CN105582927B - 1,4 cyclohexanedimethanol catalyst and its preparation method - Google Patents
1,4 cyclohexanedimethanol catalyst and its preparation method Download PDFInfo
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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
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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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6156211A (en) * | 1997-01-31 | 2000-12-05 | Lynntech, Inc. | Enhanced photocatalytic conversion of methane to methanol using a porous semiconductor membrane |
| CN103664524A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing 1, 4-cyclohexanedimethanol through hydrogenation of 1, 4-cyclohexanedicarboxylic acid |
| CN103877991A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Preparation method for trans-1,4-cyclohexanedimethanol, and catalyst used therefor |
| CN103894193A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | High-activity Pt-Ru bimetallic catalyst, and preparation method and use thereof |
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| JPH06228028A (en) * | 1993-01-29 | 1994-08-16 | Arakawa Chem Ind Co Ltd | Production of 1,4-cyclohexanedimethanol |
| US6916763B2 (en) * | 2002-11-27 | 2005-07-12 | Solutia Inc. | Process for preparing a catalyst for the oxidation and ammoxidation of olefins |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6156211A (en) * | 1997-01-31 | 2000-12-05 | Lynntech, Inc. | Enhanced photocatalytic conversion of methane to methanol using a porous semiconductor membrane |
| CN103664524A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing 1, 4-cyclohexanedimethanol through hydrogenation of 1, 4-cyclohexanedicarboxylic acid |
| CN103877991A (en) * | 2012-12-19 | 2014-06-25 | 中国石油化工股份有限公司 | Preparation method for trans-1,4-cyclohexanedimethanol, and catalyst used therefor |
| CN103894193A (en) * | 2012-12-27 | 2014-07-02 | 中国石油化工股份有限公司 | High-activity Pt-Ru bimetallic catalyst, and preparation method and use thereof |
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