CN104549266B - Trans-1,4-cyclohexane dicarboxylic acids catalyst and preparation method thereof - Google Patents
Trans-1,4-cyclohexane dicarboxylic acids catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to produce trans 1, the preparation method of 4 cyclohexane dicarboxylic acid catalyst, the catalyst obtained, and described catalyst is trans 1, application in 4 cyclohexane dicarboxylic acid synthesis, mainly solve present in prior art terephthalic acid (TPA) Hydrogenation for 1, the problem that in 4 cyclohexane dicarboxylic acids, catalyst is the highest to trans Isosorbide-5-Nitrae cyclohexane dicarboxylic acid selectivity.The present invention by use trans Isosorbide-5-Nitrae cyclohexane dicarboxylic acid catalyst preparation method, including: with containing Mo compound and the compound solution oxide impregnation aluminium Han W, drying, roasting prepare presoma I；Use H2Process presoma I with the gaseous mixture of alkane, obtain complex carrier；Load is containing Pd compound and the compound Han Pt；The compound of Pd and Pt is reduced to metal, obtains the technical scheme of described catalyst, preferably solve this problem, can be used in the industrial production of trans Isosorbide-5-Nitrae cyclohexane dicarboxylic acid.
Description
Technical field
The present invention relates to the preparation method of t-CHDA catalyst and the catalyst of preparation, and the application that described catalyst is in t-CHDA synthesizes.
Background technology
1,4-cyclohexane dicarboxylic acid is widely used as the raw material of medicine, synthetic resin, synthetic fibers and dyestuff.Further, since t-CHDA is as the superiority produced in terms of heat resistance, against weather and high physical strength resin and fibrous raw material, accordingly, it would be desirable to produce the Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid of high concentration t-CHDA.At present, the Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid prepared by terephthalic acid (TPA) direct hydrogenation is typically mixing Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, as United States Patent (USP) US2888484(is entitled: Production of
Hexahydroterephthalic acid), Chinese patent CN1229322(entitled: the hydrogenation of phthalic acid) and Chinese patent CN1915958(entitled: terephthalic acid (TPA) is through benzene ring hydrogenation system 1, the method of 4-cyclohexane cyclohexanedimethanodibasic) and product in anti-form-1, the concentration of 4-cyclohexane dicarboxylic acid is all less than 50%, and used catalyst is mainly Pd/C catalyst and Ru/Al2O3Catalyst.Industrial in order to improve anti-form-1, the concentration of 4-cyclohexane dicarboxylic acid, it is generally all by melted cis 1, (the CN1608042 that the isomerization of 4-cyclohexane dicarboxylic acid is carried out, entitled: anti-form-1, the production method of 4-cyclohexane dicarboxylic acid), the operation of the method and operation are the most complex, and energy consumption is higher.
Summary of the invention
One of the technical problem to be solved be present in prior art terephthalic acid (TPA) Hydrogenation for 1, in 4-cyclohexane dicarboxylic acid, catalyst is to anti-form-1, the problem that the selectivity of 4-cyclohexane dicarboxylic acid is the highest, one is provided to be used for producing anti-form-1, the preparation method of the catalyst of 4-cyclohexane dicarboxylic acid, the feature that the catalyst of the method is active and the highest.
The two of the technical problem to be solved are to provide the catalyst that the described preparation method corresponding with the problems referred to above obtains.
The three of the technical problem to be solved be above-mentioned technical problem two described in catalyst trans-1,4-cyclohexane dicarboxylic acids synthesize in application.
In order to solve one of above-mentioned technical problem, technical scheme is as follows: anti-form-1, the preparation method of 4-cyclohexane dicarboxylic acid catalyst, comprises the following steps: a) with containing Mo compound and the compound solution oxide impregnation aluminium Han W, drying, roasting prepare presoma I；B) H is used2With the gaseous mixture of alkane in a heated condition to presoma I process, obtain complex carrier A；C) with containing Pd compound and the compound Han Pt molten dipping complex carrier A, drying, roasting prepare catalyst precursor II；D) with reducing agent, the compound of Pd and Pt in catalyst precursor II is reduced to metal, obtains finished catalyst；In described complex carrier A, the content of Mo is 1～the mol ratio of 10g/L, Mo and W is 1:(0.1～1)；In described catalyst, Pd content is 0.5～the mass ratio of 3g/L, Pd and Pt is 1:(0.1～1).
In technique scheme, step a) and the baking temperature described in step c) are preferably 80～110 DEG C, and sintering temperature is preferably 450～600 DEG C.
The preferred C of alkane described in step b) in technique scheme4~C7Alkane, the described H in step b)2With alkane and H in alkane gaseous mixture2Volume ratio be preferably 1:(1～10), more preferably 1:(2～4).
In technique scheme in complex carrier A described in step b) Mo content be preferably 3～the mol ratio of 5g/L, Mo and W be preferably 1:(0.3～0.6).
The temperature processed in step b) in technique scheme is preferably 650～800 DEG C.The time processed in step b) is preferably 0.5～5 hour, more preferably 2～3 hours.
In catalyst described in technique scheme, preferred Pd content is 1～the mass ratio of 2g/L, Pd and Pt is 1:(0.3～0.6).
In technique scheme, the reducing agent described in step c) is preferably hydrogen, and reduction temperature is preferably 450～600 DEG C.Preferably with the gas dilution hydrogen to reactionlessness, this preferred nitrogen of gas to reactionlessness, the nitrogen dilution of more preferably 5～10 times of volumes.
In order to solve the two of above-mentioned technical problem, technical scheme is as follows: use the catalyst that any of the above-described preparation method obtains.
In order to solve the three of above-mentioned technical problem, technical scheme is as follows: the application in t-CHDA synthesizes of the catalyst described in the technical scheme of the two of above-mentioned technical problem.
Inventor has surprisingly found that, uses the selectivity of technique scheme rear catalyst to be greatly improved.Test result indicate that, prior art makes 1, the yield of 4-cyclohexane dicarboxylic acid is 87.6%, the selectivity of t-CHDA is 43.8%, and the inventive method under equal conditions can make 1, the yield of 4-cyclohexane dicarboxylic acid is 95.7%, the selectivity of t-CHDA is up to 96.8%, achieves preferable technique effect.
Detailed description of the invention
[embodiment
1
】
The preparation of carrier: by (NH4)6Mo7O24(NH4)6H2W12O40Soluble in water obtain 400 milliliters of maceration extracts, in this maceration extract Mo content be the mol ratio of 4g, Mo and W be 1:0.5, the alumina balls of gained maceration extract and 1 liter of a diameter of 2mm are mixed, stands 12h, at 90 DEG C, be dried 3h, in Muffle furnace, roasting 3h at 500 DEG C, obtains presoma I；Presoma I is existedV(C5H12)/V(H2In the mixed atmosphere of)=1:3 700 DEG C process 2h, cooling, obtain complex carrier A, through ICP-AES analyze, in complex carrier A, Mo content is 4g/L, W content be the mol ratio of 3.83g/L, i.e. Mo Yu W be 1:0.5.
The preparation of catalyst: by K2PdCl4And K2PtCl6Soluble in water obtain 400 milliliters of maceration extracts, in this maceration extract Pd content be the mass ratio of 1.5g, Pd and Pt be 1:0.4, by above-mentioned to gained maceration extract and 1 liter complex carrier A mix, stand 12h, being dried 3h at 90 DEG C, at 500 DEG C, roasting 3h obtains catalyst precursor, and catalyst precursor is finally placed at 500 DEG C the hydrogen reducing 3h with 7.5 times of nitrogen dilutions, obtain finished catalyst, through ICP-AES analyze, the Pd content in catalyst be 1.5g/L, Pt content be 0.6g/L.
The evaluation of catalyst: 200g terephthalic acid (TPA) is added autoclave, add the catalyst of 20ml embodiment 1 gained, add 1000g water, open stirring, first it is passed through nitrogen to replace three times, is being passed through hydrogen exchange three times, then pass to hydrogen and make pressure rise to 4MPa and keep stable, maintain reaction temperature 200 DEG C, and be passed through hydrogen reaction 3h continuously.After reaction terminates, filtering catalyst while hot, filtrate cooled and filtered, obtain filter cake, filter cake dries to obtain solid product at 120 DEG C.Content and the content of t-CHDA of Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid in solid product can be obtained, such that it is able to calculate the yield of Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid and the selectivity of t-CHDA with liquid-phase chromatographic analysis solid product.
Compare for convenience, embodiment 1 used catalyst preparation condition, gained catalyst composition and the evaluating catalyst gained Isosorbide-5-Nitrae-yield of cyclohexane dicarboxylic acid and the selectivity of t-CHDA are shown in Table 1.
[embodiment
2-8
】
By the pentane (C in embodiment 15H12) substitute with methane, ethane, propane, butane, hexane, heptane, octane respectively, remaining operation is with embodiment 1, compare for convenience, by embodiment 2-8 used catalyst preparation condition, gained catalyst composition and evaluating catalyst gained 1, the yield of 4-cyclohexane dicarboxylic acid and the selectivity of t-CHDA are shown in Table 1.
[embodiment
9-12
】
By in embodiment 1V(C5H12)/V(H2) value change 1:1,1:2,1:4,1:10 into, remaining operation with embodiment 1.Compare for convenience, embodiment 9-12 used catalyst preparation condition, gained catalyst composition and the evaluating catalyst gained Isosorbide-5-Nitrae-yield of cyclohexane dicarboxylic acid and the selectivity of t-CHDA are shown in Table 1.
[embodiment
13-16
】
The preparation of carrier: by (NH4)6Mo7O24(NH4)6H2W12O40Soluble in water obtain 400 milliliters of maceration extracts, changing Mo content in maceration extract is 1g, 3g, 5g and 10g, the mol ratio maintaining Mo Yu W is 1:0.5, the alumina balls of gained maceration extract and 1 liter of a diameter of 2mm are mixed, stand 12h, being dried 3h at 90 DEG C, in Muffle furnace, roasting 3h at 500 DEG C, obtains presoma I；Presoma I is existedV(C5H12)/V(H2In the mixed atmosphere of)=1:3,700 DEG C process 2h, cooling, obtain complex carrier A, analyze through ICP-AES, in complex carrier A, Mo content is respectively 1g/L, 3g/L, 5g/L and 10g/L, and the corresponding mol ratio that W content is 0.96g/L, 2.87g/L, 4.79g/L and 9.58g/L, i.e. Mo Yu W is 1:0.5.
The preparation of catalyst: by K2PdCl4And K2PtCl6nullSoluble in water obtain 400 milliliters of maceration extracts，In maceration extract, Pd content is 1.5g，The mass ratio of Pd Yu Pt is 1:0.4，Above-mentioned to gained maceration extract and 1 liter complex carrier A is mixed，Stand 12h，3h it is dried at 90 DEG C，At 500 DEG C, roasting 3h obtains catalyst precursor，Finally catalyst precursor is placed at 500 DEG C the hydrogen reducing 3h with 7.5 times of nitrogen dilutions，Obtain finished catalyst，Analyze through ICP-AES，Pd content in catalyst is 1.5g/L，Pt content is 0.6g/L，Remaining operation is with embodiment 1，Compare for convenience，By embodiment 25-28 used catalyst preparation condition、Gained catalyst composition and evaluating catalyst gained 1,The yield of 4-cyclohexane dicarboxylic acid and anti-form-1,The selectivity of 4-cyclohexane dicarboxylic acid is shown in Table 1.
[embodiment
17-20
】
The preparation of carrier: by (NH4)6Mo7O24(NH4)6H2W12O40Soluble in water obtain 400 milliliters of maceration extracts, maintaining Mo content in this maceration extract is that 4g is constant, the mol ratio changing Mo Yu W is 1:0.1,1:0.3,1:0.6,1:1, the alumina balls of gained maceration extract and 1 liter of a diameter of 2mm are mixed, stand 12h, being dried 3h at 90 DEG C, in Muffle furnace, roasting 3h at 500 DEG C, obtains presoma I；Presoma I is existedV(C5H12)/V(H2In the mixed atmosphere of)=1:3,700 DEG C process 2h, cooling, obtain complex carrier A, analyze through ICP-AES, in complex carrier A, Mo content is 4g/L, and W content is respectively 0.77g/L, 2.30g/L, 4.60g/L, 7.66g/L, i.e. the mol ratio of Mo Yu W is respectively 1:0.1,1:0.3,1:0.6,1:1.
The preparation of catalyst: by K2PdCl4And K2PtCl6nullSoluble in water obtain 400 milliliters of maceration extracts，In this maceration extract, Pd content is 1.5g，The mass ratio of Pd Yu Pt is 1:0.4，Above-mentioned to gained maceration extract and 1 liter complex carrier A is mixed，Stand 12h，3h it is dried at 90 DEG C，At 500 DEG C, roasting 3h obtains catalyst precursor，Finally catalyst precursor is placed at 500 DEG C the hydrogen reducing 3h with 7.5 times of nitrogen dilutions，Obtain finished catalyst，Analyze through ICP-AES，Pd content in catalyst is 1.5g/L，Pt content is 0.6g/L，Remaining operation is with embodiment 1，Compare for convenience，By embodiment 17-20 used catalyst preparation condition、Gained catalyst composition and evaluating catalyst gained 1,The yield of 4-cyclohexane dicarboxylic acid and anti-form-1,The selectivity of 4-cyclohexane dicarboxylic acid is shown in Table 1..
[embodiment
21-24
】
Treatment temperature in the preparation of carrier in embodiment 1 700 DEG C changes into 500 DEG C, 650 DEG C, 800 DEG C, 900 DEG C, and remaining operation is with embodiment 1.Compare for convenience, embodiment 21-24 used catalyst preparation condition, gained catalyst composition and the evaluating catalyst gained Isosorbide-5-Nitrae-yield of cyclohexane dicarboxylic acid and the selectivity of t-CHDA are shown in Table 1.
[embodiment
25-28
】
The preparation of carrier: by (NH4)6Mo7O24(NH4)6H2W12O40Soluble in water obtain 400 milliliters of maceration extracts, in this maceration extract Mo content be the mol ratio of 4g, Mo and W be 1:0.5, the alumina balls of gained maceration extract and 1 liter of a diameter of 2mm are mixed, stands 12h, at 90 DEG C, be dried 3h, in Muffle furnace, roasting 3h at 500 DEG C, obtains presoma I；Presoma I is existedV(C5H12)/V(H2In the mixed atmosphere of)=1:3 700 DEG C process 2h, cooling, obtain complex carrier A, through ICP-AES analyze, in complex carrier A, Mo content is 4g/L, W content be the mol ratio of 3.83g/L, i.e. Mo Yu W be 1:0.5.
The preparation of catalyst: by K2PdCl4And K2PtCl6nullSoluble in water obtain 400 milliliters of maceration extracts，The Pd content changed in maceration extract is respectively 0.5g、1g、2g、3g，The mass ratio maintaining Pd with Pt is that 1:0.4 is constant，Gained maceration extract is mixed with 1 liter of above-mentioned complex carrier A respectively，Stand 12h，3h it is dried at 90 DEG C，At 500 DEG C, roasting 3h obtains catalyst precursor，Finally catalyst precursor is placed at 500 DEG C the hydrogen reducing 3h with 7.5 times of nitrogen dilutions，Obtain finished catalyst，Analyze through ICP-AES，Pd content in catalyst is respectively 0.5g/L、1g/L、2g/L、3g/L，Corresponding Pt content is respectively 0.2g/L、0.4g/L、0.8g/L、1.2g/L，Remaining operation is with embodiment 1，Compare for convenience，By embodiment 25-28 used catalyst preparation condition、Gained catalyst composition and evaluating catalyst gained 1,The yield of 4-cyclohexane dicarboxylic acid and anti-form-1,The selectivity of 4-cyclohexane dicarboxylic acid is shown in Table 1.
[embodiment
29-32
】
The preparation of carrier: by (NH4)6Mo7O24(NH4)6H2W12O40Soluble in water obtain 400 milliliters of maceration extracts, in this maceration extract Mo content be the mol ratio of 4g, Mo and W be 1:0.5, the alumina balls of gained maceration extract and 1 liter of a diameter of 2mm are mixed, stands 12h, at 90 DEG C, be dried 3h, in Muffle furnace, roasting 3h at 500 DEG C, obtains presoma I；Presoma I is existedV(C5H12)/V(H2In the mixed atmosphere of)=1:3 700 DEG C process 2h, cooling, obtain complex carrier A, through ICP-AES analyze, in complex carrier A, Mo content is 4g/L, W content be the mol ratio of 3.83g/L, i.e. Mo Yu W be 1:0.5.
The preparation of catalyst: by K2PdCl4And K2PtCl6Soluble in water obtain 400 milliliters of maceration extracts, the Pd content in maceration extract is maintained to be respectively 1.5g constant, the mass ratio changing Pd Yu Pt is respectively 1:0.1, 1:0.3, 1:0.6, 1:1, gained maceration extract is mixed with 1 liter of above-mentioned complex carrier A respectively, stand 12h, 3h it is dried at 90 DEG C, at 500 DEG C, roasting 3h obtains catalyst precursor, finally catalyst precursor is placed at 500 DEG C the hydrogen reducing 3h with 7.5 times of nitrogen dilutions, obtain finished catalyst, analyze through ICP-AES, Pd content 1.5g/L in catalyst, corresponding Pt content is respectively 0.15g/L, 0.45g/L, 0.9g/L, 1.5g/L, remaining operation is with embodiment 1.Compare for convenience, embodiment 29-32 used catalyst preparation condition, gained catalyst composition and the evaluating catalyst gained Isosorbide-5-Nitrae-yield of cyclohexane dicarboxylic acid and the selectivity of t-CHDA are shown in Table 1.
[comparative example
1
】
The preparation of catalyst: by K2PdCl4And K2PtCl6nullSoluble in water obtain 400 milliliters of maceration extracts，In maceration extract, Pd content is 1.5g，The mass ratio of Pd Yu Pt is 1:0.4，Above-mentioned to gained maceration extract and 1 liter complex carrier A is mixed，Stand 12h，3h it is dried at 90 DEG C，At 500 DEG C, roasting 3h obtains catalyst precursor，Finally catalyst precursor is placed at 500 DEG C the hydrogen reducing 3h with 7.5 times of nitrogen dilutions，Obtain finished catalyst，Analyze through ICP-AES，Pd content in catalyst is 1.5g/L，Pt content is 0.6g/L，Remaining operation is with embodiment 1，Compare for convenience，By comparative example 1 used catalyst preparation condition、Gained catalyst composition and evaluating catalyst gained 1,The yield of 4-cyclohexane dicarboxylic acid and anti-form-1,The selectivity of 4-cyclohexane dicarboxylic acid is shown in Table 1.
[comparative example
2
】
The preparation of carrier: by (NH4)6Mo7O24(NH4)6H2W12O40Soluble in water obtain 400 milliliters of maceration extracts, in this maceration extract, Mo content is 4g, and the mol ratio changing Mo Yu W is 1:0.1,1:0.3,1:0.6,1:1, is mixed by the alumina balls of gained maceration extract and 1 liter of a diameter of 2mm, stand 12h, being dried 3h at 90 DEG C, in Muffle furnace, roasting 3h at 500 DEG C, obtains presoma I, analyze through ICP-AES, in complex carrier A, Mo content is 4g/L, W content be the mol ratio of 3.83g/L, i.e. Mo Yu W be 1:0.5.
The preparation of catalyst: by K2PdCl4And K2PtCl6nullSoluble in water obtain 400 milliliters of maceration extracts，In maceration extract, Pd content is 1.5g，The mass ratio of Pd Yu Pt is 1:0.4，Above-mentioned to gained maceration extract and 1 liter complex carrier A is mixed，Stand 12h，3h it is dried at 90 DEG C，At 500 DEG C, roasting 3h obtains catalyst precursor，Finally catalyst precursor is placed at 500 DEG C the hydrogen reducing 3h with 7.5 times of nitrogen dilutions，Obtain finished catalyst，Analyze through ICP-AES，Pd content in catalyst is 1.5g/L，Pt content is 0.6g/L，Remaining operation is with embodiment 1，Compare for convenience，By comparative example 2 used catalyst preparation condition、Gained catalyst composition and evaluating catalyst gained 1,The yield of 4-cyclohexane dicarboxylic acid and anti-form-1,The selectivity of 4-cyclohexane dicarboxylic acid is shown in Table 1.
[comparative example
3
】
The preparation of carrier: by (NH4)6Mo7O24Soluble in water obtaining 400 milliliters of maceration extracts, in this maceration extract, Mo content is 7.83g, is mixed by the alumina balls of gained maceration extract and 1 liter of a diameter of 2mm, stands 12h, is dried 3h at 90 DEG C, and in Muffle furnace, roasting 3h at 500 DEG C, obtains presoma I；Presoma I is existedV(C5H12)/V(H2In the mixed atmosphere of)=1:3,700 DEG C process 2h, cooling, obtain complex carrier A, analyze through ICP-AES, and in complex carrier A, Mo content is 7.83g/L.
The preparation of catalyst: by K2PdCl4And K2PtCl6nullSoluble in water obtain 400 milliliters of maceration extracts，In maceration extract, Pd content is 1.5g，The mass ratio of Pd Yu Pt is 1:0.4，Above-mentioned to gained maceration extract and 1 liter complex carrier A is mixed，Stand 12h，3h it is dried at 90 DEG C，At 500 DEG C, roasting 3h obtains catalyst precursor，Finally catalyst precursor is placed at 500 DEG C the hydrogen reducing 3h with 7.5 times of nitrogen dilutions，Obtain finished catalyst，Analyze through ICP-AES，Pd content in catalyst is 1.5g/L，Pt content is 0.6g/L，Remaining operation is with embodiment 1，Compare for convenience，By comparative example 3 used catalyst preparation condition、Gained catalyst composition and evaluating catalyst gained 1,The yield of 4-cyclohexane dicarboxylic acid and anti-form-1,The selectivity of 4-cyclohexane dicarboxylic acid is shown in Table 1.
[comparative example
4
】
The preparation of carrier: by (NH4)6H2W12O40Soluble in water obtaining 400 milliliters of maceration extracts, in this maceration extract, W content is 7.83g, is mixed by the alumina balls of gained maceration extract and 1 liter of a diameter of 2mm, stands 12h, is dried 3h at 90 DEG C, and in Muffle furnace, roasting 3h at 500 DEG C, obtains presoma I；Presoma I is existedV(C5H12)/V(H2In the mixed atmosphere of)=1:3,700 DEG C process 2h, cooling, obtain complex carrier A, analyze through ICP-AES, and in complex carrier A, W content is 7.83g/L.
The preparation of catalyst: by K2PdCl4And K2PtCl6nullSoluble in water obtain 400 milliliters of maceration extracts，In maceration extract, Pd content is 1.5g，The mass ratio of Pd Yu Pt is 1:0.4，Above-mentioned to gained maceration extract and 1 liter complex carrier A is mixed，Stand 12h，3h it is dried at 90 DEG C，At 500 DEG C, roasting 3h obtains catalyst precursor，Finally catalyst precursor is placed at 500 DEG C the hydrogen reducing 3h with 7.5 times of nitrogen dilutions，Obtain finished catalyst，Analyze through ICP-AES，Pd content in catalyst is 1.5g/L，Pt content is 0.6g/L，Remaining operation is with embodiment 1，Compare for convenience，By comparative example 4 used catalyst preparation condition、Gained catalyst composition and evaluating catalyst gained 1,The yield of 4-cyclohexane dicarboxylic acid and anti-form-1,The selectivity of 4-cyclohexane dicarboxylic acid is shown in Table 1.
[comparative example
5
】
The preparation of carrier: by (NH4)6Mo7O24(NH4)6H2W12O40Soluble in water obtain 400 milliliters of maceration extracts, in this maceration extract Mo content be the mol ratio of 4g, Mo and W be 1:0.5, the alumina balls of gained maceration extract and 1 liter of a diameter of 2mm are mixed, stands 12h, at 90 DEG C, be dried 3h, in Muffle furnace, roasting 3h at 500 DEG C, obtains presoma I；Presoma I is existedV(C5H12)/V(H2In the mixed atmosphere of)=1:3 700 DEG C process 2h, cooling, obtain complex carrier A, through ICP-AES analyze, in complex carrier A, Mo content is 4g/L, W content be the mol ratio of 3.83g/L, i.e. Mo Yu W be 1:0.5.
The preparation of catalyst: by K2PdCl4Soluble in water obtain 400 milliliters of maceration extracts, in this maceration extract, Pd content is 2.1g, above-mentioned to gained maceration extract and 1 liter complex carrier A is mixed, stand 12h, 3h it is dried at 90 DEG C, at 500 DEG C, roasting 3h obtains catalyst precursor, finally catalyst precursor is placed at 500 DEG C the hydrogen reducing 3h with 7.5 times of nitrogen dilutions, obtain finished catalyst, analyze through ICP-AES, Pd content in catalyst is 2.1g/L, remaining operation is with embodiment 1, compare for convenience, by comparative example 5 used catalyst preparation condition, gained catalyst composition and evaluating catalyst gained 1, the yield of 4-cyclohexane dicarboxylic acid and anti-form-1, the selectivity of 4-cyclohexane dicarboxylic acid is shown in Table 1.
[comparative example
6
】
The preparation of carrier: by (NH4)6Mo7O24(NH4)6H2W12O40Soluble in water obtain 400 milliliters of maceration extracts, in this maceration extract Mo content be the mol ratio of 4g, Mo and W be 1:0.5, the alumina balls of gained maceration extract and 1 liter of a diameter of 2mm are mixed, stands 12h, at 90 DEG C, be dried 3h, in Muffle furnace, roasting 3h at 500 DEG C, obtains presoma I；Presoma I is existedV(C5H12)/V(H2In the mixed atmosphere of)=1:3 700 DEG C process 2h, cooling, obtain complex carrier A, through ICP-AES analyze, in complex carrier A, Mo content is 4g/L, W content be the mol ratio of 3.83g/L, i.e. Mo Yu W be 1:0.5.
The preparation of catalyst: by K2PtCl6Soluble in water obtain 400 milliliters of maceration extracts, in this maceration extract, Pt content is 2.1g, above-mentioned to gained maceration extract and 1 liter complex carrier A is mixed, stand 12h, 3h it is dried at 90 DEG C, at 500 DEG C, roasting 3h obtains catalyst precursor, finally catalyst precursor is placed at 500 DEG C the hydrogen reducing 3h with 7.5 times of nitrogen dilutions, obtain finished catalyst, analyze through ICP-AES, Pt content in catalyst is 2.1g/L, remaining operation is with embodiment 1, compare for convenience, by comparative example 6 used catalyst preparation condition, gained catalyst composition and evaluating catalyst gained 1, the yield of 4-cyclohexane dicarboxylic acid and anti-form-1, the selectivity of 4-cyclohexane dicarboxylic acid is shown in Table 1.
Table 1(is continued)
Table 1(continues 1)
Table 1(continues 2)
Table 1(continues 3)
| (Pd+Pt) content, g/L | Pd Yu Pt mass ratio | The yield of Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, % | The selectivity of t-CHDA, % | |
| Embodiment 25 | 0.7 | 1:0.4 | 88.3 | 91.5 |
| Embodiment 26 | 1.4 | 1:0.4 | 94.6 | 96.3 |
| Embodiment 27 | 2.8 | 1:0.4 | 95.5 | 96.7 |
| Embodiment 28 | 4.2 | 1:0.4 | 94.8 | 95.6 |
| Embodiment 29 | 1.65 | 1:0.1 | 95.2 | 92.1 |
| Embodiment 30 | 1.95 | 1:0.3 | 95.6 | 95.8 |
| Embodiment 31 | 2.4 | 1:0.6 | 95.8 | 96.5 |
| Embodiment 32 | 3.0 | 1:1 | 94.9 | 93.7 |
| Comparative example 1 | 2.1 | 1:0.4 | 87.6 | 43.8 |
| Comparative example 2 | 2.1 | 1:0.4 | 85.2 | 41.6 |
| Comparative example 3 | 2.1 | 1:0.4 | 88.3 | 52.3 |
| Comparative example 4 | 2.1 | 1:0.4 | 89.2 | 53.4 |
| Comparative example 5 | 2.1 | 1:0 | 92.5 | 53.5 |
| Comparative example 6 | 2.1 | 0:1 | 91.8 | 51.8 |
Claims (10)
1. the preparation method of t-CHDA catalyst, comprises the following steps: a) with containing Mo compound with containing W
Compound solution oxide impregnation aluminium, drying, roasting prepare presoma I；B) H is used2Heating with the gaseous mixture of alkane
Under the conditions of to presoma I process, obtain complex carrier A；C) with containing Pd compound with containing the leaching of Pt compound solution
Stain complex carrier A, drying, roasting prepare catalyst precursor II；D) with reducing agent by catalyst precursor II
The compound of Pd and Pt be reduced to metal, obtain finished catalyst；In described complex carrier A the content of Mo be 1～
The mol ratio of 10g/L, Mo and W is 1:(0.1～1)；In described catalyst, Pd content is 0.5～3g/L, Pd and Pt
Mass ratio be 1:(0.1～1).
Method the most according to claim 1, it is characterised in that the baking temperature in described step a) and step c) be 80～
110 DEG C, sintering temperature is 450～600 DEG C.
Method the most according to claim 1, it is characterised in that H in described step b)2With alkane in the gaseous mixture of alkane with
H2Volume ratio be 1:(1～10).
Method the most according to claim 1, it is characterised in that in complex carrier A, the content of Mo is 3～5g/L, Mo with
The mol ratio of W is 1:(0.3～0.6).
Method the most according to claim 1, it is characterised in that the temperature processed in described step b) is 650～800 DEG C.
Method the most according to claim 1, it is characterised in that the time processed in described step b) is 0.5～5 hour.
Method the most according to claim 1, it is characterised in that in described catalyst, Pd content is 1～2g/L, Pd and Pt
Mass ratio is 1:(0.3～0.6).
Method the most according to claim 1, it is characterised in that described reducing agent is to dilute with the nitrogen of 5～10 times of volumes
H2, reduction temperature is 450～600 DEG C.
9. the catalyst that prepared by the method according to any one of claim 1 to 8.
10. the application in trans-1,4-cyclohexane dicarboxylic acids synthesizes of the catalyst described in claim 9.
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| US6291706B1 (en) * | 1999-06-17 | 2001-09-18 | Eastman Chemical Company | Hydrogenation of phthalic acids to cyclohexanedicarboxylic acid |
| JP2002363126A (en) * | 2001-06-07 | 2002-12-18 | Fuji Photo Film Co Ltd | Method for trans-1,4-cyclohexanedicarboxylic acid preparation |
| CN1915958A (en) * | 2005-08-17 | 2007-02-21 | 中国石化上海石油化工股份有限公司 | Method for producing 1,4 - cyclohexane diformate by hydrogenation on benzene ring of terephthalic acid |
| CN1935773A (en) * | 2001-10-26 | 2007-03-28 | 三菱化学株式会社 | Process for producing trans-1,4-cyclohexanedicarboxylic acid |
| CN101543776A (en) * | 2009-04-28 | 2009-09-30 | 华烁科技股份有限公司 | Dehydrogenation catalyst for feed gas containing carbon monoxide, preparation method and application method thereof |
| CN103288596A (en) * | 2012-02-27 | 2013-09-11 | 中国科学院大连化学物理研究所 | Method for preparing monohydric alcohol or dihydric alcohol through organic acid hydrogenation |
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| US6291706B1 (en) * | 1999-06-17 | 2001-09-18 | Eastman Chemical Company | Hydrogenation of phthalic acids to cyclohexanedicarboxylic acid |
| JP2002363126A (en) * | 2001-06-07 | 2002-12-18 | Fuji Photo Film Co Ltd | Method for trans-1,4-cyclohexanedicarboxylic acid preparation |
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