CN103877991B - Anti-form-1, the production method of 4-cyclohexanedimethanol and used catalyst thereof - Google Patents
Anti-form-1, the production method of 4-cyclohexanedimethanol and used catalyst thereof Download PDFInfo
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Abstract
The present invention relates to anti-form-1, the production method of 4-cyclohexanedimethanol and used catalyst thereof, mainly solve in prior art the terephthalic acid (TPA) direct hydrogenation existed and to prepare in 1,4-CHDM catalyst to anti-form-1, the selective not high problem of 4-cyclohexanedimethanol.Catalyst of the present invention is carrier by adopting with active carbon, Pd and Pt is active component, Sn and Cu is auxiliary agent, and in catalyst, Pt content is the mol ratio of 1 ~ 6wt%, Pd and Pt is 1:1, Sn content is 1 ~ 6wt%, the technical scheme that the mol ratio of Sn and Cu is 0.5 ~ 2, Pd and Pt is precursor with the different binuclear complex of Pd-Pt, solves this problem preferably, can be used for the industrial production of trans 1,4-CHDM.
Description
Technical field
The present invention relates to anti-form-1, the production method of 4-cyclohexanedimethanol and used catalyst thereof.
Background technology
1,4-cyclohexanedimethanol (being called for short CHDM) is the important Organic Chemicals of producing mylar, the mylar being substituted ethylene glycol or the production of other polyalcohol by it has good heat endurance and thermoplasticity, can keep stable physical property and electrical property at a higher temperature, the product obtained by this kind of resin-made then has good chemical resistance and environment resistant.The technique of current suitability for industrialized production 1,4-CHDM take mainly dimethyl terephthalate (DMT) as raw material, and first benzene ring hydrogenation prepares Isosorbide-5-Nitrae-dimethyl hexahydrophthalate, then prepares 1,4-CHDM by ester through hydrogenation reaction.Due to the relatively low and abundance of terephthalic acid (TPA) (PTA) price, therefore occurred taking terephthalic acid (TPA) as the trend that 1,4-CHDM prepared by raw material in recent years.In prior art, relative maturity is two step hydrogenation methods, namely first terephthalic acid (TPA) hydrogenation is generated Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic, and repeated hydrogenation generates 1,4-CHDM, and two-step reaction adopts different catalysts.Also have and propose employing one step hydrogenation method production 1,4-cyclohexanedimethanol, as Japan Patent JP2002069016 proposes to adopt Ru-Sn-Re to be the loaded catalyst of active component, hydrogenation reaction 5h under 250 DEG C and 15MPa condition, 1,4-CHDM yield is 42%.It is carrier that JP200007596 then adopts with active carbon, and active component is the catalyst of Ru-Sn-Pt, and hydrogenation reaction 4h under 150 DEG C and 15MPa condition, 1,4-CHDM yield is 28.3%.Chinese patent CN100465145(title is: the preparation method of Isosorbide-5-Nitrae cyclohexanedimethanol) adopt Ru-Sn-B/Al
2o
3catalyst, hydrogenation reaction 4h under 230 DEG C and 10MPa condition, 1,4-CHDM yield is 85.7%, substantially increases the yield of 1,4-CHDM.
Except obtaining product 1,4-CHDM, also must consider its structure, because 1,4-CHDM has 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.1,4-CHDM cis-trans-isomer ratio and constant very important, because cis is different with the crystal structure of trans CHDM polyester, thus the melt temperature of polyester and density are also different.Although above-mentioned catalyst can obtain 1, 4-cyclohexanedimethanol, but catalyst is to anti-form-1, not 4-cyclohexanedimethanol (t-CHDM) selective all not high, anti-form-1 in products therefrom, 4-cyclohexanedimethanol containing quantity not sufficient 30wt%, and due to anti-form-1, the melting range (315 ~ 320 DEG C) of the high polymer of 4-cyclohexanedimethanol and terephthalic acid (TPA) is than cis-1, 4-cyclohexanedimethanol is with high with the melting range (260 ~ 267 DEG C) of the high polymer of terephthalic acid (TPA), therefore 1 of polymerization is required, 4-cyclohexanedimethanol contains more a high proportion of anti-form-1, 4-cyclohexanedimethanol.
Summary of the invention
One of technical problem to be solved by this invention is that the terephthalic acid (TPA) direct hydrogenation existed in prior art prepares 1, in 4-cyclohexanedimethanol, catalyst is to anti-form-1, the selective not high problem of 4-cyclohexanedimethanol, there is provided a kind of for the production of anti-form-1, the catalyst of 4-cyclohexanedimethanol, this catalyst has active and selective high feature.
Two of technical problem to be solved by this invention is to provide a kind of anti-form-1 adopting above-mentioned catalyst, the production method of 4-cyclohexanedimethanol.
In order to one of solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of for the production of anti-form-1,4-cyclohexanedimethanol catalyst, described catalyst take active carbon as carrier, Pd and Pt is active component, Sn and Cu is auxiliary agent, in catalyst, Pt content is 1 ~ 6wt%, the mol ratio of Pd and Pt mol ratio to be 1:1, Sn content be 1 ~ 6wt%, Sn and Cu is 0.5 ~ 2; Described catalyst obtains by comprising following step: a) with the compound solution impregnated carrier active carbon containing Sn and Cu of aequum, then drying obtains catalyst precursor I; B) with the Pd-Pt isodigeranyl caryogamy polymer solution impregnated catalyst presoma I of aequum, then drying obtains catalyst precursor II; C) with reducing agent, the compound of Pd, Pt, Sn and Cu in presoma II is reduced to metal, obtains finished catalyst; The different binuclear complex of described Pd-Pt is such as formula [PdPtCl
2xm] shown complex, wherein X=PPh
2py, Me
2pCH
2pMe
2, Ph
2pCH
2pPh
2, Ph
2pCH
2cH
2pPh
2, Ph
2pCH
2cH
2cH
2pPh
2, Ph
2pCH
2cH
2cH
2cH
2pPh
2, PMe
3, PPh
3, m=1 or 2.
In catalyst described in technique scheme, Pt content is preferably 3 ~ 5wt%, and in described catalyst, Sn content is preferably 3 ~ 5wt%, and the mol ratio of Sn and Cu is preferably 0.75 ~ 1.25; Described active carbon preferably processes the coconut husk charcoal of 3 ~ 5h at 60 ~ 80 DEG C through the salpeter solution of 35wt%; Described baking temperature is preferably 110 ~ 150 DEG C; Described reducing agent is preferably the hydrogen with the nitrogen dilution of 5 ~ 10 times of volumes, and reduction temperature is preferably 400 ~ 600 DEG C.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: under catalyst described in any one of one of above-mentioned technical problem exists, take water as solvent, reaction temperature be 250 ~ 300 DEG C, reaction pressure is 5 ~ 15MPa, the reaction time is 3 ~ 7h, catalyst and terephthalic acid (TPA) mass ratio are that 1:10 ~ 100 time hydrogen and terephthalic acid (TPA) carry out reaction and prepare anti-form-1,4 cyclohexanedimethanols.
In technique scheme, be preferably 3 ~ 10:1 according to described water and terephthalic acid (TPA) mass ratio; Described reaction temperature is preferably 265 ~ 285 DEG C, reaction pressure is preferably 8 ~ 12MPa, the reaction time is preferably 4 ~ 6h, catalyst and terephthalic acid (TPA) mass ratio are preferably 1:20 ~ 50.
The discovery that inventor is surprised, adopts selective being greatly improved of technique scheme rear catalyst.Experimental result shows, prior art makes 1, the yield of 4-cyclohexanedimethanol is 85.6%, anti-form-1, the selective of 4-cyclohexanedimethanol is 26.5%, and the inventive method under equal conditions can make 1, the yield of 4-cyclohexanedimethanol is 92.3%, anti-form-1,4-cyclohexanedimethanol selective up to 98.3%, achieves good technique effect.
Detailed description of the invention
[embodiment 1]
The pretreatment of carrier: by active carbon in the solution containing 35wt% nitric acid, reflux at 65 DEG C 3h, terminates rear deionized water and fully wash to neutrality, and then constant temperature 80 DEG C of dry 12h in vacuum drying chamber, stand-by.
The preparation of catalyst: be first 3wt% and Sn/Cu mol ratio according to the load capacity of Sn in Pd-Pt-Sn-Cu/C catalyst be 1 SnCl taking respective quality
2and CuCl
2and be dissolved in aqueous hydrochloric acid solution and form maceration extract, gained maceration extract is mixed through above-mentioned pretreated active carbon with 50 grams, dipping 12h, filter, at 120 DEG C, dry 3h obtains catalyst precursor I, then is the different binuclear complex [PdPtCl of Pd-Pt that 1wt% takes respective quality according to the content of Pt in Pd-Pt-Sn-Cu/C catalyst
2(PPh
2] and be dissolved in chloroformic solution and form maceration extract py), mixed with catalyst precursor I by gained maceration extract, dipping 12h, filters, at 120 DEG C, dry 3h obtains catalyst precursor II, finally catalyst precursor II is placed in the hydrogen reducing 3h with 7.5 times of nitrogen dilutions at 500 DEG C, obtains Pd-Pt-Sn-Cu/C finished catalyst, analyze through ICP-AES, Pt content in catalyst is 1wt%, Sn content is 3wt%, Cu content is 1.63wt%, and meeting Sn/Cu mol ratio is 1:1.
[embodiment 2-5]
Change the load capacity of Pt in catalyst, do not change the different binuclear complex of Pd-Pt, all the other operations are with embodiment 1, and the Pt content in each embodiment gained catalyst is as shown in table 1.
[embodiment 6-14]
Do not change the load capacity of Pt in catalyst, change Pd-Pt different binuclear complex, all the other operations are with embodiment 3, and in the different binuclear complex of each embodiment Pd-Pt used and gained catalyst, Pt content is as shown in table 1.
[embodiment 15-22]
Change load capacity and the Sn/Cu mol ratio of Sn in catalyst, all the other operations with embodiment 3, the Sn content in each embodiment gained catalyst and Sn/Cu mol ratio as shown in table 1.
[comparative example 1]
The method provided according to Chinese patent CN100465145 prepares Ru-Sn-B/Al
2o
3catalyst, its process is as follows: be first 5wt%, Ru/Sn mol ratio according to the load capacity of Ru be 1.4, takes the RuCl of respective quality
3and SnCl
2be dissolved in respectively in the respective aqueous solution and form maceration extract, first by gained SnCl
2maceration extract and 50 grams of carrier A l
2o
3mixing, dipping 12h, filter, at 120 DEG C, dry 3h obtains catalyst precursor I, then by the RuCl of gained
3maceration extract mixes with catalyst precursor I, and dipping 12h, filter, at 120 DEG C, dry 3h obtains catalyst precursor II, adds NaBH
4the aqueous solution reduces, NaBH
4addition be 6 to carry out according to the mol ratio of B/ (Ru+Sn), after reduction terminates, after filtration, washing, dry and roasting obtain catalyst precursor III, and the hydrogen finally catalyst precursor III being placed in 300 DEG C reduces 3h, obtains Ru-Sn-B/Al
2o
3finished catalyst, analyze through ICP-AES, the Ru content in catalyst is 5wt%, Sn content is 4.2wt%, and meeting Ru/Sn mol ratio is 1.4.
[comparative example 2]
Adopt K
2pdCl
4and H
2ptCl
6the aqueous solution substitute [PdPtCl
2(PPh
2py) chloroformic solution] is maceration extract, and guarantee Pt content is the mol ratio of 3wt% and Pd and Pt is 1:1, and all the other operations are with embodiment 3, and the results are shown in Table 1 for it.
[comparative example 3]
Adopt K
2pdCl
4the aqueous solution and [Pt
2cl
2(PPh
2py) chloroformic solution] substitutes [PdPtCl
2(PPh
2py) chloroformic solution] is maceration extract, step impregnation Kaolinite Preparation of Catalyst, and guarantee Pt content is the mol ratio of 3wt% and Pd and Pt is 1:1, and all the other operations are with embodiment 3, and the results are shown in Table 1 for it.
[comparative example 4]
Adopt H
2ptCl
6the aqueous solution and [Pd
2cl
2(PPh
2py) chloroformic solution] substitutes [PdPtCl
2(PPh
2py) chloroformic solution] is maceration extract, step impregnation Kaolinite Preparation of Catalyst, and guarantee Pt content is the mol ratio of 3wt% and Pd and Pt is 1:1, and all the other operations are with embodiment 3, and the results are shown in Table 1 for it.
[comparative example 5]
Adopt [Pd
2cl
2(PPh
2] and [Pt py)
2cl
2(PPh
2py) chloroformic solution] substitutes [PdPtCl
2(PPh
2py) chloroformic solution] is maceration extract, and guarantee Pt content is the mol ratio of 3wt% and Pd and Pt is 1:1, and all the other operations are with embodiment 3, and the results are shown in Table 1 for it.
[embodiment 23-44]
Evaluating catalyst: 100g terephthalic acid (TPA) is added autoclave, add the Pd-Pt-Sn-Cu/C catalyst of 5g embodiment 1 ~ 22 gained respectively, add 1000g water again, open and stir, first pass into nitrogen and replace three times, passing into hydrogen exchange three times, then pass into hydrogen and make pressure rise to 10MPa and keep stable, maintain reaction temperature 285 DEG C, and pass into hydrogen reaction 4h continuously.After reaction terminates, filtering catalyst after cooling pressure release, reactant liquor gas chromatographic analysis, by internal standard method production concentration.Adopt acid value measuring method, calculate unreacted raw material P-phthalic acid at concentration, the results are shown in Table 2 for it, wherein the conversion ratio of terephthalic acid (TPA), the molar yield of Isosorbide-5-Nitrae cyclohexanedimethanol and anti-form-1, and the optionally computing formula of 4 cyclohexanes is as follows:
[embodiment 45-60]
Change the mass ratio of the mass ratio of the water in embodiment 25 and terephthalic acid (TPA), catalyst and terephthalic acid (TPA), reaction temperature, reaction pressure and reaction time, all the other operate with embodiment 25, and the results are shown in Table 3 for it.
[comparative example 6-10]
Adopt the catalyst of comparative example 1 ~ 5 gained to repeat embodiment 23, the conversion ratio of gained terephthalic acid (TPA), the yield of 1,4-CHDM and anti-form-1, the selective of 4-cyclohexanedimethanol is listed in table 2.
Table 1
Table 2
| The conversion ratio of PTA, % | The yield of CHDM, % | T-CHDM's is selective, % | |
| Embodiment 23 | 85.7 | 72.3 | 98.2 |
| Embodiment 24 | 97.6 | 83.1 | 98.6 |
| Embodiment 25 | 100 | 92.3 | 98.3 |
| Embodiment 26 | 100 | 92.6 | 98.3 |
| Embodiment 27 | 100 | 92.8 | 98.2 |
| Embodiment 28 | 100 | 92.5 | 98.4 |
| Embodiment 29 | 100 | 92.1 | 97.9 |
| Embodiment 30 | 100 | 92.8 | 98.1 |
| Embodiment 31 | 100 | 92.8 | 98.4 |
| Embodiment 32 | 100 | 92.3 | 98.6 |
| Embodiment 33 | 100 | 92.8 | 98.3 |
| Embodiment 34 | 100 | 92.2 | 98.5 |
| Embodiment 35 | 100 | 89.2 | 91.3 |
| Embodiment 36 | 100 | 85.3 | 87.6 |
| Embodiment 37 | 100 | 92.2 | 96.5 |
| Embodiment 38 | 100 | 92.5 | 98.2 |
| Embodiment 39 | 100 | 91.8 | 97.9 |
| Embodiment 40 | 100 | 86.2 | 95.6 |
| Embodiment 41 | 100 | 78.2 | 93.5 |
| Embodiment 42 | 100 | 65.4 | 93.3 |
| Embodiment 43 | 100 | 92.6 | 97.6 |
| Embodiment 44 | 100 | 91.7 | 96.8 |
| Comparative example 6 | 100 | 85.6 | 26.5 |
| Comparative example 7 | 100 | 92.1 | 31.5 |
| Comparative example 8 | 100 | 92.2 | 48.6 |
| Comparative example 9 | 100 | 91.8 | 47.5 |
| Comparative example 10 | 100 | 92.5 | 69.8 |
3(is continued for table)
| The mass ratio of water and terephthalic acid (TPA) | The mass ratio of catalyst and terephthalic acid (TPA) | Reaction temperature, DEG C | Reaction pressure, MPa | Reaction time, h | |
| Embodiment 45 | 1:1 | 1:20 | 285 | 10 | 4 |
| Embodiment 46 | 3:1 | 1:20 | 285 | 10 | 4 |
| Embodiment 47 | 6:1 | 1:20 | 285 | 10 | 4 |
| Embodiment 48 | 10:1 | 1:10 | 285 | 10 | 4 |
| Embodiment 49 | 10:1 | 1:50 | 285 | 10 | 4 |
| Embodiment 50 | 10:1 | 1:100 | 285 | 10 | 4 |
| Embodiment 51 | 10:1 | 1:20 | 250 | 10 | 4 |
| Embodiment 52 | 10:1 | 1:20 | 265 | 10 | 4 |
| Embodiment 53 | 10:1 | 1:20 | 300 | 10 | 4 |
| Embodiment 54 | 10:1 | 1:20 | 285 | 5 | 4 |
| Embodiment 55 | 10:1 | 1:20 | 285 | 8 | 4 |
| Embodiment 56 | 10:1 | 1:20 | 285 | 12 | 4 |
| Embodiment 57 | 10:1 | 1:20 | 285 | 15 | 4 |
| Embodiment 58 | 10:1 | 1:20 | 285 | 10 | 3 |
| Embodiment 59 | 10:1 | 1:20 | 285 | 10 | 6 |
| Embodiment 60 | 10:1 | 1:20 | 285 | 10 | 7 |
Table 3(continues)
| The conversion ratio of PTA, % | The yield of CHDM, % | T-CHDM's is selective, % | |
| Embodiment 45 | 72 | 58 | 97.6 |
| Embodiment 46 | 100 | 91.3 | 98.5 |
| Embodiment 47 | 100 | 92.5 | 98.4 |
| Embodiment 48 | 100 | 87.5 | 98.3 |
| Embodiment 49 | 98.7 | 91.8 | 98.6 |
| Embodiment 50 | 67.5 | 61.3 | 98.4 |
| Embodiment 51 | 95.5 | 88.7 | 98.3 |
| Embodiment 52 | 100 | 92.4 | 98.5 |
| Embodiment 53 | 100 | 89.6 | 98.1 |
| Embodiment 54 | 86.8 | 81.6 | 98.3 |
| Embodiment 55 | 99.8 | 92.3 | 98.6 |
| Embodiment 56 | 100 | 92.6 | 98.5 |
| Embodiment 57 | 100 | 89.5 | 98.3 |
| Embodiment 58 | 95.6 | 89.3 | 98.2 |
| Embodiment 59 | 100 | 93.5 | 98.4 |
| Embodiment 60 | 100 | 88.6 | 98.2 |
Claims (9)
1. one kind for the production of anti-form-1, the catalyst of 4-cyclohexanedimethanol, described catalyst take active carbon as carrier, Pd and Pt is active component, Sn and Cu is auxiliary agent, and in catalyst, Pt content is 1 ~ 6wt%, Pd and Pt mol ratio is 1:1, Sn content is the mol ratio of 1 ~ 6wt%, Sn and Cu is 0.5 ~ 2; Described catalyst obtains by comprising following step: a) with the compound solution impregnated carrier active carbon containing Sn and Cu of aequum, then drying obtains catalyst precursor I; B) with the Pd-Pt isodigeranyl caryogamy polymer solution impregnated catalyst presoma I of aequum, then drying obtains catalyst precursor II; C) with reducing agent, the compound of Pd, Pt, Sn and Cu in presoma II is reduced to metal, obtains finished catalyst; The different binuclear complex of described Pd-Pt is such as formula [PdPtCl
2xm] shown complex, wherein X=PPh
2py, Me
2pCH
2pMe
2, Ph
2pCH
2pPh
2, Ph
2pCH
2cH
2pPh
2, Ph
2pCH
2cH
2cH
2pPh
2, Ph
2pCH
2cH
2cH
2cH
2pPh
2, PMe
3, PPh
3, m=1 or 2.
2. catalyst according to claim 1, is characterized in that in described catalyst, Pt content is 3 ~ 5wt%.
3. catalyst according to claim 1, is characterized in that Sn content in described catalyst be the mol ratio of 3 ~ 5wt%, Sn and Cu is 0.75 ~ 1.25.
4. catalyst according to claim 1, is characterized in that salpeter solution that described active carbon is through 35wt% processes the coconut husk charcoal of 3 ~ 5h at 60 ~ 80 DEG C.
5. catalyst according to claim 1, is characterized in that described baking temperature is 110 ~ 150 DEG C.
6. catalyst according to claim 1, it is characterized in that described reducing agent is the hydrogen of the nitrogen dilution with 5 ~ 10 times of volumes, reduction temperature is 400 ~ 600 DEG C.
7. an anti-form-1, the production method of 4-cyclohexanedimethanol, under such as catalyst according to any one of claim 1 to 6 exists, take water as solvent, reaction temperature be 250 ~ 300 DEG C, reaction pressure is 5 ~ 15MPa, the reaction time is 3 ~ 7h, catalyst and terephthalic acid (TPA) mass ratio are that 1:10 ~ 100 time hydrogen and terephthalic acid (TPA) carry out reaction and prepare anti-form-1,4 cyclohexanedimethanols.
8. anti-form-1 according to claim 7, the production method of 4-cyclohexanedimethanol, is characterized in that described water and terephthalic acid (TPA) mass ratio are 3 ~ 10:1.
9. anti-form-1 according to claim 7, the production method of 4-cyclohexanedimethanol, is characterized in that described reaction temperature is 265 ~ 285 DEG C, reaction pressure is 8 ~ 12MPa, the reaction time is 4 ~ 6h, catalyst and terephthalic acid (TPA) mass ratio 1:20 ~ 50.
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| CN105562123A (en) * | 2014-10-17 | 2016-05-11 | 中国石油化工股份有限公司 | Prereduction method for catalyst for synthesizing rubber antioxidant |
| CN105582914B (en) * | 2014-10-24 | 2018-04-06 | 中国石油化工股份有限公司 | The hydrogenation catalyst of terephthalic acid (TPA) |
| CN105582927B (en) * | 2014-10-24 | 2018-04-06 | 中国石油化工股份有限公司 | 1,4 cyclohexanedimethanol catalyst and its preparation method |
| CN104829431B (en) * | 2015-05-20 | 2017-03-22 | 南京大学连云港高新技术研究院 | Application of catalyst in improving proportion of trans-1, 4-cyclohexanedimethanol |
| JP6623042B2 (en) * | 2015-11-24 | 2019-12-18 | 公益財団法人微生物化学研究会 | Catalyst, method for producing the same, and method for producing optically active anti-1,2-nitroalkanol compound |
| CN112645800B (en) * | 2020-12-09 | 2023-02-03 | 山东兴强化工产业技术研究院有限公司 | Resorcinol synthesis process |
| CN114436772B (en) * | 2022-01-29 | 2022-08-02 | 浙江清和新材料科技有限公司 | Preparation method of 1, 4-cyclohexanedimethanol |
| CN114409525B (en) * | 2022-01-29 | 2022-11-08 | 浙江清和新材料科技有限公司 | Preparation method of 1,4-cyclohexanedicarboxylic acid |
| CN114685241B (en) * | 2022-04-29 | 2023-11-03 | 浙江清和新材料科技有限公司 | Method for preparing 1, 4-cyclohexanedimethanol by one-step hydrogenation of terephthalic acid |
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