CN103664524B - The method of 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol - Google Patents
The method of 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol Download PDFInfo
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- CN103664524B CN103664524B CN201210324514.3A CN201210324514A CN103664524B CN 103664524 B CN103664524 B CN 103664524B CN 201210324514 A CN201210324514 A CN 201210324514A CN 103664524 B CN103664524 B CN 103664524B
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- cyclohexane dimethanol
- catalyzer
- carrier
- active ingredient
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- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 16
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 13
- 229910052718 tin Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004480 active ingredient Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012429 reaction media Substances 0.000 claims abstract description 4
- 230000003245 working effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000010955 niobium Substances 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 5
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- LNGAGQAGYITKCW-UHFFFAOYSA-N dimethyl cyclohexane-1,4-dicarboxylate Chemical compound COC(=O)C1CCC(C(=O)OC)CC1 LNGAGQAGYITKCW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method of 1,4 cyclohexane dimethanol processed, mainly solve in prior art short problem in catalyzer work-ing life of existing.The present invention is by adopting a kind of 1,4-cyclohexane cyclohexanedimethanodibasic Hydrogenation 1, the method of 4-cyclohexanedimethanol in the presence of a catalyst, take water as reaction medium, hydrogen and 1,4-cyclohexane cyclohexanedimethanodibasic carries out reaction and prepares 1,4 cyclohexane dimethanol under the reaction pressure of the temperature of reaction of 180 ~ 250 DEG C and 8 ~ 15MPa, and described catalyzer is made up of active ingredient and carrier, wherein said active ingredient is Ru and Sn, and described carrier is Al
2o
3and Nb
2o
5mixture, wherein Al
2o
3and Nb
2o
5mass ratio be 100:(0.005 ~ 10) technical scheme, solve this problem preferably, can be used in the industrial production of 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol.
Description
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 being substituted ethylene glycol or the production of other polyvalent alcohol by it has good thermostability and thermoplasticity, can keep stable physical properties and electrical property at a higher temperature, the product obtained by this kind of resin-made then has good chemical resistant properties and environment resistant.The technique of current suitability for industrialized production 1,4 cyclohexane dimethanol take mainly dimethyl terephthalate (DMT) as raw material, and first benzene ring hydrogenation prepares 1,4 cyclohexanedicarboxylic acid dimethyl ester, then prepares 1,4 cyclohexane dimethanol by ester through hydrogenation reaction.Due to the relatively low and abundance of terephthalic acid price, therefore occurred taking terephthalic acid as the trend that 1,4 cyclohexane dimethanol prepared by raw material in recent years.Its process also needs usually through two-step reaction, first be that phenyl ring selec-tive hydrogenation produces 1,4-cyclohexane cyclohexanedimethanodibasic, then 1,4 cyclohexanedicarboxylic acid 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 DEG C and 8 ~ 15MPa generates 1,4 cyclohexane dimethanol, and wherein 1,4-cyclohexane cyclohexanedimethanodibasic hydrogenation generates the committed step that 1,4 cyclohexane dimethanol is whole technology.At present, most patent all adopts noble metal catalyst to realize this process, as US Patent No. 6294703 adopts Ru-Sn-Pt/C catalyzer to carry 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, when not using Pt and Re, still obtaining good 1,4 cyclohexane dimethanol yield, is 90.1 ~ 95.4%, but the life-span of its catalyzer is not long, and after reusing 5 times, 1,4 cyclohexane dimethanol yield sharply declines.
Summary of the invention
Technical problem to be solved by this invention is the problem that in the method for the 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol existed in prior art, catalyzer work-ing life is short.There is provided a kind of method of 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol, 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, in the presence of a catalyst, take water as reaction medium, hydrogen and 1,4 cyclohexanedicarboxylic acid carry out reaction preparation 1 under the reaction pressure of the temperature of reaction of 180 ~ 250 DEG C and 8 ~ 15MPa, 4-cyclohexanedimethanol, described catalyzer is made up of active ingredient and carrier, and wherein said active ingredient is Ru and Sn, and described carrier is Al
2o
3and Nb
2o
5mixture, wherein Al
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), be more preferably 100:(0.007 ~ 0.01).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 is 92.8% and yield sharply declines after reusing 5 times, 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, achieves good technique effect.
Embodiment
[embodiment 1]
The preparation method of carrier is as follows: by 100g aluminum oxide (Al
2o
3) to impregnated in niobium content be in the niobium oxalate aqueous solution of 7g, leaves standstill 6h, after dipping, first vacuum-drying 3h at 85 DEG C, then roasting 5h at 550 DEG C, obtains Al
2o
3-Nb
2o
5carrier mixture.With the aluminium content in ICP-AES mensuration carrier mixture and content of niobium, 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, leave standstill aging 15h, dry 2h at 85 DEG C, getting granularity 80 ~ 200 object particle after grinding is catalyst precursor, then 3h is reduced in the hydrogen of 7.5 times of nitrogen dilutions, reduction temperature is 550 DEG C, and hydrogen flowing quantity is 120ml/min, reduction terminate after be cooled to room temperature anti-applications catalyst.Adopt ICP-AES to measure the content of Ru and Sn in gained catalyzer, be respectively Ru4.7wt% and Sn4.8wt%, active component content (i.e. Ru and Sn summation) is 9.5wt% in the catalyst.
Evaluating catalyst method is as follows: 15g1,4-cyclohexane cyclohexanedimethanodibasic and 150g water are jointly placed in the autoclave of 300ml, adds the above-mentioned catalyzer of 4g.Extract air in still after enclosed high pressure still out and pass into hydrogen exchange air, under hydrogen pressure 2.0MPa, being heated with stirring to temperature of reaction 230 DEG C, then passing into hydrogen to reaction pressure 10MPa, start to react timing, keeping the hydrogen pressure needed for reaction until react end.Filtration catalizer after cooling, uses gas chromatographic analysis reaction solution, calculates target product concentration by marker method.
[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 operations are with embodiment 1, and carrier composition, specific surface area and reaction product yield obtained by each embodiment are as shown in table 1.Adopt ICP-AES to measure the content of Ru and Sn in gained catalyzer, be respectively Ru4.7wt% and Sn4.8wt%, active component content (i.e. Ru and Sn summation) is 9.5wt% in the catalyst.
[embodiment 9-16]
The obtained catalyzer of above-described embodiment 1-8 is adopted to evaluate respectively successively, evaluation method is as embodiment 1, difference is not more raw catalyst and repeat evaluation 10 times at identical conditions continuously after often dropping into a collection of raw catalyst, its evaluate at every turn in the yield of reaction product as shown in table 2.
[comparative example 1]
Ru-Sn/Al is prepared according to the method for the embodiment 1 of Chinese patent CN1911504
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, leave standstill aging 15h, at 85 DEG C of dry 2h, getting granularity 80 ~ 200 object particle after grinding is catalyst precursor, heating hydrogen reducing, and hydrogen flowing quantity is 150ml/min, namely obtains anti-applications catalyst.Adopt ICP-AES to measure the content of Ru and Sn in gained catalyzer, be respectively Ru4.7wt% and Sn4.8wt%, active component content (i.e. Ru and Sn summation) is 9.5wt% in the catalyst.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 operations are with embodiment 1, and carrier composition, specific surface area and reaction product yield obtained by comparative example 2 are as shown in table 1.Adopt ICP-AES to measure the content of Ru and Sn in gained catalyzer, be respectively Ru4.7wt% and Sn4.8wt%, active component content (i.e. Ru and Sn summation) is 9.5wt% in the catalyst.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
Claims (3)
1. one kind 1,4-cyclohexane cyclohexanedimethanodibasic Hydrogenation 1, the method of 4-cyclohexanedimethanol, in the presence of a catalyst, with water reaction medium, hydrogen and 1,4-cyclohexane cyclohexanedimethanodibasic carries out reaction and prepares 1,4 cyclohexane dimethanol under the reaction pressure of the temperature of reaction of 180 ~ 250 DEG C and 8 ~ 15MPa, it is characterized in that described catalyzer is made up of active ingredient and carrier, wherein said active ingredient is Ru and Sn, and described carrier is Al
2o
3and Nb
2o
5mixture, wherein Al
2o
3and Nb
2o
5mass ratio be 100:(0.005 ~ 10); The granularity of described catalyzer is 20 ~ 200 orders; The specific surface area of described carrier is 100 ~ 200m
2/ g; In described catalyzer, the mass ratio of active ingredient Ru and Sn is 1:(0.6 ~ 2.4); In described catalyzer, the content of active ingredient is 5 ~ 20wt%.
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).
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|---|---|---|---|
| CN201210324514.3A CN103664524B (en) | 2012-09-05 | 2012-09-05 | The method of 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol |
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| CN201210324514.3A CN103664524B (en) | 2012-09-05 | 2012-09-05 | The method of 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol |
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| CN103664524B true CN103664524B (en) | 2016-01-13 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498763B (en) * | 2014-09-25 | 2018-02-13 | 中国石油化工股份有限公司 | 1,4 cyclohexanedimethanol catalyst |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| CN114308035B (en) * | 2022-01-14 | 2024-08-06 | 浙江大学衢州研究院 | Hydrogenation catalyst for 1, 4-cyclohexanedicarboxylic acid, preparation method and application thereof |
| CN114436772B (en) * | 2022-01-29 | 2022-08-02 | 浙江清和新材料科技有限公司 | Preparation method of 1, 4-cyclohexanedimethanol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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