CN102381976B - Method for preparing 1, 4-cyclohexane dimethyl phthalate - Google Patents
Method for preparing 1, 4-cyclohexane dimethyl phthalate Download PDFInfo
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- CN102381976B CN102381976B CN 201010269793 CN201010269793A CN102381976B CN 102381976 B CN102381976 B CN 102381976B CN 201010269793 CN201010269793 CN 201010269793 CN 201010269793 A CN201010269793 A CN 201010269793A CN 102381976 B CN102381976 B CN 102381976B
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- 238000000034 method Methods 0.000 title claims abstract description 21
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 title abstract 4
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 title abstract 2
- 229960001826 dimethylphthalate Drugs 0.000 title abstract 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims abstract description 102
- 239000000243 solution Substances 0.000 claims abstract description 30
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 150000002940 palladium Chemical class 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 5
- LNGAGQAGYITKCW-UHFFFAOYSA-N dimethyl cyclohexane-1,4-dicarboxylate Chemical compound COC(=O)C1CCC(C(=O)OC)CC1 LNGAGQAGYITKCW-UHFFFAOYSA-N 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 12
- 239000012267 brine Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000010936 titanium Substances 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002808 molecular sieve Substances 0.000 abstract description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 238000005303 weighing Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 9
- 239000002994 raw material Substances 0.000 description 7
- 230000009466 transformation Effects 0.000 description 6
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910007926 ZrCl Inorganic materials 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229920001634 Copolyester Polymers 0.000 description 1
- 229910019074 Mg-Sn Inorganic materials 0.000 description 1
- 229910019382 Mg—Sn Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005644 polyethylene terephthalate glycol copolymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing 1, 4-cyclohexane dimethyl phthalate; contacting dimethyl terephthalate with hydrogen at a temperature of 150-300 ℃ and a hydrogen pressure of 3-8 MPa absolute in the presence of a supported catalyst, wherein the catalyst comprises 0.1-3% by weight of Pd, 0.01-3% by weight of Mg, 0.01-3% by weight of tetravalent metal M, and the balance of alumina, silica, molecular sieves, titanium oxide or a mixture of these oxides; m4+Selected from Ti4+、Zr4+、Sn4+、Mn4+、Cr4+One or more of (a) water-soluble M4+Salt and water-soluble Mg2+Dissolving salt in water, adding the solution into alkaline aqueous solution containing carrier, and making into MgM4+Al-LDHs/Al2O3Placing the solution in a palladium salt water solution; the catalyst has the characteristics of small using amount of active components, high dispersity, low hydrogenation reaction pressure, high catalytic activity and the like.
Description
Technical field
The present invention relates to a kind of method that is made 1,4 cyclohexanedicarboxylic acid dimethyl ester (DMCD) by dimethyl terephthalate (DMT) (DMT) hydrogenation.
Background technology
The 1,4 cyclohexanedicarboxylic acid dimethyl ester is the intermediate of preparation 1,4 cyclohexane dimethanol.1, the 4-cyclohexanedimethanol is a kind of important new polyester raw materials for production, maximum purposes is with 1, the 4-cyclohexanedimethanol is the synthetic PETG copolyesters of raw material, through extruding or injection molding processing obtains goods such as bottle, sheet material and thick material, its product has the good transparency, shock-resistance, wear-resisting wound property and erosion resistance again.Other unsaturated polyester resin that modification is synthetic also can be used for producing high quality coating and electronic product etc.
1,4 cyclohexane dimethanol also can be used for the production of saturated polyester resin.Made high-performance polyester glaze, be used for electrostatic powder coating, water base or contain coatings volatile organic compounds, have a lot of excellent characteristic, the high symmetry of its structure can make the hardness of coating, crystallinity and the second-order transition temperature of vibrin improve, and the stability of coating and sintering resistance are all improved.In addition, the gained vibrin has higher symmetry, thermostability and weathering resistance preferably, and vibrin synthetic under the high esterification temperature is painted still very little, can be used for making makeup, medical high-performance bottle and extraordinary special-purpose bottle.
As the intermediate of preparation 1,4 cyclohexane dimethanol, DMCD has been produced more than 50 year.Middle nineteen nineties, Yisiman Chemical Company takes the lead in making a breakthrough publication number at middle isobaric hydrogen addition technology: described employing Pd/Rh/AL in the CN 1099745A patent document
2O
3Catalyzer, and add second component (VIII subgroup metal is as Ni, Ru, Pt) raising hydrogenation activity, 140～220 ℃ of temperature of reaction, pressure 5～17Mpa, raw material (DMT and DMCD mixture, mass ratio 3: 7) air speed are 1～30/h
-1, made the method for 1,4 cyclohexanedicarboxylic acid dimethyl ester (DMCD) by dimethyl terephthalate (DMT) (DMT) hydrogenation.Wherein contain the Pd that minimum value is 1% (weight) in the catalyzer, the dispersity of Pd is all less than 40%, and real reaction pressure is up to 12.5Mpa.
In being the patent document of ZL 01110643.3, the patent No. described by Pd/C and carrier AL
2O
3Form, and added the catalyzer that first kind of promoter metal Ca or Ba, Mg and second kind of metal Rh or Ru, Pt make, at 210～230 ℃ of temperature of reaction, pressure 6Mpa, H
2/ DMT (mol/mol) ratio 80～120, raw material (18gDMT/500mL ethyl acetate) air speed 10h
-1Under the condition, made the method for 1,4 cyclohexanedicarboxylic acid dimethyl ester (DMCD) by dimethyl terephthalate (DMT) (DMT) hydrogenation.Wherein contain the Pd that minimum value is 1% (weight) in the catalyzer.
All in all, make 1 by dimethyl terephthalate (DMT) (DMT) hydrogenation in the prior art at present, what employed catalyzer adopted in the method for 4-dimethyl hexahydrophthalate (DMCD) is traditional aqueous solution immersion process for preparing, have mainly that the active noble metals dispersity is lower, preparation process noble metal consumption is big, and required reaction pressure high-technology defective in the production method is if prolonged application must be expensive in its expense of industrial production.
Summary of the invention
The purpose of this invention is to provide a kind of by dimethyl terephthalate (DMT) (DMT) hydrogenation production 1, the method of 4-dimethyl hexahydrophthalate (DMCD), the active ingredient consumption is few in the used catalyzer of this method, dispersity is high, characteristics such as hydrogenation reaction pressure is low, catalytic activity height.
A kind of method of being produced 1,4 cyclohexanedicarboxylic acid dimethyl ester (DMCD) by dimethyl terephthalate (DMT) (DMT) hydrogenation of the present invention.Method of the present invention is included in 150～300 ℃ of temperature and hydrogen pressure is under 3～8MPa absolute pressure, dimethyl terephthalate (DMT) is contacted with hydrogen being stated from the presence of the supported catalyst, described catalyzer comprises 0.1%～3% Pd, 0.01%～3% Mg and 0.01%～3% tetravalent metal (M) by weight, the best is 0.1～0.5% Pd, 0.1～2% Mg and 0.1～2% tetravalent metal M, M
4+Be selected from Ti
4+, Zr
4+, Sn
4+, Mn
4+And Cr
4+In one or more, surplus is alumina catalyst support or silicon oxide, molecular sieve, titanium oxide and these hopcalites; Described catalyzer can obtain with following method:
(a) with water-soluble M
4+Salt and water-soluble Mg
2+The water-soluble solution that is configured to of salt joins described solution in the alkaline aqueous solution that contains carrier, makes MgM
4+Al-LDHs/Al
2O
3
(b) water-soluble palladium salt is configured to the palladium salt brine solution, the MgM that step (a) is obtained
4+Al-LDHs/Al
2O
3Place the palladium salt brine solution, through leaving standstill, filter, obtaining described catalyzer after dry, the roasting.
Catalyzer of the present invention can obtain with following method: with the water-soluble aqueous solution of urea that is configured to of urea, wherein the concentration of urea is 0.2～2mol/L, and concentration is 0.5～2mol/L preferably; The Al that will have certain geometrical shape
2O
3Carrier (Al
2O
3The shape of carrier can be ball-type, one or more of shape such as trifolium-shaped and sheet, as long as this shape can not cause liquid starting material excessive channel in reactor) add in the above-mentioned aqueous solution of urea, its crystalline form can be selected from one or more among δ, β, γ, θ, η and the α, better can select θ-Al
2O
3And α-Al
2O
3Composition be carrier, its add-on is to add 1～6g Al in the above-mentioned aqueous solution of urea of every 100mL
2O
3, add-on is to add 2～3g Al in the above-mentioned aqueous solution of urea of every 100mL preferably
2O
3Under 80～150 ℃ of conditions, stirred 3～15 hours, because concentration, temperature and pH value during LDHs (LDHs is that the English of hydrotalcite intercalation material is called for short) nucleation can be controlled the speed of crystal nucleation, can control crystalline growth velocity by modulation LDHs crystallization time, temperature and crystallization method, therefore, nucleation temperature is 90～130 ℃ preferably, and nucleation time is 13～15 hours preferably.Take by weighing an amount of water-soluble M by catalyst loadings
4+Salt and water-soluble Mg
2+Salt adds corresponding pickup deionized water with it and forms salts solution, M preferably
4+And Mg
2+Mol ratio is 1: 1; Described salts solution is joined in the described aqueous solution of urea, make wherein Mg
2+, M
4+The concentration of ion remains on 0.01～1mol/L.Under 80～160 ℃ of temperature, stirred 3～15 hours, be preferably at 90～150 ℃ and stirred 13～15 hours down.Cold filtration is used deionized water wash, is dried to constant weight under 80～120 ℃, obtains MgM
4+Al-LDHs/Al
2O
3(LDHs is that the English of hydrotalcite intercalation material is called for short).
Take by weighing an amount of water-soluble palladium salt by the Pd charge capacity and be configured to the palladium salt brine solution, be preferably and make the concentration of Pd in the palladium salt brine solution remain on 0.03～0.3mol/L; With MgM
4+Al-LDHs/Al
2O
3Precursor places above-mentioned palladium salt brine solution, placed 1～24 hour in 50～90 ℃, filter, with the solid deionized water wash that obtains, under 70～120 ℃, be dried to constant weight, 300～900 ℃ roasting temperature 2～24 hours, be preferably 400～500 ℃ of following roastings 6～12 hours then.Baked sample is positioned in the fixed bed reducing apparatus, uses H
2Reduction was handled 2～24 hours under 200～600 ℃ temperature, was preferably to reduce under 300～500 ℃ temperature to handle 2～5 hours, obtained catalyzer of the present invention.
(Shimadzu) content that records Pd in this catalyzer can reach below 1% (weight) for ICP-ES, ICP-7500 by the inductively coupled plasma emmission spectrum.With H
2-TPR/TPD (Micromeritics ChemiSorb 2720), under the nitrogen atmosphere at 200 ℃ of following purge 2h, after pass to hydrogen-argon-mixed, speed with 10 ℃/min is carried out temperature programmed reduction(TPR), end of processing to be restored, sample are down to the laggard line program desorption by heating of room temperature, and the dispersity that records Pd in the catalyzer can reach more than 40%, only be 20%～25% and adopt the dispersity of Pd in the catalyzer that traditional dipping method obtains, its dispersing property is able to obvious improvement.
Method of the present invention specifically is to realize like this.The catalyzer of the present invention's preparation is passed through fixed-bed catalytic hydrogenation micro-reaction device, loaded catalyst 3.5mL, normal pressure H
2In the atmosphere behind 300 ℃ of reductase 12 h, during test with pump in the storage tank with 1, the stock liquid of the dimethyl terephthalate (DMT) of 4-dimethyl hexahydrophthalate dissolving is sent in the mixing tank, mix with hydrogen, the DMCD/DMT weight ratio is 1: 4～9: 1, be preferably 2: 1～3: 1, after the interchanger preheating, enter in the reactor and to contact with catalyzer and carry out hydrogenation reaction, reaction bed temperature control is at 150 ℃～250 ℃, working pressure control is at 5.0MPa～8.0MPa, and the volume space velocity LHSV of raw material is 0.5～10.0, H
2/ DMT (mol/mol) is 80～140, H
2Flow 5.8～33.9L/h.The reaction product of coming out from reactor enters separator and carries out gas-liquid separation through condenser, the hydrogen emptying of separating or purify after be circulated to reactor, the thick product of separating enters the product storage tank, separates desired product and purifying subsequently.
Embodiment
Embodiment 1:
Taking by weighing 4g urea and be dissolved in deionized water and be configured to 80mL solution, is the spherical η-Al of 60 orders with the 2g granularity
2O
3Add in the above-mentioned solution, under 130 ℃ of conditions, stirred 12 hours.Take by weighing 12g Mg (NO
3)
26H
2O, 6g TiCl
4Be dissolved in deionized water and be configured to 20mL solution, join said mixture, stirred 12 hours under 130 ℃ of temperature, cold filtration is used deionized water wash, and is dry under 80 ℃, obtains MgAl-LDHs/Al
2O
3Take by weighing the 0.04g Palladous chloride and be configured to the aqueous solution, with the MgTiAl-LDHs/Al that obtains
2O
3Place palladium chloride aqueous solution, in 50 ℃ shaking bath, placed 24 hours, filter, with the solid deionized water wash that obtains, in 80 ℃ down dry, then 450 ℃ roasting temperature 8 hours, baked sample is positioned in the fixed bed reducing apparatus, uses H
2Reduction was handled 3 hours under 300 ℃ temperature, obtained catalyzer of the present invention.The catalyzer that obtains consist of Pd-Mg-Ti/Al
2O
3, wherein the content of component Pd is that the content of 1.2%, Mg is that the content of 1.0%, Ti is 1.2%, with H
2The dispersity of the Pd that-TPR/TPD test obtains is 39.0%.
By fixed-bed catalytic hydrogenation micro-reaction device, carry out the dimethyl terephthalate (DMT) shortening with the catalyzer that obtains and generate the 1,4 cyclohexanedicarboxylic acid dimethyl ester, reaction conditions is: loaded catalyst 3.5mL, 220 ℃ of temperature of reaction, H
2Press and be 7.0MPa, H
2/ DMT (mol/mol) is 80, and the dimethyl terephthalate (DMT) of dissolving with the 1,4 cyclohexanedicarboxylic acid dimethyl ester is raw material (the DMT/DMCD weight part ratio is 3: 7), and the raw material volume space velocity is 1.0h
-1, liquid feed rate 3.5mL/h, H
2Flow 14.5L/h, reaction times 6h, the dimethyl terephthalate (DMT) transformation efficiency is 95% as a result, 1,4 cyclohexanedicarboxylic acid dimethyl ester selectivity 96%.
For the catalytic performance of comparative sample, we take by weighing 12g Mg (NO
3)
26H
2O, 6g TiCl
4Utilize the co-impregnation preparation at Al with the 0.04g Palladous chloride
2O
3Carrier surface, under identical appreciation condition, obtaining the result is 88% for the dimethyl terephthalate (DMT) transformation efficiency, 1,4 cyclohexanedicarboxylic acid dimethyl ester selectivity 80%.
Embodiment 2:
Taking by weighing 8g urea and be dissolved in deionized water and be configured to 70mL solution, is the spherical θ-Al of 100 orders with the 3g granularity
2O
3And α-Al
2O
3Composition add in the above-mentioned solution, under 100 ℃ of conditions, stirred 15 hours.Take by weighing 16g Mg (NO
3)
26H
2O, 6g ZrCl
4Be dissolved in deionized water and be configured to 30mL solution, join said mixture, stirred 14 hours under 110 ℃ of temperature, cold filtration is used deionized water wash, and is dry under 100 ℃, obtains MgZrAl-LDHs/Al
2O
3Take by weighing the 0.3g Palladous chloride and be configured to the aqueous solution, with the MgZrAl-LDHs/Al that obtains
2O
3Place palladium chloride aqueous solution, in 80 ℃ shaking bath, placed 12 hours, filter, with the solid deionized water wash that obtains, in 120 ℃ down dry, then 500 ℃ roasting temperature 6 hours, baked sample is positioned in the fixed bed reducing apparatus, uses H
2Reduction was handled 2.5 hours under 400 ℃ temperature, obtained catalyzer of the present invention.The catalyzer that obtains consist of Pd-Mg-Zr/Al
2O
3, wherein the content of active ingredient Pd is that the content of 0.33%, Mg is that the content of 0.75%, Zr is 1.6%, with H
2The dispersity of the Pd that-TPR/TPD test obtains is 42.6%
With the condition with embodiment 1 this catalyzer is carried out the application performance test, the dimethyl terephthalate (DMT) transformation efficiency is 96% as a result, 1,4 cyclohexanedicarboxylic acid dimethyl ester selectivity 94%.
For the catalytic performance of comparative sample, we take by weighing 16g Mg (NO
3)
26H
2O, 6g ZrCl
4Utilize the co-impregnation preparation at Al with the 0.3g Palladous chloride
2O
3Carrier surface, under identical appreciation condition, obtaining the result is 92% for the dimethyl terephthalate (DMT) transformation efficiency, 1,4 cyclohexanedicarboxylic acid dimethyl ester selectivity 88%.
Embodiment 3:
Taking by weighing 6g urea and be dissolved in deionized water and be configured to 60mL solution, is 40 order spherical gamma-Al with the 3g granularity
2O
3Add in the above-mentioned solution, under 100 ℃ of conditions, stirred 15 hours.Take by weighing 9gMg (NO
3)
26H
2O, 4g SnCl
4Be dissolved in deionized water and be configured to 60mL solution, join said mixture, stirred 10 hours under 120 ℃ of temperature, cold filtration is used deionized water wash, and is dry under 90 ℃, obtains MgSnAl-LDHs/Al
2O
3Take by weighing the 0.3g Palladous chloride and be configured to the aqueous solution, with the MgSnAl-LDHs/Al that obtains
2O
3Place palladium chloride aqueous solution, in 90 ℃ shaking bath, placed 14 hours, filter, with the solid deionized water wash that obtains, in 100 ℃ down dry, then 400 ℃ roasting temperature 9 hours, baked sample is positioned in the fixed bed reducing apparatus, uses H
2Reduction was handled 4 hours under 300 ℃ temperature, obtained catalyzer of the present invention.The catalyzer that obtains consist of Pd-Mg-Sn/Al
2O
3, wherein the content of active ingredient Pd is that the content of 0.8%, Mg is that the content of 0.8%, Ti is 1.7%, with H
2The dispersity of the Pd that-TPR/TPD test obtains is 40.7%.
With the condition with embodiment 1 this catalyzer is carried out the application performance test, the dimethyl terephthalate (DMT) transformation efficiency is 92% as a result, 1,4 cyclohexanedicarboxylic acid dimethyl ester selectivity 92%.
For the catalytic performance of comparative sample, we take by weighing 9g Mg (NO
3)
26H
2O, 4g SnCl
4Utilize the co-impregnation preparation at Al with the 0.3g Palladous chloride
2O
3Carrier surface, under identical appreciation condition, obtaining the result is 85% for the dimethyl terephthalate (DMT) transformation efficiency, 1,4 cyclohexanedicarboxylic acid dimethyl ester selectivity 78%.
Claims (5)
1. one kind prepares 1, the method of 4-dimethyl hexahydrophthalate, it is characterized in that: be under 3～8MPa absolute pressure in 150～300 ℃ of temperature and hydrogen pressure, dimethyl terephthalate (DMT) is contacted with hydrogen being stated from the presence of the supported catalyst, catalyzer comprises 0.1～3% Pd, 0.01～3% Mg and 0.01～3% tetravalent metal M, M by weight
4+Be selected from Ti
4+, Zr
4+, Sn
4+, Mn
4+, Cr
4+In one or more, surplus is alumina catalyst support; Described catalyzer obtains with following method:
(a) with water-soluble M
4+Salt and water-soluble Mg
2+The water-soluble solution that is configured to of salt joins described solution in the alkaline aqueous solution that contains carrier, makes MgM
4+Al-LDHs/Al
2O
3
(b) water-soluble palladium salt is configured to the palladium salt brine solution, the MgM that step (a) is obtained
4+Al-LDHs/Al
2O
3Place above-mentioned palladium salt brine solution, through leaving standstill, filter, obtaining described catalyzer after dry, the roasting.
2. preparation 1 according to claim 1, the method of 4-dimethyl hexahydrophthalate, it is characterized in that: be under 3～8MPa absolute pressure in 150～300 ℃ of temperature and hydrogen pressure, dimethyl terephthalate (DMT) is contacted with hydrogen being stated under the supported catalyst existence condition, described catalyzer comprises 0.1～0.5% Pd, 0.1～2% Mg and 0.1～2% tetravalent metal M, M by weight
4+Be selected from Ti
4+, Zr
4+, Sn
4+In one or more.
3. preparation 1 according to claim 2, the method of 4-dimethyl hexahydrophthalate, it is characterized in that: be under 3～8MPa absolute pressure in 150～300 ℃ of temperature and hydrogen pressure, dimethyl terephthalate (DMT) is contacted with hydrogen being stated under the supported catalyst existence condition, described catalyzer comprises 0.1～0.5% Pd, 0.1～2% Mg and 0.1～2% tetravalent metal M, M by weight
4+Be selected from Ti
4+, Zr
4+, Sn
4+In one or more, surplus is alumina catalyst support; Described catalyzer obtains with following method:
(a) with water-soluble M
4+Salt and water-soluble Mg
2+The water-soluble solution that is configured to of salt, M in the solution
4+And Mg
2+Mol ratio 1:1 joins described solution and contains Al
2O
3The concentration of carrier is in 0.5～2mol/L aqueous solution of urea, makes wherein Mg
2+, M
4+The concentration of ion remains on 0.01～1mol/L, adds 1～6gAl in every 100mL aqueous solution of urea
2O
3, stirred 13～15 hours down in 90～130 ℃, make MgM
4+Al-LDHs/Al
2O
3
(b) water-soluble palladium salt is configured to the palladium salt brine solution, the MgM that step (a) is obtained
4+Al-LDHs/Al
2O
3Place above-mentioned palladium salt brine solution, through leave standstill, filter, drying, obtain described catalyzer after 6～12 hours in 400～500 ℃ of following roastings.
4. the method for preparing the 1,4 cyclohexanedicarboxylic acid dimethyl ester according to claim 1 and 2, it is characterized in that: wherein said carrier is aluminum oxide, and its crystalline form can be selected from one or more among δ, β, γ, θ, η and the α.
5. the method for preparing the 1,4 cyclohexanedicarboxylic acid dimethyl ester according to claim 1 and 2, it is characterized in that: described carrier is θ-Al
2O
3And α-Al
2O
3Composition.
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| CN103157469A (en) * | 2013-04-11 | 2013-06-19 | 北京化工大学 | Supported bimetal nanocrystal catalyst and preparation method thereof |
| CN104148063B (en) * | 2014-06-19 | 2017-01-04 | 北京化工大学 | A kind of reforming catalyst of active center stable dispersion and preparation method thereof |
| CN110152648B (en) * | 2018-02-12 | 2022-01-04 | 中国石油化工股份有限公司 | Preparation method of tin catalyst, tin catalyst and application thereof |
| TWI684585B (en) * | 2018-11-14 | 2020-02-11 | 中國石油化學工業開發股份有限公司 | A method for preparing dimethyl 1,4-cyclohexanedicarboxylate |
| TWI690510B (en) * | 2018-12-04 | 2020-04-11 | 南亞塑膠工業股份有限公司 | Hydrogenation method for improving yield of diisooctyl cyclohexane-1,4-dicarboxylate |
| CN110683518A (en) * | 2019-10-29 | 2020-01-14 | 中国科学院深圳先进技术研究院 | Process for producing metal oxide |
| CN115364866B (en) * | 2022-08-26 | 2023-12-29 | 南京工业大学 | Ni-M@NiO-Al 2 O 3 Catalyst, preparation and application thereof |
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