of 1,4-cyclohexanedimethanol |
| US6284932B1 (en) * | 1997-05-16 | 2001-09-04 | Basf Aktiengesellschaft | Method for producing alcohols containing cycloaliphatic groups |
| JP2002060356A (en) * | 2000-08-18 | 2002-02-26 | Mitsubishi Chemicals Corp | Method for hydrogenating terephthalic acid |
| CN1089082C (en) * | 1996-06-28 | 2002-08-14 | Sknjc株式会社 | Process for the preparation of cyclohexanedimethanol |
| US6495730B1 (en) * | 1999-09-21 | 2002-12-17 | Asahi Kasei Kabushiki Kaisha | Catalysts for hydrogenation of carboxylic acid |
| CN1806913A (en) * | 2005-01-18 | 2006-07-26 | 如皋市恒祥化工有限责任公司 | Catalyst for preparation of 1,4-cyclohexane dimethanol by hydrogenation of dimethyl terephthalate and preparation method thereof |
| CN1911885A (en) * | 2005-08-09 | 2007-02-14 | 中国石化上海石油化工股份有限公司 | Method of preparing 1,4-cyclohexane dimethanol by direct hydrogenation of terephthalic acid |
-
2007
- 2007-06-01 CN CNB2007100415921A patent/CN100465145C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089082C (en) * | 1996-06-28 | 2002-08-14 | Sknjc株式会社 | Process for the preparation of cyclohexanedimethanol |
| US6284932B1 (en) * | 1997-05-16 | 2001-09-04 | Basf Aktiengesellschaft | Method for producing alcohols containing cycloaliphatic groups |
| JP2000007596A (en) * | 1998-06-22 | 2000-01-11 | Mitsubishi Chemicals Corp | Production of 1,4-cyclohexanedimethanol |
| US6495730B1 (en) * | 1999-09-21 | 2002-12-17 | Asahi Kasei Kabushiki Kaisha | Catalysts for hydrogenation of carboxylic acid |
| JP2002060356A (en) * | 2000-08-18 | 2002-02-26 | Mitsubishi Chemicals Corp | Method for hydrogenating terephthalic acid |
| CN1806913A (en) * | 2005-01-18 | 2006-07-26 | 如皋市恒祥化工有限责任公司 | Catalyst for preparation of 1,4-cyclohexane dimethanol by hydrogenation of dimethyl terephthalate and preparation method thereof |
| CN1911885A (en) * | 2005-08-09 | 2007-02-14 | 中国石化上海石油化工股份有限公司 | Method of preparing 1,4-cyclohexane dimethanol by direct hydrogenation of terephthalic acid |
Non-Patent Citations (4)
| Title |
|---|
| 1,4-环己烷二甲醇专利生产技术进展. 李琰等.石化技术与应用，第21卷第1期. 2003 |
| 1,4-环己烷二甲醇专利生产技术进展. 李琰等.石化技术与应用，第21卷第1期. 2003 * |
| 低压加氢制备1,4-环己烷二甲醇的研究. 孙绪江等.燃料化学学报，第31卷第3期. 2003 |
| 低压加氢制备1,4-环己烷二甲醇的研究. 孙绪江等.燃料化学学报，第31卷第3期. 2003 * |
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Granted publication date: 20090304 Termination date: 20120601 |