CN108160079A - A kind of preparation method of the adjustable disubstituted cyclohexane carboxylate of purposes and cis-trans ratio of catalyst - Google Patents
A kind of preparation method of the adjustable disubstituted cyclohexane carboxylate of purposes and cis-trans ratio of catalyst Download PDFInfo
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- CN108160079A CN108160079A CN201611118460.XA CN201611118460A CN108160079A CN 108160079 A CN108160079 A CN 108160079A CN 201611118460 A CN201611118460 A CN 201611118460A CN 108160079 A CN108160079 A CN 108160079A
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- cyclohexane carboxylate
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- disubstituted cyclohexane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- C07B2200/09—Geometrical isomers
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Abstract
Invention is related to a kind of purposes of catalyst and the preparation method of the adjustable disubstituted cyclohexane carboxylate of cis-trans ratio, which is used to adjust the cis-trans ratio of the disubstituted cyclohexane carboxylate of aromatic carboxylic acid esters hydrogenation reaction generation.The preparation method is：Using aromatic carboxylic acid esters as raw material, hydrogenation reaction generates disubstituted cyclohexane carboxylate under the conditions of existing for catalyst, and the disubstituted cyclohexane carboxylate includes cis and trans, and the active component of the catalyst is one or more in Ru, Pd and Ni.The preparation method of the present invention can obtain the different disubstituted cyclohexane carboxylate of cis-trans ratio, and when the active component of catalyst is Ni, disubstituted cyclohexane carboxylate cis ratio accounts for 40 ~ 65%；When the active component of catalyst is Ru, disubstituted cyclohexane carboxylate cis ratio accounts for 75 ~ 90%；When the active component of catalyst is Pd, disubstituted cyclohexane carboxylate cis ratio accounts for 95 ~ 98%.
Description
Technical field
The present invention relates to a kind of preparations of the adjustable disubstituted cyclohexane carboxylate of purposes and cis-trans ratio of catalyst
Method.
Background technology
Aromatic carboxylic acid esters' compound is widely used in medicine, fragrance, pesticide etc. as a kind of important raw material of industry
Field.But since the presence of its phenyl ring causes portioned product that cannot meet the requirement of people in terms of toxicity, environmental protection, there is an urgent need to
Seek substitute products.
Two ester type compound of cyclohexane cyclohexanedimethanodibasic (by taking adjacent cyclohexane carboxylate as an example) is as in non-aromatic ring class plasticizer
One kind its main feature is that migration of element rate is at a fairly low, has excellent toxicological characteristics, and biodegradable, one kind is had excellent performance
The replacement product of toy, medical instrument and food contact phthalate esters PVC plasticizer.
Cyclohexane carboxylate under certain reaction condition, adds hydrogen generally by aromatic carboxylic acid esters by the effect of catalyst
It obtains.Noble metal of the phenyl ring selective hydrocatalyst reported at present generally based on Pd, Ru and non-expensive based on Ni
Metal is active component, Al2O3、SiO2, activated carbon, TiO2Based on the load type metal catalyst for carrier.Chinese patent
CN101417950A, which is reported, to be used with Al2O3For the catalyst that the transition metal such as carrier, Pd, Ru are active constituent, 180~
210 DEG C, through benzene ring hydrogenation diisononyl phthalate to be made adjacent cyclohexane cyclohexanedimethanodibasic two under conditions of 3.0~12MPa different
Nonyl ester, the yield maximum of target product are close to 100%.A kind of support type Ru catalysis is described in United States Patent (USP) US3027398
Agent, by the standby adjacent hexamethylene diformazan of repefral Hydrogenation under conditions of 110~140 DEG C, 3.5~10.5MPa
Dimethyl phthalate.Ru-Al prepared by a kind of infusion process is elaborated in Chinese patent CN1915962A2O3Catalyst, 130~170
DEG C, under conditions of 3.0~5.0MPa by dimethyl terephthalate (DMT) Hydrogenation for Isosorbide-5-Nitrae-dimethyl hexahydrophthalate, yield can
Up to more than 95%.
Although more comprehensive for the research of such reaction at present, rarely have about catalyst system and process conditions to production
The report that object cis-trans content influences.Since disubstituted cyclohexane substratess matter exists along anti-two kinds of isomers, and cis-trans-isomer
Difference on physico-chemical property can cause it to generate difference in downstream application.For example, when adjacent cyclohexane cyclohexanedimethanodibasic diisobutyl ester
During gas phase adsorption solvent as ALMA technique productions cis-butenedioic anhydrides, it is desirable that its cis-content will reach more than 95%；In terephthaldehyde
In the technique of dimethyl phthalate Hydrogenation 1,4-CHDM, if trans- 1,4-CHDM content in product>70%
When, then there can be superior performance by its downstream polyester product obtained.Therefore, Study of Catalyst system and process conditions pair
The influence of cis-trans-isomer content is of great significance for downstream application.
Invention content
The present invention provides the purposes and cis-trans of a kind of catalyst for technological deficiency existing for prior art described above
The preparation method of the adjustable disubstituted cyclohexane carboxylate of ratio, the catalyst are given birth to for adjusting aromatic carboxylic acid esters hydrogenation reaction
Into disubstituted cyclohexane carboxylate cis-trans ratio.The preparation method is：Using aromatic carboxylic acid esters as raw material, in catalyst
Hydrogenation reaction generates disubstituted cyclohexane carboxylate under the conditions of existing, and the disubstituted cyclohexane carboxylate includes cis- and anti-
Formula, the active component of the catalyst are one or more in Ru, Pd and Ni.The preparation method of the present invention can obtain along anti-
The different disubstituted cyclohexane carboxylate of formula ratio, when the active component of catalyst is Ni, disubstituted cyclohexane carboxylate is suitable
Formula ratio accounts for 40~65%；When the active component of catalyst is Ru, disubstituted cyclohexane carboxylate cis ratio accounts for 75~
90%；When the active component of catalyst is Pd, disubstituted cyclohexane carboxylate cis ratio accounts for 95~98%.
The present invention is achieved by the following technical solutions：
First aspect present invention provides a kind of purposes of catalyst, for adjusting the generation of aromatic carboxylic acid esters hydrogenation reaction
The cis-trans ratio of disubstituted cyclohexane carboxylate, the catalyst include active component and carrier, and the active component is selected from
One or more in Ru, Pd and Ni, the content of active component is 1~10wt%, such as 1~2.5wt%, 2.5~3wt%, 3~
5wt%, 5~10wt%.
Preferably, when the active component of catalyst is Ni, disubstituted cyclohexane carboxylate cis ratio accounts for 40~65%；
When the active component of catalyst is Ru, disubstituted cyclohexane carboxylate cis ratio accounts for 75~90%；When the activity of catalyst
When component is Pd, disubstituted cyclohexane carboxylate cis ratio accounts for 95~98%.
Above-mentioned catalyst is obtained by prior art preparation, such as：By active component salt solution and carrier incipient impregnation,
Then dry, roasting and activation are to get the catalyst.
Second aspect of the present invention provides a kind of preparation method of the adjustable disubstituted cyclohexane carboxylate of cis-trans ratio, with
Aromatic carboxylic acid esters are raw material, the hydrogenation reaction generation disubstituted cyclohexane carboxylate under the conditions of existing for catalyst, described two
Substituted cyclohexane carboxylate includes cis- disubstituted cyclohexane carboxylate and trans- disubstituted cyclohexane carboxylate, described to urge
Agent includes active component and carrier, and the active component is one or more in Ru, Pd and Ni, the content of active component
For 1~10wt%.
Preferably, the carrier is selected from Al2O3、SiO2, activated carbon and TiO2In it is one or more.
It is highly preferred that the carrier is selected from Al2O3And SiO2At least one of.
Preferably, the aromatic carboxylic acid esters are for adjacent benzene, isophthalic or to benzene dicarboxylic acid esters.
Preferably, reaction temperature is 60~180 DEG C, and reaction pressure is 2.0~6.0MPa, and hydrogen ester ratio is 50~400:1, such as
Reaction temperature is 60~80 DEG C, 80~100 DEG C, 100~120 DEG C, 120~160 DEG C or 160~180 DEG C；Reaction pressure is 2.0
~3.0MPa, 3.0~4.0MPa, 4.0~5.0MPa or 5.0~6.0MPa；Hydrogen ester ratio is 50~100:1st, 100~125:1、
125~200:1st, 200~300:1 or 300~400:1.
Preferably, reactant quality air speed is 0.1~1.2h-1, such as 0.1~0.3h-1, 0.3~0.6h-1, 0.6~1h-1Or
1~1.2h-1。
It is highly preferred that reaction temperature is 80~160 DEG C, reaction pressure is 3.0~5.0MPa, and hydrogen ester ratio is 100~300:
1。
It is highly preferred that reactant quality air speed is 0.3~1.0h-1。
Preferably, disubstituted cyclohexane carboxylate cis-content is more than 40%.
It is highly preferred that when the active component of catalyst is Ni, disubstituted cyclohexane carboxylate cis ratio accounts for 40~
65%；When the active component of catalyst is Ru, disubstituted cyclohexane carboxylate cis ratio accounts for 75~90%；When catalyst
When active component is Pd, disubstituted cyclohexane carboxylate cis ratio accounts for 95~98%.
The present invention provides the purposes of catalyst and the preparation method of the adjustable disubstituted cyclohexane carboxylate of cis-trans ratio,
One of at least have the advantages that：
(1) the disubstituted cyclohexane carboxylic acid containing different cis-trans has been obtained on different metal active constituent catalyst
Ester, wherein, when the active component of catalyst is Ni, disubstituted cyclohexane carboxylate cis ratio accounts for 40~65%；Work as catalysis
When the active component of agent is Ru, disubstituted cyclohexane carboxylate cis ratio accounts for 75~90%；When the active component of catalyst is
During Pd, disubstituted cyclohexane carboxylate cis ratio accounts for 95~98%；
(2) on same active constituent catalyst, reaction temperature influences cis-trans content in product the most apparent, performance
For with the raising of temperature, cis-isomer content continuously decreases, and reaction pressure, hydrogen ester ratio and the load of same active component
Amount has not significant impact cis-trans ratio.
Description of the drawings
Fig. 1 is diisobutyl phthalate in 1.0wt%Pd/Al2O3On hydrogenation products chromatogram.
Specific embodiment
Illustrate technical scheme of the present invention below by way of specific specific example.It should be understood that the present invention mention one or
Multiple method and steps do not repel before and after the combination step that also there are other methods step or the steps specifically mentioned at these
Other methods step can also be inserted between rapid；It should also be understood that these embodiments are merely to illustrate the present invention rather than limitation
The scope of the present invention.Moreover, unless otherwise indicated, the number of various method steps is only to differentiate the convenient tool of various method steps,
Rather than ordering or the enforceable range of the restriction present invention, the change of relativeness or tune for limitation various method steps
It is whole, in the case where changing technology contents without essence, when being also considered as the enforceable scope of the present invention.
Embodiment 1
Weigh 0.3298g Pd (NO3)2(Pd content 15.16wt%) adds in 6.5g deionized waters, after its all dissolving
Add in 4.95g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings must be urged after roasting 4h at 400 DEG C
Agent precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 1wt%Pd-Al in (volume fraction) atmosphere2O3
Finished catalyst.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis (Fig. 1 is shown in chromatography) afterwards corresponds to trans- 1,2- cyclohexane cyclohexanedimethanodibasics diisobutyl ester, RT at RT=22.2min
Then correspond to cis- 1,2- cyclohexane cyclohexanedimethanodibasics diisobutyl ester at=23.2min, obtain reaction evaluating and the results are shown in Table 1.
Embodiment 2
Weigh 1.6490g Pd (NO3)2(Pd content 15.16wt%) adds in 6.2g deionized waters, after its all dissolving
Add in 4.75g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings must be urged after roasting 4h at 400 DEG C
Agent precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 5wt%Pd-Al in (volume fraction) atmosphere2O3
Finished catalyst.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 1.
Embodiment 3
Weigh 3.2980g Pd (NO3)2(Pd content 15.16wt%) adds in 5.9g deionized waters, after its all dissolving
Add in 4.50g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings must be urged after roasting 4h at 400 DEG C
Agent precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 10wt%Pd-Al in (volume fraction) atmosphere2O3
Finished catalyst.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 1.
Embodiment 4
Weigh 0.3298g Pd (NO3)2(Pd content 15.16wt%) adds in 6.5g deionized waters, after its all dissolving
Add in 4.95g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings must be urged after roasting 4h at 400 DEG C
Agent precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 1wt%Pd-Al in (volume fraction) atmosphere2O3
Finished catalyst.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
80 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 1.
Embodiment 5
Weigh 2.4771g Ni (NO3)2·6H2O adds in 6.0g deionized waters, and 4.5g is added in after its all dissolving
Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst precarsor after roasting 4h at 400 DEG C.It will
Catalyst precarsor is in 10%H2/N2500 DEG C of activation 4h are to get 10wt%Ni-Al in (volume fraction) atmosphere2O3Finished catalyst.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 2.
Embodiment 6
Weigh 0.7431g Ni (NO3)2·6H2O adds in 6.0g deionized waters, and 4.85g is added in after its all dissolving
Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst precarsor after roasting 4h at 400 DEG C.It will
Catalyst precarsor is in 10%H2/N2500 DEG C of activation 4h are to get 3wt%Ni-Al in (volume fraction) atmosphere2O3Finished catalyst.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 2.
Embodiment 7
Weigh 0.2477g Ni (NO3)2·6H2O adds in 6.0g deionized waters, and 4.95g is added in after its all dissolving
Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst precarsor after roasting 4h at 400 DEG C.It will
Catalyst precarsor is in 10%H2/N2500 DEG C of activation 4h are to get 1wt%Ni-Al in (volume fraction) atmosphere2O3Finished catalyst.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 2.
Embodiment 8
Weigh 2.4771g Ni (NO3)2·6H2O adds in 6.0g deionized waters, and 4.5g is added in after its all dissolving
Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst precarsor after roasting 4h at 400 DEG C.It will
Catalyst precarsor is in 10%H2/N2500 DEG C of activation 4h are to get 10wt%Ni-Al in (volume fraction) atmosphere2O3Finished catalyst.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
160 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 2.
Embodiment 9
Weigh 2.4771g Ni (NO3)2·6H2O adds in 6.0g deionized waters, and 4.5g is added in after its all dissolving
Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst precarsor after roasting 4h at 400 DEG C.It will
Catalyst precarsor is in 10%H2/N2500 DEG C of activation 4h are to get 10wt%Ni-Al in (volume fraction) atmosphere2O3Finished catalyst.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
80 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 2.
Embodiment 10
Weigh 0.3378g RuCl3(Ru content 37wt%) adds in 6.5g deionized waters, is added in after its all dissolving
4.875g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst after roasting 4h at 400 DEG C
Precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 2.5wt%Ru-Al in (volume fraction) atmosphere2O3It urges
Agent finished product.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 3.
Embodiment 11
Weigh 0.1351g RuCl3(Ru content 37wt%) adds in 6.5g deionized waters, is added in after its all dissolving
4.95 g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst after roasting 4h at 400 DEG C
Precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 1wt%Ru-Al in (volume fraction) atmosphere2O3Catalysis
Agent finished product.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 3.
Embodiment 12
Weigh 1.3512g RuCl3(Ru content 37wt%) adds in 6.5g deionized waters, is added in after its all dissolving
4.5g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings are before roasting 4h and obtaining catalyst at 400 DEG C
Body.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 10wt%Ru-Al in (volume fraction) atmosphere2O3Catalyst
Finished product.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 3.
Embodiment 13
Weigh 0.3378g RuCl3(Ru content 37wt%) adds in 7.5g deionized waters, is added in after its all dissolving
4.875g SiO2Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst after roasting 4h at 400 DEG C
Precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 2.5wt%Ru-SiO in (volume fraction) atmosphere2Catalysis
Agent finished product.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 3.
Embodiment 14
Weigh 0.3378g RuCl3(Ru content 37wt%) adds in 7.0g deionized waters, is added in after its all dissolving
4.875g TiO2Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst after roasting 4h at 400 DEG C
Precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 2.5wt%Ru-TiO in (volume fraction) atmosphere2Catalysis
Agent finished product.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 3.
Embodiment 15
Weigh 0.3378g RuCl3(Ru content 37wt%) adds in 6.5g deionized waters, is added in after its all dissolving
4.875g absorbent charcoal carriers stir evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings must be catalyzed after roasting 4h at 400 DEG C
Agent precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are catalyzed to get 2.5wt%Ru-C in (volume fraction) atmosphere
Agent finished product.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 3.
Embodiment 16
Weigh 0.3378g RuCl3(Ru content 37wt%) adds in 7.5g deionized waters, is added in after its all dissolving
4.875g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst after roasting 4h at 400 DEG C
Precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 2.5wt%Ru-Al in (volume fraction) atmosphere2O3It urges
Agent finished product.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
80 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 3.
Embodiment 17
Weigh 0.3378g RuCl3(Ru content 37wt%) adds in 7.5g deionized waters, is added in after its all dissolving
4.875g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst after roasting 4h at 400 DEG C
Precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 2.5wt%Ru-Al in (volume fraction) atmosphere2O3It urges
Agent finished product.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
100 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 3.
Embodiment 18
Weigh 0.3378g RuCl3(Ru content 37wt%) adds in 7.5g deionized waters, is added in after its all dissolving
4.875g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst after roasting 4h at 400 DEG C
Precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 2.5wt%Ru-Al in (volume fraction) atmosphere2O3It urges
Agent finished product.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
160 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 3.
Embodiment 19
Weigh 0.3378g RuCl3(Ru content 37wt%) adds in 7.5g deionized waters, is added in after its all dissolving
4.875g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst after roasting 4h at 400 DEG C
Precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 2.5wt%Ru-Al in (volume fraction) atmosphere2O3It urges
Agent finished product.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 4.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 3.
Embodiment 20
Weigh 0.3378g RuCl3(Ru content 37wt%) adds in 7.5g deionized waters, is added in after its all dissolving
4.875g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst after roasting 4h at 400 DEG C
Precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 2.5wt%Ru-Al in (volume fraction) atmosphere2O3It urges
Agent finished product.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 3.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 3.
Embodiment 21
Weigh 0.3378g RuCl3(Ru content 37wt%) adds in 6.5g deionized waters, is added in after its all dissolving
4.875 g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings must be catalyzed after roasting 4h at 400 DEG C
Agent precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 2.5wt%Ru-Al in (volume fraction) atmosphere2O3
Finished catalyst.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 200, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 3.
Embodiment 22
Weigh 0.3378g RuCl3(Ru content 37wt%) adds in 6.5g deionized waters, is added in after its all dissolving
4.875g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst after roasting 4h at 400 DEG C
Precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 2.5wt%Ru-Al in (volume fraction) atmosphere2O3It urges
Agent finished product.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 300, reactant quality air speed are 0.6h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 3.
Embodiment 23
Weigh 0.3378g RuCl3(Ru content 37wt%) adds in 6.5g deionized waters, is added in after its all dissolving
4.875g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst after roasting 4h at 400 DEG C
Precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 2.5wt%Ru-Al in (volume fraction) atmosphere2O3It urges
Agent finished product.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.3h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 3.
Embodiment 24
Weigh 0.3378g RuCl3(Ru content 37wt%) adds in 6.5g deionized waters, is added in after its all dissolving
4.875g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst after roasting 4h at 400 DEG C
Precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 2.5wt%Ru-Al in (volume fraction) atmosphere2O3It urges
Agent finished product.
Diisobutyl phthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes,
120 DEG C of reaction temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 1.0h-1, reaction beginning is for 24 hours
Sampling analysis afterwards obtains reaction evaluating and the results are shown in Table 3.
Embodiment 25
Weigh 0.3378g RuCl3(Ru content 37wt%) adds in 6.5g deionized waters, is added in after its all dissolving
4.875g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst after roasting 4h at 400 DEG C
Precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 2.5wt%Ru-Al in (volume fraction) atmosphere2O3It urges
Agent finished product.
Dimethyl terephthalate (DMT) hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes, instead
Answer 120 DEG C of temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, after reaction starts for 24 hours
Sampling analysis obtains reaction evaluating and the results are shown in Table 3.
Embodiment 26
Weigh 0.3378g RuCl3(Ru content 37wt%) adds in 6.5g deionized waters, is added in after its all dissolving
4.875g Al2O3Carrier stirs evenly, and 25 DEG C of volumetrics impregnate 12h, and 95 DEG C of dryings obtain catalyst after roasting 4h at 400 DEG C
Precursor.By catalyst precarsor in 10%H2/N2300 DEG C of activation 4h are to get 2.5wt%Ru-Al in (volume fraction) atmosphere2O3It urges
Agent finished product.
Dimethyl isophthalate hydrogenation reaction carries out in the fixed bed reactors equipped with 10mm internal diameter stainless steel tubes, instead
Answer 120 DEG C of temperature, Hydrogen Vapor Pressure 5.0MPa, H2/ ester molar ratio 125, reactant quality air speed are 0.6h-1, after reaction starts for 24 hours
Sampling analysis obtains reaction evaluating and the results are shown in Table 3.
Table 1：Reaction evaluating result on Pd catalyst
Table 2：Reaction evaluating result on Ni catalyst
Table 3：Reaction evaluating result on Ru catalyst
a：The reactant used is dimethyl terephthalate (DMT)
b：The reactant used is dimethyl isophthalate
The above, only presently preferred embodiments of the present invention, not to the present invention in any form with substantial limitation,
It should be pointed out that for those skilled in the art, under the premise of the method for the present invention is not departed from, can also make
Several improvement and supplement, these are improved and supplement also should be regarded as protection scope of the present invention.All those skilled in the art,
Without departing from the spirit and scope of the present invention, when made using disclosed above technology contents it is a little more
Dynamic, modification and the equivalent variations developed, are the equivalent embodiment of the present invention；Meanwhile all substantial technologicals pair according to the present invention
The variation, modification and evolution of any equivalent variations that above-described embodiment is made still fall within the range of technical scheme of the present invention
It is interior.
Claims (10)
1. a kind of purposes of catalyst, for adjusting the disubstituted cyclohexane carboxylate of aromatic carboxylic acid esters hydrogenation reaction generation
Cis-trans ratio, the catalyst include active component and carrier, the one kind or more of the active component in Ru, Pd and Ni
Kind, the content of active component is 1~10wt%.
2. purposes as described in claim 1, which is characterized in that when the active component of catalyst is Ni, disubstituted cyclohexane
Carboxylate cis ratio accounts for 40~65%；When the active component of catalyst is Ru, disubstituted cyclohexane carboxylate cis ratio
Account for 75~90%；When the active component of catalyst is Pd, disubstituted cyclohexane carboxylate cis ratio accounts for 95~98%.
3. a kind of preparation method of the adjustable disubstituted cyclohexane carboxylate of cis-trans ratio, which is characterized in that with aromatic series carboxylic
Acid esters is raw material, and hydrogenation reaction generates disubstituted cyclohexane carboxylate, the two substitutions hexamethylene under the conditions of existing for catalyst
Alkane carboxylate includes cis- disubstituted cyclohexane carboxylate and trans- disubstituted cyclohexane carboxylate, and the catalyst includes
Active component and carrier, the active component is one or more in Ru, Pd and Ni, the content of active component for 1~
10wt%.
4. preparation method as claimed in claim 3, which is characterized in that the carrier is selected from Al2O3、SiO2, activated carbon and TiO2
In it is one or more.
5. preparation method as claimed in claim 4, which is characterized in that the carrier is selected from Al2O3And SiO2In at least one
Kind.
6. preparation method as claimed in claim 3, which is characterized in that the aromatic carboxylic acid esters are for adjacent benzene, isophthalic or to benzene
Dicarboxylic ester.
7. preparation method as claimed in claim 3, which is characterized in that reaction temperature is 60~180 DEG C, reaction pressure 2.0
~6.0MPa, hydrogen ester ratio are 50~400:1.
8. preparation method as claimed in claim 7, which is characterized in that reaction temperature is 80~160 DEG C, reaction pressure 3.0
~5.0MPa, hydrogen ester ratio are 100~300:1.
9. preparation method as claimed in claim 3, which is characterized in that disubstituted cyclohexane carboxylate cis-content for 40% with
On.
10. preparation method as claimed in claim 3, which is characterized in that when the active component of catalyst is Ni, two substitution rings
Cyclohexane carboxylic-acid ester cis ratio accounts for 40~65%；When the active component of catalyst is Ru, disubstituted cyclohexane carboxylate is cis-
Ratio accounts for 75~90%；When the active component of catalyst is Pd, disubstituted cyclohexane carboxylate cis ratio accounts for 95~98%.
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| CN105582961A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | 1,4-cyclohexan dimethyl dicarboxylate hydrogenation catalyst |
| CN106552618A (en) * | 2015-09-25 | 2017-04-05 | 上海华谊能源化工有限公司 | A kind of catalyst of aromatic carboxylic acid esters' phenyl ring selective hydrogenation and its preparation method and application |
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2016
- 2016-12-07 CN CN201611118460.XA patent/CN108160079B/en active Active
Patent Citations (6)
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|---|---|---|---|---|
| JPS58198439A (en) * | 1982-05-12 | 1983-11-18 | Toray Ind Inc | Preparation of 1,4-cyclohexanedicarboxylic acid |
| WO2003029168A2 (en) * | 2001-09-24 | 2003-04-10 | Oxeno Olefinchemie Gmbh | Mixture of alicyclic polycarboxylic acid esters having a high cis isomer content |
| CN101050184A (en) * | 2007-05-23 | 2007-10-10 | 宁波万华聚氨酯有限公司 | Method for producing H12MDA through hydrogenation reaction |
| CN101417950A (en) * | 2008-10-27 | 2009-04-29 | 中国科学院大连化学物理研究所 | Method for preparing 1,2-cyclohexane cyclohexanedimethanol dibasic ester |
| CN105582961A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | 1,4-cyclohexan dimethyl dicarboxylate hydrogenation catalyst |
| CN106552618A (en) * | 2015-09-25 | 2017-04-05 | 上海华谊能源化工有限公司 | A kind of catalyst of aromatic carboxylic acid esters' phenyl ring selective hydrogenation and its preparation method and application |
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