CN104549251A - Catalyst for synthesizing 1, 4-cyclohexanedimethanol and preparation method of catalyst - Google Patents
Catalyst for synthesizing 1, 4-cyclohexanedimethanol and preparation method of catalyst Download PDFInfo
- Publication number
- CN104549251A CN104549251A CN201310512630.2A CN201310512630A CN104549251A CN 104549251 A CN104549251 A CN 104549251A CN 201310512630 A CN201310512630 A CN 201310512630A CN 104549251 A CN104549251 A CN 104549251A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- catalyst
- content
- carrier
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for synthesizing 1, 4-cyclohexanedimethanol by using 1,4-cyclohexanedicarboxylic acid through hydrogenation, a preparation method of the catalyst and a method for synthesizing 1, 4-cyclohexanedimethanol in order to mainly solve the problem of short service life of the catalyst in the prior art. The problem is better solved through the technical scheme that the catalyst for synthesizing 1, 4-cyclohexanedimethanol comprises active components Ru and Sn and a carrier C@Al2O3, wherein the catalyst contains 1-10wt% of Ru, the mass ratio of Ru to Sn is 1: (0.5-2), and the carrier contains 1-20wt% of C. The catalyst can be used for industrial production of 1, 4-cyclohexanedimethanol prepared by using 1, 4-cyclohexanedicarboxylic acid through hydrogenation.
Description
Technical field
The present invention relates to the synthetic method of the catalyzer of 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol, the preparation method of catalyzer and 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, is first that phenyl ring selec-tive hydrogenation produces 1,4 cyclohexanedicarboxylic acid, then 1,4 cyclohexanedicarboxylic acid repeated hydrogenation generates 1,4 cyclohexane dimethanol, wherein 1,4 cyclohexanedicarboxylic acid 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, the yield of its 1,4 cyclohexane dimethanol is 91.8%, and the Ru-Sn-Re/C catalyzer that US6495730 adopts carries out hydrogenation reaction, it is 1 years old, the yield of 4-cyclohexanedimethanol is only 75%, and rare metal Pt and Re of this type of catalyzer owing to using price very expensive in a large number, therefore production cost is very high.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.
Summary of the invention
One of technical problem to be solved by this invention is short problem in catalyzer work-ing life of existing in prior art.There is provided a kind of catalyzer for 1,4 cyclohexane dimethanol synthesis, this catalyzer tool good stability, the feature that the life-span is long.
Two of technical problem to be solved by this invention is to provide the preparation method of one of a kind of above-mentioned technical problem catalyzer.
Three of the technical problem to be solved in the present invention is the synthetic methods of the 1,4 cyclohexane dimethanol adopting one of technical problem described catalyzer.
In order to one of solve the problems of the technologies described above, the technical solution used in the present invention is as follows: for the production of the catalyzer of 1,4 cyclohexane dimethanol, and described catalyzer comprises active constituent Ru and Sn, and support C@Al
2o
3, wherein in catalyzer, Ru content is the mass ratio of 1 ~ 10wt%, Ru and Sn is 1:(0.5 ~ 2), C content 1 ~ 20wt% in carrier.Boron is preferably included, more preferably boracic in described support of the catalyst in described support of the catalyst
0.3 ~ 0.5 wt%.
In catalyzer described in technique scheme, Ru content is the mass ratio of 3 ~ 5wt%, Ru and Sn is 1:(0.8 ~ 1.5).C content in described carrier is 10 ~ 12wt%.
In order to solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: the preparation method of catalyzer described in the described technical scheme of one of above-mentioned technical problem, comprises the following steps:
A) with the aqueous impregnation Al of at least one in starch, sucrose or glucose sugar
2o
3, then drying, carbonize to obtain described carrier;
B) be steeping fluid with the aqueous solution being dissolved with tensio-active agent and aequum Ru compound and Sn compound, impregnated carrier, then drying, roasting obtains catalyst precursor;
C) with reductive agent, the compound of Ru and Sn in catalyst precursor is reduced to metal, obtains described catalyzer.
As the preparation method of the catalyzer of the technical scheme of boracic preferred in above-mentioned catalyzer, boron passes through in step a) for flooding Al
2o
3the aqueous solution in add boric acid form load simultaneously when preparing carrier introduced in catalyzer.
Tensio-active agent described in technique scheme is that general molecular formula is preferably R-O-(CH
2cH
2o) fatty alcohol-polyoxyethylene ether of n-H, R is preferably C
12-18alkyl, preferred n=10 ~ 12.
Dosage of surfactant described in technique scheme is preferably step b) 0.5 ~ 2.5wt% of described carrier quality.
In technique scheme, step a) is preferably 80 ~ 110 DEG C with temperature dry described in step b).
Carry out under in technique scheme, step charing a) and step b) roasting are preferably preferably the condition of 400 ~ 600 DEG C at inert atmosphere and temperature.Step a) described in the inert atmosphere preferably inert gas atmosphere of zero group in nitrogen atmosphere or the periodic table of elements.
Step c in technique scheme) described in reductive agent be preferably hydrogen, reduction temperature is preferably 400 ~ 600 DEG C.Preferably with the gas dilution hydrogen to reactionlessness, this is to the gas preferred nitrogen of reactionlessness, the more preferably nitrogen dilution of 5 ~ 10 times of volumes.
In order to solve the problems of the technologies described above three, the technical solution used in the present invention is as follows: 1, the synthetic method of 4-cyclohexanedimethanol, with to 1,4-cyclohexane cyclohexanedimethanodibasic and hydrogen are raw material, water is solvent, under catalyzer according to any one of the described technical scheme of one of technical problem exists, be obtained by reacting 1,4 cyclohexane dimethanol.
In technique scheme, solvent and 1, the mass ratio of 4-cyclohexane cyclohexanedimethanodibasic is preferably (8 ~ 15): 1, catalyzer and 1, the mass ratio of 4-cyclohexane cyclohexanedimethanodibasic is preferably (0.2 ~ 0.3): 1, and the mol ratio of hydrogen and 1,4 cyclohexanedicarboxylic acid is preferably (8 ~ 10): 1, temperature of reaction is preferably 220 ~ 240 DEG C, and reaction pressure is preferably 8 ~ 12MPa.
The discovery that contriver is surprised, adopts the activity of technique scheme rear catalyst, selectivity and life-span to be all greatly improved.Experimental result shows, the catalyzer use of prior art significantly declines to the yield of 1,4 cyclohexane dimethanol when the tenth time; And the yield of catalyzer of the present invention under equal conditions 1,4 cyclohexane dimethanol is substantially constant, achieves good technique effect.
Embodiment
[embodiment 1]
Support C@Al
2o
3preparation method as follows: get 50g Al
2o
3-, then according to glucose and Al
2o
3mass ratio be that 0.65:1 prepares 100ml D/W, by 50g Al
2o
3add wherein with 1.5g boric acid, dipping 12h.After dipping terminates, dry 3h at 90 DEG C in loft drier in a vacuum, then 500 DEG C of roasting 3h under nitrogen atmosphere protection, obtain support C@B-Al
2o
3, its carbon content is 10.1wt% after measured, boracic 0.42wt%.
Method for preparing catalyst is as follows: 4.53gRuCl
33H
2o is dissolved in 50ml deionized water, then adds 3.91gSnCl
22H
2o dissolves, then adds 35g support C@B-Al
2o
3stir with 0.35g dodecyl polyoxyethylene (10) ether, leave standstill aging 15h, at 90 DEG C, dry 2h obtains catalyst precursor.Then gained presoma is reduced 3h in the hydrogen of 7.5 times of nitrogen dilutions, reduction temperature is 500 DEG C, and hydrogen flowing quantity is 120ml/min, be cooled to after reduction terminates 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%.
Catalyst life evaluation method step is as follows:
(1) catalyzer initial activity is evaluated: 15g1,4-cyclohexane cyclohexanedimethanodibasic and 150g water are jointly placed in the autoclave of 300ml, add 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, and calculates first time 1,4 cyclohexane dimethanol yield.
(2) catalytic agent reuse test: step (1) used catalyzer to be once again once considered as second time by the method evaluation of step (1), the rest may be inferred, proceeds to the tenth test like this altogether.Filtration catalizer after cooling, uses gas chromatographic analysis reaction solution, calculates target product concentration, and calculate the tenth 1,4 cyclohexane dimethanol yield by marker method.
By the tenth time and first time 1,4 cyclohexane dimethanol yield are compared the life-span judging catalyzer, it is larger that yield reduces amplitude, is considered as the life-span lower.
Conveniently compare, the yield of Key Experiment condition used for this embodiment, gained catalyzer composition and evaluating catalyst gained 1,4 cyclohexane dimethanol is listed in table 1.
[embodiment 2-5]
The input amount changing boric acid is followed successively by 0.65g, 1.0g, 1.65g and 1.98g, all the other operations are with embodiment 1, conveniently compare, the yield of Key Experiment condition used for each embodiment, gained catalyzer composition and evaluating catalyst gained 1,4 cyclohexane dimethanol is listed in table 1.
[embodiment 6]
Support C@Al
2o
3preparation method as follows: get 50g Al
2o
3-, then according to glucose and Al
2o
3mass ratio be that 0.65:1 prepares 100ml D/W, by 50g Al
2o
3add wherein, dipping 12h.After dipping terminates, dry 3h at 90 DEG C in loft drier in a vacuum, then 500 DEG C of roasting 3h under nitrogen atmosphere protection, obtain support C@Al
2o
3, its carbon content is 10.1wt% after measured.
Method for preparing catalyst is as follows: 4.53gRuCl
33H
2o is dissolved in 50ml deionized water, then adds 3.91gSnCl
22H
2o dissolves, then adds 35g support C@Al
2o
3stir with 0.35g dodecyl polyoxyethylene (10) ether, leave standstill aging 15h, at 90 DEG C, dry 2h obtains catalyst precursor.Then gained presoma is reduced 3h in the hydrogen of 7.5 times of nitrogen dilutions, reduction temperature is 500 DEG C, and hydrogen flowing quantity is 120ml/min, be cooled to after reduction terminates 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%.
Catalyst life evaluation method step is as follows:
(1) catalyzer initial activity is evaluated: 15g1,4-cyclohexane cyclohexanedimethanodibasic and 150g water are jointly placed in the autoclave of 300ml, add 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, and calculates first time 1,4 cyclohexane dimethanol yield.
(2) catalytic agent reuse test: step (1) used catalyzer to be once again once considered as second time by the method evaluation of step (1), the rest may be inferred, proceeds to the tenth test like this altogether.Filtration catalizer after cooling, uses gas chromatographic analysis reaction solution, calculates target product concentration, and calculate the tenth 1,4 cyclohexane dimethanol yield by marker method.
By the tenth time and first time 1,4 cyclohexane dimethanol yield are compared the life-span judging catalyzer, it is larger that yield reduces amplitude, is considered as the life-span lower.
Conveniently compare, the yield of Key Experiment condition used for this embodiment, gained catalyzer composition and evaluating catalyst gained 1,4 cyclohexane dimethanol is listed in table 1.
[embodiment 7-10]
Change RuCl
33H
2o and SnCl
22H
2the input amount of O is followed successively by 0.94gRuCl
33H
2o and 1.38gSnCl
22H
2o, 3gRuCl
33H
2o and 3.62gSnCl
22H
2o, 5.2gRuCl
33H
2o and 5.7gSnCl
22H
2o, 10.7gRuCl
33H
2o and 4.6gSnCl
22H
2o, all the other operations, with embodiment 6, are conveniently compared, and the yield of Key Experiment condition used for each embodiment, gained catalyzer composition and evaluating catalyst gained 1,4 cyclohexane dimethanol is listed in table 1.
[embodiment 11-15]
Change glucose and Al
2o
3mass ratio 0.06:1,0.25:1,0.75:1,1:1,1.5:1, all the other operations are with embodiment 6, conveniently compare, the yield of Key Experiment condition used for each embodiment, gained catalyzer composition and evaluating catalyst gained 1,4 cyclohexane dimethanol is listed in table 1.
[embodiment 16-19]
Carrier in change embodiment 6 and the maturing temperature of catalyzer are 350 DEG C, 400 DEG C, 600 DEG C, 650 DEG C, all the other operations are with embodiment 6, conveniently compare, the yield of Key Experiment condition used for each embodiment, gained catalyzer composition and evaluating catalyst gained 1,4 cyclohexane dimethanol is listed in table 1.
[embodiment 20-24]
Change dodecyl polyoxyethylene (10) the ether consumption in embodiment 6, all the other operations are with embodiment 6, conveniently compare, the yield of Key Experiment condition used for each embodiment, gained catalyzer composition and evaluating catalyst gained 1,4 cyclohexane dimethanol is listed in table 1.
[embodiment 25]
Support C@Al
2o
3preparation method as follows: get 50g Al
2o
3-, then according to glucose and Al
2o
3mass ratio be that 0.65:1 prepares 100ml D/W, by 50g Al
2o
3flood wherein 12h.After dipping terminates, dry 3h at 90 DEG C in loft drier in a vacuum, then 500 DEG C of roasting 3h under nitrogen atmosphere protection, obtain support C@Al
2o
3, its carbon content is 10.1wt% after measured.
Method for preparing catalyst is as follows: by 4.53gRuCl
33H
2o is dissolved in 50ml deionized water, then adds 3.91gSnCl
22H
2o dissolves, then adds 35g support C@Al
2o
3stir, leave standstill aging 15h, at 85 DEG C of dry 2h, at 500 DEG C, roasting 3h obtains catalyst precursor, then gained presoma is reduced 3h in the hydrogen of 7.5 times of nitrogen dilutions, reduction temperature is 500 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%.Gained catalyzer is evaluated according to the method for embodiment 1, and the yield of its each reaction product is as shown in table 1.
[embodiment 26]
Support C@Al
2o
3preparation method as follows: get 50g Al
2o
3-, then according to glucose and Al
2o
3mass ratio be that 0.65:1 prepares 100ml D/W, by 50g Al
2o
3flood wherein 12h.After dipping terminates, dry 3h at 90 DEG C in loft drier in a vacuum, then 500 DEG C of roasting 3h under nitrogen atmosphere protection, obtain support C@Al
2o
3, its carbon content is 10.1wt% after measured.
Method for preparing catalyst is as follows: by 4.53gRuCl
33H
2o is dissolved in 50ml deionized water, then adds 3.91gSnCl
22H
2o dissolves, then adds 35g support C@Al
2o
3stir with 0.35g n-nonane polyoxyethylene (10) ether, leave standstill aging 15h, at 85 DEG C of dry 2h, at 500 DEG C, roasting 3h obtains catalyst precursor, then gained presoma is reduced 3h in the hydrogen of 7.5 times of nitrogen dilutions, reduction temperature is 500 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%.Gained catalyzer is evaluated according to the method for embodiment 1, and the yield of its each reaction product is as shown in table 1.
[embodiment 27]
Support C@Al
2o
3preparation method as follows: get 50g Al
2o
3-, then according to glucose and Al
2o
3mass ratio be that 0.65:1 prepares 100ml D/W, by 50g Al
2o
3flood wherein 12h.After dipping terminates, dry 3h at 90 DEG C in loft drier in a vacuum, then 500 DEG C of roasting 3h under nitrogen atmosphere protection, obtain support C@Al
2o
3, its carbon content is 10.1wt% after measured.
Method for preparing catalyst is as follows: by 4.53gRuCl
33H
2o is dissolved in 50ml deionized water, then adds 3.91gSnCl
22H
2o dissolves, then adds 35g support C@Al
2o
3stir with 0.35g octadecyl polyoxyethylene (10) ether, leave standstill aging 15h, at 85 DEG C of dry 2h, at 500 DEG C, roasting 3h obtains catalyst precursor, then gained presoma is reduced 3h in the hydrogen of 7.5 times of nitrogen dilutions, reduction temperature is 500 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%.Gained catalyzer is evaluated according to the method for embodiment 1, and the yield of its each reaction product is as shown in table 1.
[embodiment 28]
Support C@Al
2o
3preparation method as follows: get 50g Al
2o
3-, then according to glucose and Al
2o
3mass ratio be that 0.65:1 prepares 100ml D/W, by 50g Al
2o
3flood wherein 12h.After dipping terminates, dry 3h at 90 DEG C in loft drier in a vacuum, then 500 DEG C of roasting 3h under nitrogen atmosphere protection, obtain support C@Al
2o
3, its carbon content is 10.1wt% after measured.
Method for preparing catalyst is as follows: by 4.53gRuCl
33H
2o is dissolved in 50ml deionized water, then adds 3.91gSnCl
22H
2o dissolves, then adds 35g support C@Al
2o
3stir with 0.35g octadecyl polyoxyethylene (12) ether, leave standstill aging 15h, at 85 DEG C of dry 2h, at 500 DEG C, roasting 3h obtains catalyst precursor, then gained presoma is reduced 3h in the hydrogen of 7.5 times of nitrogen dilutions, reduction temperature is 500 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%.Gained catalyzer is evaluated according to the method for embodiment 1, and the yield of its each reaction product is as shown in table 1.
[embodiment 29]
Support C@Al
2o
3preparation method as follows: get 50g Al
2o
3-, then according to glucose and Al
2o
3mass ratio be that 0.65:1 prepares 100ml D/W, by 50g Al
2o
3flood wherein 12h.After dipping terminates, dry 3h at 90 DEG C in loft drier in a vacuum, then 500 DEG C of roasting 3h under nitrogen atmosphere protection, obtain support C@Al
2o
3, its carbon content is 10.1wt% after measured.
Method for preparing catalyst is as follows: by 4.53gRuCl
33H
2o is dissolved in 50ml deionized water, then adds 3.91gSnCl
22H
2o dissolves, then adds 35g support C@Al
2o
3stir with 0.35g nonadecyl polyoxyethylene (13) ether, leave standstill aging 15h, at 85 DEG C of dry 2h, at 500 DEG C, roasting 3h obtains catalyst precursor, then gained presoma is reduced 3h in the hydrogen of 7.5 times of nitrogen dilutions, reduction temperature is 500 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%.Gained catalyzer is evaluated according to the method for embodiment 1, and the yield of its each reaction product is as shown in table 1.
[embodiment 30]
Support C@Al
2o
3preparation method as follows: get 50g Al
2o
3-, then according to starch and Al
2o
3mass ratio be that 0.65:1 prepares 100ml amidin, by 50g Al
2o
3flood wherein 12h.After dipping terminates, dry 3h at 90 DEG C in loft drier in a vacuum, then 500 DEG C of roasting 3h under nitrogen atmosphere protection, obtain support C@Al
2o
3, its carbon content is 10.1wt% after measured.
Method for preparing catalyst is as follows: by 4.53gRuCl
33H
2o is dissolved in 50ml deionized water, then adds 3.91gSnCl
22H
2o dissolves, then adds 35g support C@Al
2o
3stir with 0.33g dodecyl polyoxyethylene (10) ether, leave standstill aging 15h, at 85 DEG C of dry 2h, at 500 DEG C, roasting 3h obtains catalyst precursor, then gained presoma is reduced 3h in the hydrogen of 7.5 times of nitrogen dilutions, reduction temperature is 500 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%.Gained catalyzer is evaluated according to the method for embodiment 1, and the yield of its each reaction product is as shown in table 1.
[embodiment 31]
Support C@Al
2o
3preparation method as follows: get 50g Al
2o
3-, then according to sucrose and Al
2o
3mass ratio be that 0.65:1 prepares 100ml aqueous sucrose solution, by 50g Al
2o
3flood wherein 12h.After dipping terminates, dry 3h at 90 DEG C in loft drier in a vacuum, then 500 DEG C of roasting 3h under nitrogen atmosphere protection, obtain support C@Al
2o
3, its carbon content is 10.1wt% after measured.
Method for preparing catalyst is as follows: by 4.53gRuCl
33H
2o is dissolved in 50ml deionized water, then adds 3.91gSnCl
22H
2o dissolves, then adds 35g support C@Al
2o
3stir with 0.35g dodecyl polyoxyethylene (10) ether, 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, 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%.Gained catalyzer is evaluated according to the method for embodiment 1, and the yield of its each reaction product is as shown in table 1.
[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 50ml 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, at 500 DEG C, roasting 3h obtains catalyst precursor, then gained presoma is reduced 3h in the hydrogen of 7.5 times of nitrogen dilutions, reduction temperature is 500 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%.Gained catalyzer is evaluated according to the method for embodiment 1, and the yield of its each reaction product is as shown in table 1.
[comparative example 2]
Method for preparing catalyst is as follows: by 4.53gRuCl
33H
2o is dissolved in 50ml deionized water, then adds 3.91gSnCl
22H
2o dissolves, then adds 35g carrier A l
2o
3stir with 0.35g dodecyl polyoxyethylene (10) ether, leave standstill aging 15h, at 85 DEG C of dry 2h, at 500 DEG C, roasting 3h obtains catalyst precursor, then gained presoma is reduced 3h in the hydrogen of 7.5 times of nitrogen dilutions, reduction temperature is 500 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%.Gained catalyzer is evaluated according to the method for embodiment 1, and the yield of its each reaction product is as shown in table 1.
As can be seen from Table 1, this technology is applied to 1,4 cyclohexanedicarboxylic acid hydrogenation production 1,4 cyclohexane dimethanol process and achieves good reaction result.The carrier through one of glucose, sugarcane sugar and starch carbonization aluminum oxide gained is adopted to be applied to the Ru-Sn bimetallic catalyst of preparation, its catalyst activity and life-span are all comparatively satisfactory, especially using glucose as carbon source, add boric acid modified simultaneously, ensure that in carrier, C content is at 10 ~ 12wt%, B content is when 0.3 ~ 0.5wt%, and in catalyzer, Ru content is 3 ~ 5wt%, the mass ratio of Ru and Sn is 1:(0.8 ~ 1.5) time, its catalyst activity is higher.At solvent and 1, the mass ratio of 4-cyclohexane cyclohexanedimethanodibasic is 10:1, the mass ratio of catalyzer and 1,4 cyclohexanedicarboxylic acid is 0.27:1, and temperature of reaction is 230 DEG C, reaction pressure is 10MPa, the yield of 1,4 cyclohexane dimethanol is greater than 96% and reuse 10 activity are substantially constant, the catalyzer prepared far above prior art obtain under the same reaction conditions 1,4-cyclohexanedimethanol yield (91.8%) and activity decrease more than 50% after reuse 10 times, achieve good technique effect.
1(is continued for table)
Table 1(continues)
Claims (10)
1. for the production of the catalyzer of 1,4 cyclohexane dimethanol, described catalyzer comprises active constituent Ru and Sn, and support C@Al
2o
3, wherein in catalyzer, Ru content is the mass ratio of 1 ~ 10wt%, Ru and Sn is 1:(0.5 ~ 2), C content 1 ~ 20wt% in carrier.
2. catalyzer according to claim 1, is characterized in that Ru content in described catalyzer be the mass ratio of 3 ~ 5wt%, Ru and Sn is 1:(0.8 ~ 1.5).
3. catalyzer according to claim 1, is characterized in that the C content in described carrier is 10 ~ 12wt%.
4. the preparation method of catalyzer described in claim 1, comprises the following steps:
A) with the aqueous impregnation Al of at least one in starch, sucrose or glucose sugar
2o
3, then drying, carbonize to obtain described carrier;
B) be steeping fluid with the aqueous solution being dissolved with tensio-active agent and aequum Ru compound and Sn compound, impregnated carrier, then drying, roasting obtains catalyst precursor;
C) with reductive agent, the compound of Ru and Sn in catalyst precursor is reduced to metal, obtains described catalyzer.
5. method according to claim 4, is characterized in that described tensio-active agent be general molecular formula is R-O-(CH
2cH
2o) fatty alcohol-polyoxyethylene ether of n-H, R is C
12-18alkyl, n=10 ~ 12.
6. method according to claim 5, is characterized in that described dosage of surfactant is step b) 0.5 ~ 2.5wt% of described carrier quality.
7. method according to claim 4, it is characterized in that step a) and dry temperature described in step b) be 80 ~ 110 DEG C.
8. method according to claim 4, is characterized in that step charing a) and step b) roasting are carried out under inert atmosphere and temperature are the condition of 400 ~ 600 DEG C.
9. method according to claim 4, is characterized in that step c) described in reductive agent be hydrogen, reduction temperature is 400 ~ 600 DEG C.
The synthetic method of 10.1,4-cyclohexanedimethanol, with to 1,4 cyclohexanedicarboxylic acid and hydrogen for raw material, water is solvent, is obtained by reacting 1,4 cyclohexane dimethanol at catalyzer as claimed in claim 1 under existing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310512630.2A CN104549251A (en) | 2013-10-28 | 2013-10-28 | Catalyst for synthesizing 1, 4-cyclohexanedimethanol and preparation method of catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310512630.2A CN104549251A (en) | 2013-10-28 | 2013-10-28 | Catalyst for synthesizing 1, 4-cyclohexanedimethanol and preparation method of catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104549251A true CN104549251A (en) | 2015-04-29 |
Family
ID=53066957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310512630.2A Pending CN104549251A (en) | 2013-10-28 | 2013-10-28 | Catalyst for synthesizing 1, 4-cyclohexanedimethanol and preparation method of catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104549251A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019132537A1 (en) | 2017-12-29 | 2019-07-04 | 한화케미칼 주식회사 | Carbon-based noble metal-transition metal catalyst enabling high selective conversion and production method therefor |
| CN111683747A (en) * | 2017-12-29 | 2020-09-18 | 韩华思路信株式会社 | Noble metal-transition metal composite catalyst loaded on carbon-coated silica-alumina carrier and preparation method thereof |
| JP2021506970A (en) * | 2017-12-22 | 2021-02-22 | ハンファ ソリューションズ コーポレーション | A method for producing cyclohexanedimethanol having a high trans content and cyclohexanedimethanol produced thereby. |
| CN113272055A (en) * | 2018-12-31 | 2021-08-17 | 韩华思路信株式会社 | Carbon-based noble metal-transition metal composite catalyst and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6495730B1 (en) * | 1999-09-21 | 2002-12-17 | Asahi Kasei Kabushiki Kaisha | Catalysts for hydrogenation of carboxylic acid |
| CN1648214A (en) * | 2004-01-19 | 2005-08-03 | 中国石油化工股份有限公司 | Refined catalyst for fraction oil hydrogenation and its preparing method |
| CN1911504A (en) * | 2005-08-09 | 2007-02-14 | 中国石化上海石油化工股份有限公司 | Catalyst for preparing 1,4-cyclohexane dimethanol from hydrogenation of 1,4-cyclo hexane diformic acid |
| CN101066910A (en) * | 2007-06-01 | 2007-11-07 | 华东理工大学 | Process of preparing 1,4-cyclohexane dimethand |
| CN101209424A (en) * | 2006-12-27 | 2008-07-02 | 中国科学院大连化学物理研究所 | Carbon/aluminum oxide composite carrier catalyst for hydrazine decomposition reaction and preparation thereof |
| CN101327454A (en) * | 2008-07-29 | 2008-12-24 | 华东理工大学 | Modified carbon-coated alumina supporter with nucleocapsid structure and preparation method thereof |
| CN101940930A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Preparation method of hydrotreating catalyst |
| CN102068990A (en) * | 2010-11-25 | 2011-05-25 | 西安交通大学 | Nano carbon-covered alumina support-based preparation process of dehydrogenation catalyst |
-
2013
- 2013-10-28 CN CN201310512630.2A patent/CN104549251A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6495730B1 (en) * | 1999-09-21 | 2002-12-17 | Asahi Kasei Kabushiki Kaisha | Catalysts for hydrogenation of carboxylic acid |
| CN1648214A (en) * | 2004-01-19 | 2005-08-03 | 中国石油化工股份有限公司 | Refined catalyst for fraction oil hydrogenation and its preparing method |
| CN1911504A (en) * | 2005-08-09 | 2007-02-14 | 中国石化上海石油化工股份有限公司 | Catalyst for preparing 1,4-cyclohexane dimethanol from hydrogenation of 1,4-cyclo hexane diformic acid |
| CN101209424A (en) * | 2006-12-27 | 2008-07-02 | 中国科学院大连化学物理研究所 | Carbon/aluminum oxide composite carrier catalyst for hydrazine decomposition reaction and preparation thereof |
| CN101066910A (en) * | 2007-06-01 | 2007-11-07 | 华东理工大学 | Process of preparing 1,4-cyclohexane dimethand |
| CN101327454A (en) * | 2008-07-29 | 2008-12-24 | 华东理工大学 | Modified carbon-coated alumina supporter with nucleocapsid structure and preparation method thereof |
| CN101940930A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Preparation method of hydrotreating catalyst |
| CN102068990A (en) * | 2010-11-25 | 2011-05-25 | 西安交通大学 | Nano carbon-covered alumina support-based preparation process of dehydrogenation catalyst |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021506970A (en) * | 2017-12-22 | 2021-02-22 | ハンファ ソリューションズ コーポレーション | A method for producing cyclohexanedimethanol having a high trans content and cyclohexanedimethanol produced thereby. |
| JP7301872B2 (en) | 2017-12-22 | 2023-07-03 | ハンファ ソリューションズ コーポレーション | Process for producing cyclohexanedimethanol with high trans content and cyclohexanedimethanol produced by the same |
| WO2019132537A1 (en) | 2017-12-29 | 2019-07-04 | 한화케미칼 주식회사 | Carbon-based noble metal-transition metal catalyst enabling high selective conversion and production method therefor |
| CN111683747A (en) * | 2017-12-29 | 2020-09-18 | 韩华思路信株式会社 | Noble metal-transition metal composite catalyst loaded on carbon-coated silica-alumina carrier and preparation method thereof |
| US11517880B2 (en) | 2017-12-29 | 2022-12-06 | Hanwha Solutions Corporation | Carbon-based noble metal-transition metal catalyst enabling high selective conversion and production method therefor |
| CN111683747B (en) * | 2017-12-29 | 2023-12-29 | 韩华思路信株式会社 | Noble metal-transition metal composite catalyst supported on carbon-coated silica-alumina carrier and preparation method thereof |
| CN113272055A (en) * | 2018-12-31 | 2021-08-17 | 韩华思路信株式会社 | Carbon-based noble metal-transition metal composite catalyst and preparation method thereof |
| CN113272055B (en) * | 2018-12-31 | 2023-12-29 | 韩华思路信株式会社 | Carbon-based noble metal-transition metal composite catalyst and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103664524B (en) | The method of 1,4 cyclohexanedicarboxylic acid Hydrogenation 1,4 cyclohexane dimethanol | |
| CN102247876B (en) | Method for preparing ethylene with acetylene selective catalytic hydrogenation | |
| CN103877991B (en) | Anti-form-1, the production method of 4-cyclohexanedimethanol and used catalyst thereof | |
| CN107235829B (en) | Method for preparing 4-ethylphenol by selective hydrogenolysis of lignin | |
| CN104549251A (en) | Catalyst for synthesizing 1, 4-cyclohexanedimethanol and preparation method of catalyst | |
| CN104941634B (en) | A kind of preparing furan through decarbonylation of furfural palladium carbon catalyst and preparation method thereof | |
| CN103372441B (en) | Preparation method of methanol synthesis catalyst | |
| CN105582961A (en) | 1,4-cyclohexan dimethyl dicarboxylate hydrogenation catalyst | |
| CN103769089A (en) | Catalyst preparation method, and synthesis method of catalyst and trans-1,4-cyclohexane dicarboxylic acid | |
| CN105498763A (en) | 1, 4-cyclohexanedimethanol catalyst | |
| CN113559861A (en) | Cu-Ni bimetallic catalyst for directly converting furfural into tetrahydrofurfuryl alcohol, preparation method and application | |
| CN105879862A (en) | Preparation method of eggshell-type noble metal catalyst and method of using same for dibenzofuran hydrogenation ring opening to prepare o-phenylphenol | |
| CN1911504A (en) | Catalyst for preparing 1,4-cyclohexane dimethanol from hydrogenation of 1,4-cyclo hexane diformic acid | |
| CN1911884A (en) | Method of preparing 1,4-cyclohexane dimethanol by hydrogenation of 1,4-cyclohexane diformic acid | |
| CN103372439B (en) | The preparation method of catalst for synthesis of methanol | |
| CN103372444B (en) | A kind of preparation method of copper-based catalysts | |
| CN110624604B (en) | Modified palladium-carbon catalyst, preparation method and application thereof | |
| CN111604060B (en) | Preparation method of hydrogenation catalyst carrier and product | |
| CN107754802B (en) | Catalyst for ethylene carbonate hydrogenation, preparation method and application | |
| CN105582927B (en) | 1,4 cyclohexanedimethanol catalyst and its preparation method | |
| CN105582926B (en) | Terephthalic acid (TPA) hydrogenation catalyst | |
| CN103878022A (en) | Preparation method of catalyst for synthesizing allyl acetate | |
| CN103877998B (en) | Produce the Catalysts and its preparation method of 1,4-CHDM | |
| US10280126B2 (en) | Method for producing conjugated diene | |
| CN104549250B (en) | Catalyst for synthesizing 1, 4-cyclohexanedimethanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150429 |
|
| RJ01 | Rejection of invention patent application after publication |