CN103664524A - Method for preparing 1, 4-cyclohexanedimethanol through hydrogenation of 1, 4-cyclohexanedicarboxylic acid - Google Patents

Method for preparing 1, 4-cyclohexanedimethanol through hydrogenation of 1, 4-cyclohexanedicarboxylic acid Download PDF

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CN103664524A
CN103664524A CN201210324514.3A CN201210324514A CN103664524A CN 103664524 A CN103664524 A CN 103664524A CN 201210324514 A CN201210324514 A CN 201210324514A CN 103664524 A CN103664524 A CN 103664524A
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hydrogenation
cyclohexanedimethanol
cyclohexanedicarboxylic acid
catalyzer
carrier
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CN103664524B (en
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朱庆才
畅延青
陈大伟
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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Abstract

The invention relates to a method for preparing 1, 4-cyclohexanedimethanol through hydrogenation of 1, 4-cyclohexanedicarboxylic acid, which mainly solves the problem that a catalyst is short in service life. According to the method for preparing the 1, 4-cyclohexanedimethanol through hydrogenation of the 1, 4-cyclohexanedicarboxylic acid, in the presence of a catalyst, water is taken as a reaction medium, hydrogen and the 1, 4-cyclohexanedicarboxylic acid react at reaction temperature of 180-250 DEG C under reaction pressure of 8-15MPa so as to prepare the 1, 4-cyclohexanedimethanol, the catalyst comprises active components and a carrier, wherein the active component comprise Ru and Sn, the carrier is a mixture of Al2O3 and Nb2O5, and the mass ratio of Al2O3 to Nb2O5 is 100:(0.005-10). The method for preparing 1, 4-cyclohexanedimethanol through hydrogenation of 1, 4-cyclohexanedicarboxylic acid, which adopts the technical scheme, well solves the problem that the catalyst is short in service life, and can be used in industrial production.

Description

The method of 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol
Technical field
The present invention relates to a kind of method of 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol.
Background technology
1,4-cyclohexanedimethanol is the important Organic Chemicals of producing vibrin, the vibrin that is substituted ethylene glycol or the production of other polyvalent alcohol by it has good thermostability and thermoplasticity, can at higher temperature, keep stable physical properties and electrical property, the product being made by this resinoid has good chemical resistant properties and environment resistant.The technique of suitability for industrialized production 1,4 cyclohexane dimethanol mainly be take dimethyl terephthalate (DMT) as raw material at present, and first benzene ring hydrogenation is prepared 1,4 cyclohexanedicarboxylic acid dimethyl ester, then is reacted and prepared 1,4 cyclohexane dimethanol by ester through hydrogenation.Because terephthalic acid price is relatively low and source is abundant, therefore occurred in recent years take that terephthalic acid prepared the trend of 1,4 cyclohexane dimethanol as raw material.Its process also needs conventionally through two-step reaction, first be that phenyl ring selects hydrogenation to produce 1,4-cyclohexane cyclohexanedimethanodibasic, then 1,4 cyclohexanedicarboxylic acid be take water as reaction medium, hydrogen and 1,4-cyclohexane cyclohexanedimethanodibasic repeated hydrogenation under the reaction pressure of the temperature of reaction of 180 ~ 250 ℃ and 8 ~ 15MPa generates 1,4 cyclohexane dimethanol, and wherein 1, it is the committed step of whole technology that 4-cyclohexane cyclohexanedimethanodibasic hydrogenation generates 1,4 cyclohexane dimethanol.At present, most patents all adopt noble metal catalyst to realize this process, as adopting Ru-Sn-Pt/C catalyzer, US Patent No. 6294703 carries out hydrogenation reaction, it is 1 years old, the yield of 4-cyclohexanedimethanol is 91.8%, and the Ru-Sn-Re/C catalyzer that US6495730 adopts carries out hydrogenation reaction, the yield of its 1,4 cyclohexane dimethanol is only 75%.Recently, Chinese patent CN1911504 adopts Ru-Sn/Al 2o 3catalyzer, in the situation that not using Pt and Re, has still obtained good 1,4 cyclohexane dimethanol yield, be 90.1～95.4%, but the life-span of its catalyzer is not long, reuse 5 times after 1,4 cyclohexane dimethanol yield sharply decline.
Summary of the invention
Technical problem to be solved by this invention is catalyzer short problem in work-ing life in the method for the 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol that exists in prior art.A kind of method that 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol is provided, the catalyzer of the method has activity and selectivity is high, the feature that the life-span is long.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol, under catalyzer exists, take water as reaction medium, and hydrogen and 1,4 cyclohexanedicarboxylic acid react preparation 1 under the reaction pressure of the temperature of reaction of 180 ~ 250 ℃ and 8 ~ 15MPa, 4-cyclohexanedimethanol, described catalyzer is comprised of active ingredient and carrier, and wherein said active ingredient is Ru and Sn, and described carrier is Al 2o 3and Nb 2o 5mixture, Al wherein 2o 3and Nb 2o 5mass ratio be 100:(0.005～10).
In such scheme, described Al 2o 3and Nb 2o 5mass ratio be preferably 100:(0.005～0.5), 100:(0.007～0.01 more preferably).In described catalyzer, the mass ratio of active ingredient Ru and Sn is preferably 1:(0.6～2.4); In described catalyzer, the content of active ingredient is preferably 5～20wt%; The granularity of described catalyzer is preferably 20～200 orders; The specific surface area of described carrier is preferably 100～200m 2/ g.
The discovery that contriver is surprised, adopts after aforesaid method, and the activity of catalyzer, selectivity and life-span are all greatly improved.Experimental result shows, prior art makes 1, the yield of 4-cyclohexanedimethanol be 92.8% and reuse 5 times after yield sharply decline, and the inventive method under equal conditions can make, the yield of 4-cyclohexanedimethanol is up to 97.8% and to reuse 10 yields substantially constant, has obtained good technique effect.
Embodiment
[embodiment 1]
The preparation method of carrier is as follows: by 100g aluminum oxide (Al 2o 3) impregnated in the niobium oxalate aqueous solution that niobium content is 7g, standing 6h, after dipping, the vacuum-drying 3h at 85 ℃ of elder generation, then roasting 5h at 550 ℃, obtains Al 2o 3-Nb 2o 5carrier mixture.With ICP-AES, measure aluminium content and the content of niobium in carrier mixture, obtain Al 2o 3and Nb 2o 5mass ratio be 100:10, with ASAP2020 ratio surface area instrument, measure Al 2o 3-Nb 2o 5the BET specific surface area of carrier mixture is 185m 2/ g.
Method for preparing catalyst is as follows: by 4.53gRuCl 33H 2o is dissolved in 24.5ml deionized water, then adds 3.91gSnCl 22H 2o dissolves, then adds 35g carrier A l 2o 3-Nb 2o 5stir, standing aging 15h, dry 2h at 85 ℃, after grinding, getting granularity 80～200 object particles is catalyst precursor, then in the hydrogen with 7.5 times of nitrogen dilutions, reduce 3h, reduction temperature is 550 ℃, and hydrogen flowing quantity is 120ml/min, is cooled to room temperature and gets final product to obtain anti-applications catalyst after reduction finishes.Ru in employing ICP-AES mensuration gained catalyzer and the content of Sn, be respectively Ru4.7wt% and Sn4.8wt%, and active component content in catalyzer (being Ru and Sn summation) is 9.5wt%.
Evaluating catalyst method is as follows: by 15g1,4-cyclohexane cyclohexanedimethanodibasic and 150g water are placed in the autoclave of 300ml jointly, add the above-mentioned catalyzer of 4g.After enclosed high pressure still, extract the interior air of still out and pass into hydrogen exchange air, under hydrogen pressure 2.0MPa, being heated with stirring to 230 ℃ of temperature of reaction, then passing into hydrogen to reaction pressure 10MPa, starting to react timing, keeping the required hydrogen pressure of reaction until reaction finishes.Cooling rear filtration catalizer, uses gas chromatographic analysis reaction solution, by marker method, calculates target product concentration.
[embodiment 2-8]
Do not change niobium oxalate concentration, only change the consumption of the niobium oxalate aqueous solution, obtain Al 2o 3and Nb 2o 5the carrier of different mass ratio, all the other operate with embodiment 1, and the prepared carrier composition of each embodiment, specific surface area and reaction product yield are as shown in table 1.Ru in employing ICP-AES mensuration gained catalyzer and the content of Sn, be respectively Ru4.7wt% and Sn4.8wt%, and active component content in catalyzer (being Ru and Sn summation) is 9.5wt%.
[embodiment 9-16]
The catalyzer that adopts successively above-described embodiment 1-8 to make is respectively evaluated, evaluation method is as embodiment 1, difference is raw catalyst and repeat continuously to evaluate under identical condition 10 times more not after a collection of raw catalyst of every input, and in its each evaluation, the yield of reaction product is as shown in table 2.
[comparative example 1]
Method according to the embodiment of Chinese patent CN1911504 1 is prepared Ru-Sn/Al 2o 3.Be specially 4.53gRuCl 33H 2o is dissolved in 24.5ml deionized water, then adds 3.91gSnCl 22H 2o dissolves, then adds 35g carrier A l 2o 3stir, standing aging 15h, at 85 ℃ of dry 2h, after grinding, getting granularity 80～200 object particles is catalyst precursor, heating hydrogen reducing, hydrogen flowing quantity is 150ml/min, obtains anti-applications catalyst.Ru in employing ICP-AES mensuration gained catalyzer and the content of Sn, be respectively Ru4.7wt% and Sn4.8wt%, and active component content in catalyzer (being Ru and Sn summation) is 9.5wt%.Gained catalyzer is evaluated according to the method for embodiment 9-16, and the yield of its each reaction product is as shown in table 2.
 
[comparative example 2]
Do not change niobium oxalate concentration, only change the consumption of the niobium oxalate aqueous solution, obtain Al 2o 3: Nb 2o 5mass ratio is the carrier of 100:15, and all the other operate with embodiment 1, and the prepared carrier composition of comparative example 2, specific surface area and reaction product yield are as shown in table 1.Ru in employing ICP-AES mensuration gained catalyzer and the content of Sn, be respectively Ru4.7wt% and Sn4.8wt%, and active component content in catalyzer (being Ru and Sn summation) is 9.5wt%.Gained catalyzer is evaluated according to the method for embodiment 9-16, and the yield of its each reaction product is as shown in table 2.
 
Table 1
Table 2
Figure 585084DEST_PATH_IMAGE002

Claims (7)

1. one kind 1,4-cyclohexane cyclohexanedimethanodibasic Hydrogenation 1, the method of 4-cyclohexanedimethanol, under catalyzer exists, with water reaction medium, hydrogen and 1,4-cyclohexane cyclohexanedimethanodibasic reacts and prepares 1,4 cyclohexane dimethanol under the reaction pressure of the temperature of reaction of 180 ~ 250 ℃ and 8 ~ 15MPa, it is characterized in that described catalyzer is comprised of active ingredient and carrier, wherein said active ingredient is Ru and Sn, and described carrier is Al 2o 3and Nb 2o 5mixture, Al wherein 2o 3and Nb 2o 5mass ratio be 100:(0.005～10).
2. method according to claim 1, is characterized in that described Al 2o 3and Nb 2o 5mass ratio be 100:(0.005～0.5).
3. method according to claim 1, is characterized in that described Al 2o 3and Nb 2o 5mass ratio be 100:(0.007～0.01).
4. method according to claim 1, is characterized in that in described catalyzer, the mass ratio of active ingredient Ru and Sn is 1:(0.6～2.4).
5. method according to claim 1, is characterized in that the content of active ingredient in described catalyzer is 5～20wt%.
6. method according to claim 1, the granularity that it is characterized in that described catalyzer is 20～200 orders.
7. method according to claim 1, the specific surface area that it is characterized in that described carrier is 100～200m 2/ g.
CN201210324514.3A 2012-09-05 2012-09-05 The method of 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol Active CN103664524B (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105498763A (en) * 2014-09-25 2016-04-20 中国石油化工股份有限公司 1, 4-cyclohexanedimethanol catalyst
CN105582927A (en) * 2014-10-24 2016-05-18 中国石油化工股份有限公司 1,4-cyclohexanedimethanol catalyst and preparation method thereof
CN105727951A (en) * 2014-12-11 2016-07-06 中国石油天然气股份有限公司 Selective hydrogenation catalyst and preparation method thereof
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
KR20190081064A (en) 2017-12-29 2019-07-09 한화케미칼 주식회사 Noble metal-transition metal complex catalyst of carbon coated silica-alumina and preparation method of thereof
CN110981705A (en) * 2019-11-12 2020-04-10 万华化学集团股份有限公司 Method for preparing cyclohexane dimethylamine
CN114308035A (en) * 2022-01-14 2022-04-12 浙江大学衢州研究院 A kind of hydrogenation catalyst for 1,4-cyclohexanedicarboxylic acid, its preparation method and its application
CN114436772A (en) * 2022-01-29 2022-05-06 浙江清和新材料科技有限公司 Preparation method of 1, 4-cyclohexanedimethanol

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CN101982236A (en) * 2010-09-06 2011-03-02 常州大学 Hydrogenation catalyst and preparation method of 1,4-cyclohexanedimethanol
CN102307657A (en) * 2009-10-26 2012-01-04 国际人造丝公司 Process for making ethanol from acetic acid using acidic catalysts

Patent Citations (2)

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CN102307657A (en) * 2009-10-26 2012-01-04 国际人造丝公司 Process for making ethanol from acetic acid using acidic catalysts
CN101982236A (en) * 2010-09-06 2011-03-02 常州大学 Hydrogenation catalyst and preparation method of 1,4-cyclohexanedimethanol

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105498763A (en) * 2014-09-25 2016-04-20 中国石油化工股份有限公司 1, 4-cyclohexanedimethanol catalyst
CN105498763B (en) * 2014-09-25 2018-02-13 中国石油化工股份有限公司 1,4 cyclohexanedimethanol catalyst
CN105582927A (en) * 2014-10-24 2016-05-18 中国石油化工股份有限公司 1,4-cyclohexanedimethanol catalyst and preparation method thereof
CN105582927B (en) * 2014-10-24 2018-04-06 中国石油化工股份有限公司 1,4 cyclohexanedimethanol catalyst and its preparation method
CN105727951A (en) * 2014-12-11 2016-07-06 中国石油天然气股份有限公司 Selective hydrogenation catalyst and preparation method thereof
CN105727951B (en) * 2014-12-11 2018-08-10 中国石油天然气股份有限公司 Selective hydrogenation catalyst and preparation method thereof
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 A kind of synthetic method of tetraethyl 1,2,4,5-cyclohexanetetracarboxylic acid
KR20190081064A (en) 2017-12-29 2019-07-09 한화케미칼 주식회사 Noble metal-transition metal complex catalyst of carbon coated silica-alumina and preparation method of thereof
CN110981705A (en) * 2019-11-12 2020-04-10 万华化学集团股份有限公司 Method for preparing cyclohexane dimethylamine
CN110981705B (en) * 2019-11-12 2022-08-05 万华化学集团股份有限公司 Method for preparing cyclohexane dimethylamine
CN114308035A (en) * 2022-01-14 2022-04-12 浙江大学衢州研究院 A kind of hydrogenation catalyst for 1,4-cyclohexanedicarboxylic acid, its preparation method and its application
CN114436772A (en) * 2022-01-29 2022-05-06 浙江清和新材料科技有限公司 Preparation method of 1, 4-cyclohexanedimethanol

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