CN105582927B - 1,4 cyclohexanedimethanol catalyst and its preparation method - Google Patents

1,4 cyclohexanedimethanol catalyst and its preparation method Download PDF

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CN105582927B
CN105582927B CN201410573596.4A CN201410573596A CN105582927B CN 105582927 B CN105582927 B CN 105582927B CN 201410573596 A CN201410573596 A CN 201410573596A CN 105582927 B CN105582927 B CN 105582927B
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CN105582927A (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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Abstract

The present invention relates to Isosorbide-5-Nitrae cyclohexanedimethanol catalyst, solves the problems, such as selectively low to Isosorbide-5-Nitrae cyclohexanedimethanol for catalyst during Isosorbide-5-Nitrae cyclohexanedimethanol using Isosorbide-5-Nitrae cyclohexane cyclohexanedimethanodibasic Hydrogenation in the prior art.By using a kind of Isosorbide-5-Nitrae cyclohexanedimethanol catalyst, with TiO2And/or ZrO2For carrier, including the technical scheme that Ru, Sn and Bi at least two is active component, in the industrial production available for production Isosorbide-5-Nitrae cyclohexanedimethanol.

Description

1,4 cyclohexane dimethanol catalyst and its preparation method
Technical field
The present invention relates to a kind of 1,4-CHDM catalyst, its preparation method and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic are urged Change method of the Hydrogenation for 1,4 cyclohexane dimethanol.
Background technology
1,4-CHDM (abbreviation CHDM) is the important Organic Chemicals for producing polyester resin, and second is substituted by it Glycol or the polyester resin of other polynary alcohol productions have good heat endurance and thermoplasticity, can keep at a higher temperature Stable physical property and electrical property, and the product as made from this kind of resin then has good chemical resistance and environment resistant. The technique of industrialized production 1,4-CHDM is mainly using dimethyl terephthalate (DMT) as raw material at present, first benzene ring hydrogenation system Standby Isosorbide-5-Nitrae-dimethyl hexahydrophthalate, then 1,4-CHDM is prepared by ester through hydrogenation reaction.Due to terephthalic acid (TPA) (PTA) price is relatively low and abundance, therefore occurs preparing Isosorbide-5-Nitrae-hexamethylene by raw material of terephthalic acid (TPA) in recent years The trend of dimethanol.Relative maturity is two step hydrogenation methods in the prior art, i.e., terephthalic acid (TPA) first is hydrogenated into Isosorbide-5-Nitrae-ring Hexane dicarboxylic acid, repeated hydrogenation generation 1,4-CHDM, two-step reaction use different catalysts.Also proposition uses a step Hydrogenation method produces 1,4-CHDM, as Japan Patent JP2002069016 is proposed using Ru-Sn-Re as active component Loaded catalyst, the hydrogenation reaction 5h under the conditions of 250 DEG C and 15MPa, 1,4-CHDM yield are 42%. JP200007596 is then used using activated carbon as carrier, and active component is Ru-Sn-Pt catalyst, in 150 DEG C and 15MPa conditions Lower hydrogenation reaction 4h, 1,4-CHDM yield are 28.3%.Chinese patent CN100465145 is (entitled:1,4 hexamethylenes The preparation method of alkane dimethanol) use Ru-Sn-B/Al2O3Catalyst, the hydrogenation reaction 4h under the conditions of 230 DEG C and 10MPa, Isosorbide-5-Nitrae- Cyclohexanedimethanol yield is 85.7%, substantially increases the yield of 1,4-CHDM.
For above-mentioned patent using terephthalic acid (TPA) or dimethyl terephthalate (DMT) as raw material, cost is of a relatively high, and reacts Route is relatively long, and prepares 1,4-CHDM using terephthalyl alcohol as raw material not only course of reaction is simple, accessory substance It is few, and separating-purifying is also more convenient.The research of this technique is it has been reported that such as United States Patent (USP) US6600080 (Producing Method of alcohols such as cyclohexanedimethanol) 5%Ru/C catalyst is used, with water and methanol Mixture be solvent, carry out hydrogenation reaction, the conversion ratio of terephthalyl alcohol under the reaction conditions of 100 DEG C and 4.9MPa hydrogen pressures For 100%, 1,4-CHDM yield is 76%.Chinese patent CN101096332 is (entitled:By terephthalyl alcohol plus The method of hydrogen 1,4 cyclohexane dimethanol) use 4wt%Ru/Al2O3Catalyst, using water as solvent, at 100 DEG C and 8MPa Hydrogenation reaction is carried out under reaction condition, the conversion ratio of terephthalyl alcohol is 100%, and 1,4-CHDM yield is 91.2%.Such prior art generally uses Ru as active component, but Ru has very strong hydrogenolysis to 1,4-CHDM Effect, Isosorbide-5-Nitrae-dimethyl cyclohexane is easily generated, so as to influence the yield of 1,4-CHDM.
In addition to obtaining product 1,4-CHDM, it is necessary to its structure is considered, because 1,4-CHDM There are cis, trans two kinds of structures, syn-isomerism bulk melting point is 43 DEG C, and trans-isomerism bulk melting point is 70 DEG C.Although above-mentioned catalyst 1,4-CHDM can be obtained, but catalyst is equal to anti-form-1, the selectivity of 4- cyclohexanedimethanols (t-CHDM) Not high, anti-form-1 in products therefrom, the content of 4- cyclohexanedimethanols is less than 30wt%, and due to anti-form-1,4- hexamethylenes two The melting range (315~320 DEG C) of the high polymer of methanol and terephthalic acid (TPA) is than cis -1,4 cyclohexane dimethanol and to benzene two The melting range of the high polymer of formic acid is (260~267 DEG C) high, therefore it is required that the 1,4-CHDM of polymerization contain it is higher The trans-1,4-cyclohexane dimethanol of ratio.
The content of the invention
One of problem to be solved by this invention is that prior art uses 1,4 cyclohexanedicarboxylic acid Hydrogenation for 1,4- rings Catalyst is relatively low to the selectivity of 1,4-CHDM during hexane dimethanol, there is provided a kind of 1,4-CHDM catalysis Agent, the catalyst have the characteristics of selectively high to 1,4-CHDM.
The two of problem to be solved by this invention are the preparation methods of one of above mentioned problem catalyst.
The three of problem to be solved by this invention are the 1,4- hexamethylenes using one of the above-mentioned technical problem catalyst The synthetic method of dimethanol.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows:1,4 cyclohexane dimethanol is urged Agent, with TiO2And/or ZrO2It is active component at least two in carrier, including Ru, Sn and Bi.
In above-mentioned technical proposal, Ru contents are preferably 1~10wt%, more preferably 4~6wt%.
In above-mentioned technical proposal, Sn contents are preferably 5~10wt%, more preferably 5~6wt%.
In above-mentioned technical proposal, Bi contents are preferably 0.01~0.1wt%, more preferably 0.02~0.04wt%.
1,4-CHDM has two kinds of isomers of cis and trans, trans in 1,4-CHDM in order to improve The selectivity of isomers, in above-mentioned technical proposal, most preferably using TiO2And ZrO2The complex carrier of composition, and active component Include Ru, Sn and Bi simultaneously.Ti in more preferably described complex carrier:Zr mol ratio is 1:(0.5~1).
In order to solve the above-mentioned technical problem two, technical scheme is as follows:Any of one of above-mentioned technical problem The preparation method of catalyst, comprises the following steps described in technical scheme described in:
A) by the solution of the desired amount of compound containing Ti and the compound containing Zr, regulation pH value is 8~12, is precipitated, so The carrier is obtained by filtering, washing, dry, roasting;
B) carrier is impregnated with the desired amount of compound containing Ru, compound containing Sn and compound containing Bi;
C) Ru, Sn and Bi compound are reduced to metal simple-substance with reducing agent.
In above-mentioned technical proposal, described reducing agent is at least one in hydrogen, formaldehyde, sodium formate, hydrazine hydrate or formic acid Kind.
In above-mentioned technical proposal, the pH adjusting agent that step a) is used to adjust pH is not particularly limited, according to art technology The understanding of personnel, those alkaline matters commonly used in the art can be with.The specific embodiment of the invention employs ammoniacal liquor.Above-mentioned skill In art scheme, pH value is being adjusted to soluble polymer during 8~12, in system being present to obtained load with pH adjusting agent Body uniformity is favourable, but in order to reach comparable effect this and it is nonessential, even if preparing composite Ti O2-ZrO2Carrier is also So.When determining to use polymer, the species of polymer is not particularly limited, such as, but not limited to various molecular weight gather Ethylene glycol.In the specific embodiment of the invention, it is polyethylene glycol to prepare the polymer selected during carrier, is more specifically poly- second two Alcohol -400.
In order to solve the above-mentioned technical problem three, technical scheme is as follows:The synthesis of 1.4- cyclohexanedimethanols Method, in the presence of catalyst any one of the technical scheme in one of above-mentioned technical problem, using water as solvent, hydrogen and 1, 4- cyclohexane cyclohexanedimethanodibasics reaction generation 1,4 cyclohexane dimethanol.
In above-mentioned technical proposal, reaction temperature is preferably 220~260 DEG C, and more preferably 230~250 DEG C, Hydrogen Vapor Pressure is excellent Elect 6~10MPa, more preferably 8~10MPa, reaction time preferably 1.5~5h, more preferably 2.5~3.5h as.
In above-mentioned technical proposal, the mass ratio of Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and water is preferably 1:(1~20), more preferably 1:(5 ~10).
In above-mentioned technical proposal, catalyst and the mass ratio of Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic inventory are preferably 1:(1~20), More preferably 1:(5~10).
No matter the present invention use cis-Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, anti-form-1,4- cyclohexane cyclohexanedimethanodibasics, or it is cis with Anti-form-1,4- cyclohexane cyclohexanedimethanodibasic mixtures, obtains comparable effect.The 1,4- used in the specific embodiment of the invention Trans and trans mass ratio is 1 in cyclohexane cyclohexanedimethanodibasic:1.
The mass ratio 1 of Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic inventory and water is can be seen that from the data of embodiment:10, Catalyst and the mass ratio of 1,4 cyclohexanedicarboxylic acid inventory are 1:10,230 DEG C of reaction temperature, under Hydrogen Vapor Pressure 8.5MPa, React 3.5h, the selectivity that the conversion ratio of Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic is 100%, CHDM is up to 100%, and trans CHDM selection Property is 95%, preferable technique effect is achieved, available in CHDM production.
Embodiment
【Embodiment 1】
The preparation of carrier:According to Ti:Zr mol ratio is 1:0.75, by 1mol TiCl4It is dissolved in 100ml absolute ethyl alcohol shapes Cheng Zhong, it is then added to the ZrOCl dissolved with 0.75mol2·8H2Uniform titanium zirconium mixed solution is made into the O 100ml aqueous solution. Under ice bath, it is stirred continuously, the 15wt% ammonia spirits of the PEG-4000 containing 0.5wt% is slowly added drop-wise to mixed solution In precipitated, and adjust pH value as 9~10, stand 24h, filtering, be washed with deionized to without Cl-Untill (use 0.1mol/ L AgNO3Solution is examined), then washed 2 times with 50ml absolute ethyl alcohols, 10h is then dried under 383K and obtains oxide precursor, will The presoma is calcined 2h in 773K moving airs and obtains TiO2-ZrO2Carrier, understood through ICP-AES analyses, TiO2-ZrO2Carrier Middle Ti:Zr mol ratio is 1:0.74.
The preparation of catalyst:It is first according to Ru-Sn-Bi/TiO2-ZrO2Ru contents are that 5wt%, Sn content are in catalyst 6wt% and Bi contents are the RuCl that 0.03wt% weighs respective quality3、SnCl2And BiCl3And it is dissolved in 15wt% hydrochloric acid Middle formation 250ml maceration extracts, by gained maceration extract and 50 grams of TiO2-ZrO2Mixing, 12h is impregnated, then vacuum is done at 110 DEG C Dry 3h obtains catalyst precursor, finally obtains Ru- with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen Sn-Bi/TiO2-ZrO2Finished catalyst, analyzed through ICP-AES, the Ru contents in catalyst are 5wt%.Sn contents are 6wt% It is 0.03wt% with Bi contents, for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Ru-Sn-Bi/TiO of the above-mentioned gained of 10g2-ZrO2Catalyst, 1000g water is added, open stirring, first It is passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keep steady It is fixed, 230 DEG C of maintenance reaction temperature, and continuously it is passed through hydrogen reaction 3.5h.After reaction terminates, reaction product is analyzed, is It is convenient to compare, analysis result is listed in Table 1 below.
【Embodiment 2】
The preparation of carrier:According to Ti:Zr mol ratio is 1:0.5, by 1mol TiCl4It is dissolved in 100ml absolute ethyl alcohol shapes Cheng Zhong, it is then added to the ZrOCl dissolved with 0.5mol2·8H2Uniform titanium zirconium mixed solution is made into the O 100ml aqueous solution. Under ice bath, it is stirred continuously, the 15wt% ammonia spirits of the PEG-4000 containing 0.5wt% is slowly added drop-wise to mixed solution In precipitated, and adjust pH value as 9~10, stand 24h, filtering, be washed with deionized to without Cl-Untill (use 0.1mol/ L AgNO3Solution is examined), then washed 2 times with 50ml absolute ethyl alcohols, 10h is then dried under 383K and obtains oxide precursor, will The presoma is calcined 2h in 773K moving airs and obtains TiO2-ZrO2Carrier, understood through ICP-AES analyses, TiO2-ZrO2Carrier Middle Ti:Zr mol ratio is 1:0.49.
The preparation of catalyst:It is first according to Ru-Sn-Bi/TiO2-ZrO2Ru contents are that 5wt%, Sn content are in catalyst 6wt% and Bi contents are the RuCl that 0.03wt% weighs respective quality3、SnCl2And BiCl3And it is dissolved in 15wt% hydrochloric acid Middle formation 250ml maceration extracts, by gained maceration extract and 50 grams of TiO2-ZrO2Mixing, 12h is impregnated, then vacuum is done at 110 DEG C Dry 3h obtains catalyst precursor, finally obtains Ru- with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen Sn-Bi/TiO2-ZrO2Finished catalyst, analyzed through ICP-AES, the Ru contents in catalyst are 5wt%.Sn contents are 6wt% It is 0.03wt% with Bi contents, for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Ru-Sn-Bi/TiO of the above-mentioned gained of 10g2-ZrO2Catalyst, 1000g water is added, open stirring, first It is passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keep steady It is fixed, 230 DEG C of maintenance reaction temperature, and continuously it is passed through hydrogen reaction 3.5h.After reaction terminates, reaction product is analyzed, is It is convenient to compare, analysis result is listed in Table 1 below.
【Embodiment 3】
The preparation of carrier:According to Ti:Zr mol ratio is 1:1, by 1mol TiCl4100ml absolute ethyl alcohols are dissolved in be formed In, it is then added to the ZrOCl dissolved with 1mol2·8H2Uniform titanium zirconium mixed solution is made into the O 100ml aqueous solution.In ice Under bath, it is stirred continuously, the 15wt% ammonia spirits of the PEG-4000 containing 0.5wt% slowly is added drop-wise in mixed solution Row precipitation, and it is 9~10 to adjust pH value, stands 24h, filtering, is washed with deionized to without Cl-Untill (with 0.1mol/L AgNO3Solution is examined), then washed 2 times with 50ml absolute ethyl alcohols, 10h is then dried under 383K and obtains oxide precursor, before this Drive body is calcined 2h in 773K moving airs and obtains TiO2-ZrO2Carrier, understood through ICP-AES analyses, TiO2-ZrO2Ti in carrier: Zr mol ratio is 1:0.98.
The preparation of catalyst:It is first according to Ru-Sn-Bi/TiO2-ZrO2Ru contents are that 5wt%, Sn content are in catalyst 6wt% and Bi contents are the RuCl that 0.03wt% weighs respective quality3、SnCl2And BiCl3And it is dissolved in 15wt% hydrochloric acid Middle formation 250ml maceration extracts, by gained maceration extract and 50 grams of TiO2-ZrO2Mixing, 12h is impregnated, then vacuum is done at 110 DEG C Dry 3h obtains catalyst precursor, finally obtains Ru- with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen Sn-Bi/TiO2-ZrO2Finished catalyst, analyzed through ICP-AES, the Ru contents in catalyst are 5wt%.Sn contents are 6wt% It is 0.03wt% with Bi contents, for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Ru-Sn-Bi/TiO of the above-mentioned gained of 10g2-ZrO2Catalyst, 1000g water is added, open stirring, first It is passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keep steady It is fixed, 230 DEG C of maintenance reaction temperature, and continuously it is passed through hydrogen reaction 3.5h.After reaction terminates, reaction product is analyzed, is It is convenient to compare, analysis result is listed in Table 1 below.
【Embodiment 4】
The preparation of carrier:According to Ti:Zr mol ratio is 1:0.75, by 1mol TiCl4It is dissolved in 100ml absolute ethyl alcohol shapes Cheng Zhong, it is then added to the ZrOCl dissolved with 0.75mol2·8H2Uniform titanium zirconium mixed solution is made into the O 100ml aqueous solution. Under ice bath, it is stirred continuously, the 15wt% ammonia spirits of the PEG-4000 containing 0.5wt% is slowly added drop-wise to mixed solution In precipitated, and adjust pH value as 9~10, stand 24h, filtering, be washed with deionized to without Cl-Untill (use 0.1mol/ L AgNO3Solution is examined), then washed 2 times with 50ml absolute ethyl alcohols, 10h is then dried under 383K and obtains oxide precursor, will The presoma is calcined 2h in 773K moving airs and obtains TiO2-ZrO2Carrier, understood through ICP-AES analyses, TiO2-ZrO2Carrier Middle Ti:Zr mol ratio is 1:0.74.
The preparation of catalyst:It is first according to Ru-Sn-Bi/TiO2-ZrO2Ru contents are that 1wt%, Sn content are in catalyst 6wt% and Bi contents are the RuCl that 0.03wt% weighs respective quality3、SnCl2And BiCl3And it is dissolved in 15wt% hydrochloric acid Middle formation 250ml maceration extracts, by gained maceration extract and 50 grams of TiO2-ZrO2Mixing, 12h is impregnated, then vacuum is done at 110 DEG C Dry 3h obtains catalyst precursor, finally obtains Ru- with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen Sn-Bi/TiO2-ZrO2Finished catalyst, analyzed through ICP-AES, the Ru contents in catalyst are 1wt%.Sn contents are 6wt% It is 0.03wt% with Bi contents, for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Ru-Sn-Bi/TiO of the above-mentioned gained of 10g2-ZrO2Catalyst, 1000g water is added, open stirring, first It is passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keep steady It is fixed, 230 DEG C of maintenance reaction temperature, and continuously it is passed through hydrogen reaction 3.5h.After reaction terminates, reaction product is analyzed, is It is convenient to compare, analysis result is listed in Table 1 below.
【Embodiment 5】
The preparation of carrier:According to Ti:Zr mol ratio is 1:0.75, by 1mol TiCl4It is dissolved in 100ml absolute ethyl alcohol shapes Cheng Zhong, it is then added to the ZrOCl dissolved with 0.75mol2·8H2Uniform titanium zirconium mixed solution is made into the O 100ml aqueous solution. Under ice bath, it is stirred continuously, the 15wt% ammonia spirits of the PEG-4000 containing 0.5wt% is slowly added drop-wise to mixed solution In precipitated, and adjust pH value as 9~10, stand 24h, filtering, be washed with deionized to without Cl-Untill (use 0.1mol/ L AgNO3Solution is examined), then washed 2 times with 50ml absolute ethyl alcohols, 10h is then dried under 383K and obtains oxide precursor, will The presoma is calcined 2h in 773K moving airs and obtains TiO2-ZrO2Carrier, understood through ICP-AES analyses, TiO2-ZrO2Carrier Middle Ti:Zr mol ratio is 1:0.74.
The preparation of catalyst:It is first according to Ru-Sn-Bi/TiO2-ZrO2Ru contents are that 10wt%, Sn content are in catalyst 6wt% and Bi contents are the RuCl that 0.03wt% weighs respective quality3、SnCl2And BiCl3And it is dissolved in 15wt% hydrochloric acid Middle formation 250ml maceration extracts, by gained maceration extract and 50 grams of TiO2-ZrO2Mixing, 12h is impregnated, then vacuum is done at 110 DEG C Dry 3h obtains catalyst precursor, finally obtains Ru- with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen Sn-Bi/TiO2-ZrO2Finished catalyst, analyzed through ICP-AES, the Ru contents in catalyst are 10wt%.Sn contents are 6wt% It is 0.03wt% with Bi contents, for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Ru-Sn-Bi/TiO of the above-mentioned gained of 10g2-ZrO2Catalyst, 1000g water is added, open stirring, first It is passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keep steady It is fixed, 230 DEG C of maintenance reaction temperature, and continuously it is passed through hydrogen reaction 3.5h.After reaction terminates, reaction product is analyzed, is It is convenient to compare, analysis result is listed in Table 1 below.
【Embodiment 6】
The preparation of carrier:According to Ti:Zr mol ratio is 1:0.75, by 1mol TiCl4It is dissolved in 100ml absolute ethyl alcohol shapes Cheng Zhong, it is then added to the ZrOCl dissolved with 0.75mol2·8H2Uniform titanium zirconium mixed solution is made into the O 100ml aqueous solution. Under ice bath, it is stirred continuously, the 15wt% ammonia spirits of the PEG-4000 containing 0.5wt% is slowly added drop-wise to mixed solution In precipitated, and adjust pH value as 9~10, stand 24h, filtering, be washed with deionized to without Cl-Untill (use 0.1mol/ L AgNO3Solution is examined), then washed 2 times with 50ml absolute ethyl alcohols, 10h is then dried under 383K and obtains oxide precursor, will The presoma is calcined 2h in 773K moving airs and obtains TiO2-ZrO2Carrier, understood through ICP-AES analyses, TiO2-ZrO2Carrier Middle Ti:Zr mol ratio is 1:0.74.
The preparation of catalyst:It is first according to Ru-Sn-Bi/TiO2-ZrO2Ru contents are that 5wt%, Sn content are in catalyst 5wt% and Bi contents are the RuCl that 0.03wt% weighs respective quality3、SnCl2And BiCl3And it is dissolved in 15wt% hydrochloric acid Middle formation 250ml maceration extracts, by gained maceration extract and 50 grams of TiO2-ZrO2Mixing, 12h is impregnated, then vacuum is done at 110 DEG C Dry 3h obtains catalyst precursor, finally obtains Ru- with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen Sn-Bi/TiO2-ZrO2Finished catalyst, analyzed through ICP-AES, the Ru contents in catalyst are 5wt%.Sn contents are 5wt% It is 0.03wt% with Bi contents, for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Ru-Sn-Bi/TiO of the above-mentioned gained of 10g2-ZrO2Catalyst, 1000g water is added, open stirring, first It is passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keep steady It is fixed, 230 DEG C of maintenance reaction temperature, and continuously it is passed through hydrogen reaction 3.5h.After reaction terminates, reaction product is analyzed, is It is convenient to compare, analysis result is listed in Table 1 below.
【Embodiment 7】
The preparation of carrier:According to Ti:Zr mol ratio is 1:0.75, by 1mol TiCl4It is dissolved in 100ml absolute ethyl alcohol shapes Cheng Zhong, it is then added to the ZrOCl dissolved with 0.75mol2·8H2Uniform titanium zirconium mixed solution is made into the O 100ml aqueous solution. Under ice bath, it is stirred continuously, the 15wt% ammonia spirits of the PEG-4000 containing 0.5wt% is slowly added drop-wise to mixed solution In precipitated, and adjust pH value as 9~10, stand 24h, filtering, be washed with deionized to without Cl-Untill (use 0.1mol/ L AgNO3Solution is examined), then washed 2 times with 50ml absolute ethyl alcohols, 10h is then dried under 383K and obtains oxide precursor, will The presoma is calcined 2h in 773K moving airs and obtains TiO2-ZrO2Carrier, understood through ICP-AES analyses, TiO2-ZrO2Carrier Middle Ti:Zr mol ratio is 1:0.74.
The preparation of catalyst:It is first according to Ru-Sn-Bi/TiO2-ZrO2Ru contents are that 5wt%, Sn content are in catalyst 10wt% and Bi contents are the RuCl that 0.03wt% weighs respective quality3、SnCl2And BiCl3And it is dissolved in 15wt% hydrochloric acid Middle formation 250ml maceration extracts, by gained maceration extract and 50 grams of TiO2-ZrO2Mixing, 12h is impregnated, then vacuum is done at 110 DEG C Dry 3h obtains catalyst precursor, finally obtains Ru- with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen Sn-Bi/TiO2-ZrO2Finished catalyst, analyzed through ICP-AES, the Ru contents in catalyst are 5wt%.Sn contents are 10wt% It is 0.03wt% with Bi contents, for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Ru-Sn-Bi/TiO of the above-mentioned gained of 10g2-ZrO2Catalyst, 1000g water is added, open stirring, first It is passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keep steady It is fixed, 230 DEG C of maintenance reaction temperature, and continuously it is passed through hydrogen reaction 3.5h.After reaction terminates, reaction product is analyzed, is It is convenient to compare, analysis result is listed in Table 1 below.
【Embodiment 8】
The preparation of carrier:According to Ti:Zr mol ratio is 1:0.75, by 1mol TiCl4It is dissolved in 100ml absolute ethyl alcohol shapes Cheng Zhong, it is then added to the ZrOCl dissolved with 0.75mol2·8H2Uniform titanium zirconium mixed solution is made into the O 100ml aqueous solution. Under ice bath, it is stirred continuously, the 15wt% ammonia spirits of the PEG-4000 containing 0.5wt% is slowly added drop-wise to mixed solution In precipitated, and adjust pH value as 9~10, stand 24h, filtering, be washed with deionized to without Cl-Untill (use 0.1mol/ L AgNO3Solution is examined), then washed 2 times with 50ml absolute ethyl alcohols, 10h is then dried under 383K and obtains oxide precursor, will The presoma is calcined 2h in 773K moving airs and obtains TiO2-ZrO2Carrier, understood through ICP-AES analyses, TiO2-ZrO2Carrier Middle Ti:Zr mol ratio is 1:0.74.
The preparation of catalyst:It is first according to Ru-Sn-Bi/TiO2-ZrO2Ru contents are that 5wt%, Sn content are in catalyst 6wt% and Bi contents are the RuCl that 0.01wt% weighs respective quality3、SnCl2And BiCl3And it is dissolved in 15wt% hydrochloric acid Middle formation 250ml maceration extracts, by gained maceration extract and 50 grams of TiO2-ZrO2Mixing, 12h is impregnated, then vacuum is done at 110 DEG C Dry 3h obtains catalyst precursor, finally obtains Ru- with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen Sn-Bi/TiO2-ZrO2Finished catalyst, analyzed through ICP-AES, the Ru contents in catalyst are 5wt%.Sn contents are 6wt% It is 0.01wt% with Bi contents, for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Ru-Sn-Bi/TiO of the above-mentioned gained of 10g2-ZrO2Catalyst, 1000g water is added, open stirring, first It is passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keep steady It is fixed, 230 DEG C of maintenance reaction temperature, and continuously it is passed through hydrogen reaction 3.5h.After reaction terminates, reaction product is analyzed, is It is convenient to compare, analysis result is listed in Table 1 below.
【Embodiment 9】
The preparation of carrier:According to Ti:Zr mol ratio is 1:0.75, by 1mol TiCl4It is dissolved in 100ml absolute ethyl alcohol shapes Cheng Zhong, it is then added to the ZrOCl dissolved with 0.75mol2·8H2Uniform titanium zirconium mixed solution is made into the O 100ml aqueous solution. Under ice bath, it is stirred continuously, the 15wt% ammonia spirits of the PEG-4000 containing 0.5wt% is slowly added drop-wise to mixed solution In precipitated, and adjust pH value as 9~10, stand 24h, filtering, be washed with deionized to without Cl-Untill (use 0.1mol/ L AgNO3Solution is examined), then washed 2 times with 50ml absolute ethyl alcohols, 10h is then dried under 383K and obtains oxide precursor, will The presoma is calcined 2h in 773K moving airs and obtains TiO2-ZrO2Carrier, understood through ICP-AES analyses, TiO2-ZrO2Carrier Middle Ti:Zr mol ratio is 1:0.74.
The preparation of catalyst:It is first according to Ru-Sn-Bi/TiO2-ZrO2Ru contents are that 5wt%, Sn content are in catalyst 6wt% and Bi contents are the RuCl that 0.02wt% weighs respective quality3、SnCl2And BiCl3And it is dissolved in 15wt% hydrochloric acid Middle formation 250ml maceration extracts, by gained maceration extract and 50 grams of TiO2-ZrO2Mixing, 12h is impregnated, then vacuum is done at 110 DEG C Dry 3h obtains catalyst precursor, finally obtains Ru- with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen Sn-Bi/TiO2-ZrO2Finished catalyst, analyzed through ICP-AES, the Ru contents in catalyst are 5wt%.Sn contents are 6wt% It is 0.02wt% with Bi contents, for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Ru-Sn-Bi/TiO of the above-mentioned gained of 10g2-ZrO2Catalyst, 1000g water is added, open stirring, first It is passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keep steady It is fixed, 230 DEG C of maintenance reaction temperature, and continuously it is passed through hydrogen reaction 3.5h.After reaction terminates, reaction product is analyzed, is It is convenient to compare, analysis result is listed in Table 1 below.
【Embodiment 10】
The preparation of carrier:According to Ti:Zr mol ratio is 1:0.75, by 1mol TiCl4It is dissolved in 100ml absolute ethyl alcohol shapes Cheng Zhong, it is then added to the ZrOCl dissolved with 0.75mol2·8H2Uniform titanium zirconium mixed solution is made into the O 100ml aqueous solution. Under ice bath, it is stirred continuously, the 15wt% ammonia spirits of the PEG-4000 containing 0.5wt% is slowly added drop-wise to mixed solution In precipitated, and adjust pH value as 9~10, stand 24h, filtering, be washed with deionized to without Cl-Untill (use 0.1mol/ L AgNO3Solution is examined), then washed 2 times with 50ml absolute ethyl alcohols, 10h is then dried under 383K and obtains oxide precursor, will The presoma is calcined 2h in 773K moving airs and obtains TiO2-ZrO2Carrier, understood through ICP-AES analyses, TiO2-ZrO2Carrier Middle Ti:Zr mol ratio is 1:0.74.
The preparation of catalyst:It is first according to Ru-Sn-Bi/TiO2-ZrO2Ru contents are that 5wt%, Sn content are in catalyst 6wt% and Bi contents are the RuCl that 0.04wt% weighs respective quality3、SnCl2And BiCl3And it is dissolved in 15wt% hydrochloric acid Middle formation 250ml maceration extracts, by gained maceration extract and 50 grams of TiO2-ZrO2Mixing, 12h is impregnated, then vacuum is done at 110 DEG C Dry 3h obtains catalyst precursor, finally obtains Ru- with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen Sn-Bi/TiO2-ZrO2Finished catalyst, analyzed through ICP-AES, the Ru contents in catalyst are 5wt%.Sn contents are 6wt% It is 0.04wt% with Bi contents, for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Ru-Sn-Bi/TiO of the above-mentioned gained of 10g2-ZrO2Catalyst, 1000g water is added, open stirring, first It is passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keep steady It is fixed, 230 DEG C of maintenance reaction temperature, and continuously it is passed through hydrogen reaction 3.5h.After reaction terminates, reaction product is analyzed, is It is convenient to compare, analysis result is listed in Table 1 below.
【Embodiment 11】
The preparation of carrier:According to Ti:Zr mol ratio is 1:0.75, by 1mol TiCl4It is dissolved in 100ml absolute ethyl alcohol shapes Cheng Zhong, it is then added to the ZrOCl dissolved with 0.75mol2·8H2Uniform titanium zirconium mixed solution is made into the O 100ml aqueous solution. Under ice bath, it is stirred continuously, the 15wt% ammonia spirits of the PEG-4000 containing 0.5wt% is slowly added drop-wise to mixed solution In precipitated, and adjust pH value as 9~10, stand 24h, filtering, be washed with deionized to without Cl-Untill (use 0.1mol/ L AgNO3Solution is examined), then washed 2 times with 50ml absolute ethyl alcohols, 10h is then dried under 383K and obtains oxide precursor, will The presoma is calcined 2h in 773K moving airs and obtains TiO2-ZrO2Carrier, understood through ICP-AES analyses, TiO2-ZrO2Carrier Middle Ti:Zr mol ratio is 1:0.74.
The preparation of catalyst:It is first according to Ru-Sn-Bi/TiO2-ZrO2Ru contents are that 5wt%, Sn content are in catalyst 6wt% and Bi contents are the RuCl that 0.1wt% weighs respective quality3、SnCl2And BiCl3And it is dissolved in 15wt% hydrochloric acid 250ml maceration extracts are formed, by gained maceration extract and 50 grams of TiO2-ZrO2Mixing, 12h is impregnated, is then dried in vacuo at 110 DEG C 3h obtains catalyst precursor, finally obtains Ru- with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen Sn-Bi/TiO2-ZrO2Finished catalyst, analyzed through ICP-AES, the Ru contents in catalyst are 5wt%.Sn contents are 6wt% It is 0.1wt% with Bi contents, for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Ru-Sn-Bi/TiO of the above-mentioned gained of 10g2-ZrO2Catalyst, 1000g water is added, open stirring, first It is passed through nitrogen displacement three times, is being passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keep steady It is fixed, 230 DEG C of maintenance reaction temperature, and continuously it is passed through hydrogen reaction 3.5h.After reaction terminates, reaction product is analyzed, is It is convenient to compare, analysis result is listed in Table 1 below.
【Embodiment 12】
The preparation of carrier:By 1mol TiCl4It is dissolved in during 100ml absolute ethyl alcohols are formed, under ice bath, is stirred continuously, will The 15wt% ammonia spirits of the PEG-4000 containing 0.5wt%, which are slowly added drop-wise in mixed solution, to be precipitated, and adjusts pH It is worth for 9~10, stands 24h, filtering, be washed with deionized to without Cl-Untill (use 0.1mol/L AgNO3Solution is examined), then Washed 2 times with 50ml absolute ethyl alcohols, 10h is then dried under 383K and obtains oxide precursor, the presoma is flowed into sky in 773K 2h is calcined in gas and obtains TiO2Carrier.
The preparation of catalyst:It is first according to Ru-Sn-Bi/TiO2Ru contents are that 5wt%, Sn content are 6wt% in catalyst It is the RuCl that 0.03wt% weighs respective quality with Bi contents3、SnCl2And BiCl3And it is dissolved in being formed in 15wt% hydrochloric acid 250ml maceration extracts, by gained maceration extract and 50 grams of TiO2Mixing, 12h is impregnated, 3h is then dried in vacuo at 110 DEG C to be catalyzed Agent presoma, finally obtain Ru-Sn-Bi/TiO with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen2 Finished catalyst, analyzed through ICP-AES, the Ru contents in catalyst are 5wt%.Sn contents are that 6wt% and Bi contents are 0.03wt%, for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Ru-Sn-Bi/TiO of the above-mentioned gained of 10g2Catalyst, 1000g water is added, open stirring, be first passed through Nitrogen displacement three times, is being passed through hydrogen displacement three times, and then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keep stable, dimension 230 DEG C of reaction temperature is held, and is continuously passed through hydrogen reaction 3.5h.Reaction terminate after, reaction product is analyzed, for convenience of than Compared with analysis result is listed in Table 1 below.
【Embodiment 13】
The preparation of carrier:By the ZrOCl containing 1mol2·8H2The O 100ml aqueous solution is stirred continuously under ice bath, will be contained The 15wt% ammonia spirits of 0.5wt% PEG-4000s, which are slowly added drop-wise in mixed solution, to be precipitated, and adjusts pH value For 9~10,24h is stood, filtering, is washed with deionized to without Cl-Untill (use 0.1mol/L AgNO3Solution is examined), then use 50ml absolute ethyl alcohols are washed 2 times, and 10h is then dried under 383K and obtains oxide precursor, by the presoma in 773K moving airs Middle roasting 2h obtains ZrO2Carrier.
The preparation of catalyst:It is first according to Ru-Sn-Bi/ZrO2Ru contents are that 5wt%, Sn content are 6wt% in catalyst It is the RuCl that 0.03wt% weighs respective quality with Bi contents3、SnCl2And BiCl3And it is dissolved in being formed in 15wt% hydrochloric acid 250ml maceration extracts, by gained maceration extract and 50 grams of ZrO2Mixing, 12h is impregnated, 3h is then dried in vacuo at 110 DEG C to be catalyzed Agent presoma, finally obtain Ru-Sn-Bi/ZrO with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen2 Finished catalyst, analyzed through ICP-AES, the Ru contents in catalyst are 5wt%, and Sn contents are that 6wt% and Bi contents are 0.03wt%, for ease of comparing, gained catalyst composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Ru-Sn-Bi/ZrO of the above-mentioned gained of 10g2Catalyst, 1000g water is added, open stirring, be first passed through Nitrogen displacement three times, is being passed through hydrogen displacement three times, and then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keep stable, dimension 230 DEG C of reaction temperature is held, and is continuously passed through hydrogen reaction 3.5h.Reaction terminate after, reaction product is analyzed, for convenience of than Compared with analysis result is listed in Table 1 below.
【Embodiment 14】
The preparation of carrier:According to Ti:Zr mol ratio is 1:0.75, by 1mol TiCl4It is dissolved in 100ml absolute ethyl alcohol shapes Cheng Zhong, it is then added to the ZrOCl dissolved with 0.75mol2·8H2Uniform titanium zirconium mixed solution is made into the O 100ml aqueous solution. Under ice bath, it is stirred continuously, the 15wt% ammonia spirits of the PEG-4000 containing 0.5wt% is slowly added drop-wise to mixed solution In precipitated, and adjust pH value as 9~10, stand 24h, filtering, be washed with deionized to without Cl-Untill (use 0.1mol/ L AgNO3Solution is examined), then washed 2 times with 50ml absolute ethyl alcohols, 10h is then dried under 383K and obtains oxide precursor, will The presoma is calcined 2h in 773K moving airs and obtains TiO2-ZrO2Carrier, understood through ICP-AES analyses, TiO2-ZrO2Carrier Middle Ti:Zr mol ratio is 1:0.74.
The preparation of catalyst:It is first according to Ru-Sn/TiO2-ZrO2Ru contents are that 5wt% and Sn contents are in catalyst 6.03wt% weighs the RuCl of respective quality3And SnCl2And be dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, by institute Obtain maceration extract and 50 grams of TiO2-ZrO2Mixing, 12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally Ru-Sn-Bi/TiO is obtained with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen2-ZrO2Catalyst into Product, analyzed through ICP-AES, the Ru contents in catalyst are that 5wt% and Sn contents are 6.03wt%, for ease of comparing, by gained Catalyst composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Ru-Sn/TiO of the above-mentioned gained of 10g2-ZrO2Catalyst, 1000g water is added, open stirring, first lead to Enter nitrogen displacement three times, be passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keeps stable, 230 DEG C of maintenance reaction temperature, and continuously it is passed through hydrogen reaction 3.5h.After reaction terminates, reaction product is analyzed, for convenience Compare, analysis result is listed in Table 1 below.
【Embodiment 15】
The preparation of carrier:According to Ti:Zr mol ratio is 1:0.75, by 1mol TiCl4It is dissolved in 100ml absolute ethyl alcohol shapes Cheng Zhong, it is then added to the ZrOCl dissolved with 0.75mol2·8H2Uniform titanium zirconium mixed solution is made into the O 100ml aqueous solution. Under ice bath, it is stirred continuously, the 15wt% ammonia spirits of the PEG-4000 containing 0.5wt% is slowly added drop-wise to mixed solution In precipitated, and adjust pH value as 9~10, stand 24h, filtering, be washed with deionized to without Cl-Untill (use 0.1mol/ L AgNO3Solution is examined), then washed 2 times with 50ml absolute ethyl alcohols, 10h is then dried under 383K and obtains oxide precursor, will The presoma is calcined 2h in 773K moving airs and obtains TiO2-ZrO2Carrier, understood through ICP-AES analyses, TiO2-ZrO2Carrier Middle Ti:Zr mol ratio is 1:0.74.
The preparation of catalyst:It is first according to Ru-Bi/TiO2-ZrO2Ru contents are that 5wt% and Bi contents are in catalyst 6.03wt% weighs the RuCl of respective quality3And BiCl3And be dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, by institute Obtain maceration extract and 50 grams of TiO2-ZrO2Mixing, 12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally Ru-Bi/TiO is obtained with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen2-ZrO2Finished catalyst, Analyzed through ICP-AES, the Ru contents in catalyst are that 5wt% and Bi contents are 6.03wt%, and for ease of comparing, gained is catalyzed Agent composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Ru-Bi/TiO of the above-mentioned gained of 10g2-ZrO2Catalyst, 1000g water is added, open stirring, first lead to Enter nitrogen displacement three times, be passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keeps stable, 230 DEG C of maintenance reaction temperature, and continuously it is passed through hydrogen reaction 3.5h.After reaction terminates, reaction product is analyzed, for convenience Compare, analysis result is listed in Table 1 below.
【Embodiment 16】
The preparation of carrier:According to Ti:Zr mol ratio is 1:0.75, by 1mol TiCl4It is dissolved in 100ml absolute ethyl alcohol shapes Cheng Zhong, it is then added to the ZrOCl dissolved with 0.75mol2·8H2Uniform titanium zirconium mixed solution is made into the O 100ml aqueous solution. Under ice bath, it is stirred continuously, the 15wt% ammonia spirits of the PEG-4000 containing 0.5wt% is slowly added drop-wise to mixed solution In precipitated, and adjust pH value as 9~10, stand 24h, filtering, be washed with deionized to without Cl-Untill (use 0.1mol/ L AgNO3Solution is examined), then washed 2 times with 50ml absolute ethyl alcohols, 10h is then dried under 383K and obtains oxide precursor, will The presoma is calcined 2h in 773K moving airs and obtains TiO2-ZrO2Carrier, understood through ICP-AES analyses, TiO2-ZrO2Carrier Middle Ti:Zr mol ratio is 1:0.74.
The preparation of catalyst:It is first according to Sn-Bi/TiO2-ZrO2Sn contents are that 6wt% and Bi contents are in catalyst 5.03wt% weighs the SnCl of respective quality2And BiCl3And be dissolved in forming 250ml maceration extracts in 15wt% hydrochloric acid, by institute Obtain maceration extract and 50 grams of TiO2-ZrO2Mixing, 12h is impregnated, 3h is then dried in vacuo at 110 DEG C obtains catalyst precursor, finally Sn-Bi/TiO is obtained with the lower 160 DEG C of reduction 3h of the hydrogen 150ml/min diluted through 5 times of volume nitrogen2-ZrO2Finished catalyst, Analyzed through ICP-AES, the Sn contents in catalyst are that 6wt% and Bi contents are 6.03wt%, and for ease of comparing, gained is catalyzed Agent composition is listed in Table 1 below.
Evaluating catalyst:By marketed 1,4 cyclohexanedicarboxylic acid 100g, (analysis shows are wherein anti-along than 1:1) it is Autoclave is added, adds the Sn-Bi/TiO of the above-mentioned gained of 10g2-ZrO2Catalyst, 1000g water is added, open stirring, first lead to Enter nitrogen displacement three times, be passed through hydrogen displacement three times, then passing to hydrogen makes Hydrogen Vapor Pressure rise to 8.5MPa and keeps stable, 230 DEG C of maintenance reaction temperature, and continuously it is passed through hydrogen reaction 3.5h.After reaction terminates, reaction product is analyzed, for convenience Compare, analysis result is listed in Table 1 below.
As it can be seen from table 1 the technology takes applied to Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic Hydrogenation for 1,4-CHDM Obtained good reaction result.When with TiO2-ZrO2For carrier, while ensure Ti:Zr mol ratios are 1:(0.7~0.8), control Carried metal Ru contents are in 5~6wt%, and Sn contents are in 0.2~0.5wt%, and Bi contents are obtained by 0.02~0.04wt% Ru-Sn-Bi/TiO2-ZrO2Catalyst, while Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic conversion ratio is reached 100%, ensure CHDM Selectivity be 100%, and trans-CHDM selectivity reaches more than 95%.If but only with TiO2Or ZrO2For carrier, then High CHDA conversion ratios are not simply failed to, and trans-CHDM selectivity is very low.If it is basic to lack active metal Ru, CHDA Reaction is not participated in, and high CHDM selectivity can not then be obtained by lacking Sn, lack the selection that Bi can not then obtain high trans-CHDM Property.
Trans-CHDM of the present invention selectivity is defined as the percentage that trans-CHDM accounts for whole CHDM.
Table 1

Claims (6)

1.1,4- cyclohexanedimethanol catalyst, with TiO2And ZrO2For carrier, including Ru, Sn and Bi are active component;
And Ru contents are 1~10wt%;Sn contents are 5~10wt%;Bi contents are 0.01~0.1wt%.
2. the preparation method of catalyst according to claim 1, comprises the following steps:
A) by the solution of the desired amount of compound containing Ti and the compound containing Zr, regulation pH value is 8~12, is precipitated, Ran Houjing Filtering, washing, dry, roasting obtain the carrier;
B) carrier is impregnated with the desired amount of compound containing Ru, compound containing Sn and compound containing Bi;
C) Ru, Sn and Bi compound are reduced to metal simple-substance with reducing agent.
3. preparation method according to claim 2, it is characterised in that described reducing agent is hydrogen, formaldehyde, sodium formate, water Close at least one of hydrazine or formic acid.
The synthetic method of 4.1,4- cyclohexanedimethanols, in the presence of catalyst described in claim 1, using water as solvent, hydrogen React to obtain 1,4 cyclohexane dimethanol with 1,4 cyclohexanedicarboxylic acid.
5. synthetic method according to claim 4, it is characterised in that reaction temperature is 220~260 DEG C.
6. synthetic method according to claim 4, it is characterised in that Hydrogen Vapor Pressure is 6~10MPa.
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