CN102935365B - Catalyst and method for preparing 1,4-cyclohexane dimethyl isophthalate - Google Patents
Catalyst and method for preparing 1,4-cyclohexane dimethyl isophthalate Download PDFInfo
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- CN102935365B CN102935365B CN201210451214.1A CN201210451214A CN102935365B CN 102935365 B CN102935365 B CN 102935365B CN 201210451214 A CN201210451214 A CN 201210451214A CN 102935365 B CN102935365 B CN 102935365B
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Abstract
The invention relates to a catalyst and method for preparing 1,4-cyclohexane dimethyl isophthalate. Metal palladium serves as the main active component, metal tin serves as the auxiliary, and alumina serves as a monomer. The metal palladium occupies for 0.1-10% of the total weight of the catalyst, the metal tin serving as the auxiliary occupies for 0.01-2.0% of the total weight of the catalyst, soluble salts of the metal palladium and the metal tin are respectively prepared into water solution, then water solution containing Sn is poured into a carrier of the catalyst, after standing, ageing and drying, water solution containing Pd is poured into the obtained solid, after standing, ageing, drying and roasting, a presoma of the catalyst is obtained, and the required catalyst can be obtained by restoring the presoma through hydrogen. The reaction for preparing the 1,4-cyclohexane dimethyl isophthalate by adding hydrogen into dimethyl terephthalate has the advantages of being low in hydrogenation reaction pressure, high in catalytic activity, less in by products and the like, the conversion rate of the dimethyl terephthalate is 98-100%, and the selectivity of the 1,4-cyclohexane dimethyl isophthalate is 96-99%.
Description
Technical field
The present invention relates to the catalyst of a kind of dimethyl terephthalate (DMT) (DMT) Hydrogenation for Isosorbide-5-Nitrae-dimethyl hexahydrophthalate (DMCD).
Background technology
Isosorbide-5-Nitrae-dimethyl hexahydrophthalate is a kind of valuable chemical intermediate, the further standby 1,4-CHDM (CHDM) day by day with extensive use value of Hydrogenation, and the while itself also can be used as the monomer of polyester modification.
1,4-CHDM is mainly used in the production of the unsaturated polyester resins such as polyester sheet, sheet material, polyester bottles, polyester film, polyester engineering plastic.Due to the symmetry of CHDM structure and the existence of cyclohexane ring, make resin finished product there is good heat endurance, chemical-resistant, colorability, electrical property and corrosion resistance.
The plant-scale production of DMCD makes by dimethyl terephthalate (DMT) (DMT) catalytic hydrogenation, conventionally adopts palladium, ruthenium, nickel even load type catalyst.The method of preparing Isosorbide-5-Nitrae-dimethyl hexahydrophthalate and 1,4-CHDM with dimethyl terephthalate (DMT) as raw material has been narrated in patent US3334149 by Eastman Chemical of the U.S..The method is used palladium/aluminium oxide catalyst in the process of dimethyl terephthalate (DMT) hydrogenation generation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate, and reaction pressure is up to 34MPa.
Yisiman Chemical Company of the U.S. improves catalyst in Chinese patent CN1099745A, wherein do following explanation about catalyst: described catalyst contains the palladium being deposited on alumina support and is selected from the second group VIII metal element of nickel, platinum, ruthenium or its mixture, wherein:
(1) 0.1-5.0% that the content of palladium is catalyst weight;
(2) decentralization of palladium is at least 15%;
(3) at least 90% palladium is positioned at catalyst surface, and its degree of depth is in 200 microns;
(4) be selected from the 0.001-1.0%(weight that the content of the second group VIII metal element of nickel, platinum, ruthenium or its mixture is catalyst weight);
(5) alumina crystal is α, θ, δ, γ, η or their mixture.
This patent is in the reaction by dimethyl terephthalate (DMT) hydrogenation generation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate, and reaction pressure obtains some and reduces, but still up to more than 12.5MPa.So high pressure makes the construction cost of factory, and reaction running expense all will be very expensive.
In the Chinese patent CN1308052 of Yang Zi petrochemical industry Co., Ltd application, adopt the hydrogenation catalyst that nickel content is 40%, at pressure 3.5MPa, under 140 DEG C of conditions of temperature, carry out DMT catalytic hydrogenation, the method has reduced operating pressure and equipment investment, but DMCD yield is only 75%, cannot meet industrialization production requirements.
Summary of the invention
It is a kind of for dimethyl terephthalate (DMT) hydrogenation that the object of the invention is to provide, and produces the catalyst of Isosorbide-5-Nitrae-dimethyl hexahydrophthalate.
Technical scheme of the present invention is as follows:
Prepare a catalyst for Isosorbide-5-Nitrae-dimethyl hexahydrophthalate, catalyst is made up of main activity component metal palladium, promoter metal tin and alumina catalyst support three parts, and component and percentage by weight are as follows:
Metal Palladium 0.1-10%,
Promoter metal tin 0.01-2.0%,
Surplus is alumina catalyst support.
The main active component of the catalyst that the present invention develops is Metal Palladium.When Metal Palladium is when in total catalyst weight, proportion is less than 0.1%, catalyst activity is very low, can not reach the speed that reaction requires; Metal Palladium is when in total catalyst weight, proportion is greater than 10%, and catalyst activity is unchanged, and catalyst cost is because the increase of palladium content increases, and manufacturing process is more and more loaded down with trivial details.In range of application of the present invention, Metal Palladium should account for 0.1-10% in total catalyst weight, preferably 0.5-5.0%, further preferred 1.0-2.0%.
The auxiliary agent of the catalyst that the present invention develops is metallic tin, by adding metallic tin, can obviously improve the selective of reaction, and byproduct of reaction reduces.The addition of metallic tin accounts for 0.01-2.0% in total catalyst weight, preferably 0.05-1.0%, further preferred 0.1-0.5%.When content is less than 0.01%, the activity of catalyst is unchanged when not adding metallic tin; After content is greater than 2.0%, selectively the remaining unchanged of reaction.
The carrier of the catalyst that the present invention develops is aluminium oxide, and the aluminium oxide of selecting is γ type aluminium oxide, and its nitrogen BET specific area is at 50m
2/ g-200m
2/ g.It is rather largely known in the art that, BET surface area is the function of crystalline phase and calcination process, and in the suitable oxide phase of maintenance, BET surface area should be high as far as possible.Aluminium oxide BET specific area is at 50m
2/ g-200m
2outside/g time, the crystalline phase that aluminium oxide forms has been not suitable for the chemical reaction of the present invention's application.
Of the present invention 1, the method for preparing catalyst of 4-dimethyl hexahydrophthalate, respectively by the solubility salt of Metal Palladium and metallic tin, be mixed with the aqueous solution, then will pour in catalyst carrier containing the aqueous solution of Sn, leave standstill aging, dry after, again the aqueous solution containing Pd is poured in gained solid, standing aging, after drying, roasting, obtain catalyst precursor, finally with obtaining required catalyst after hydrogen reducing precursor.
The solubility salt of described Metal Palladium and metallic tin is PdCl
2, Pd (NO
3)
2, SnCl
22H
2o or SnCl
45H
2o.
Use catalyst of the present invention to carry out dimethyl terephthalate (DMT) hydrogenation, while producing Isosorbide-5-Nitrae-dimethyl hexahydrophthalate, all evaluation experimentals all carry out in fixed bed reactors, this system comprises that a segment length is 0.6 meter, 316 stainless steel tubes of internal diameter 12mm, loads at catalyst upper-lower section
1～2 glass marble, catalyst (10ml) is seated in the middle part of reaction tube, by the temperature of the thermocouple measurement reaction bed in reaction tube.The air path part of this reaction comprises high pressure hydrogen source of the gas, modulates required reaction pressure through pressure-regulating valve, enters reactor assembly and contacts with reaction mass, and the material after hydrogenation reaction enters high-voltage product knockout drum.The temperature of reactor maintains 190 DEG C, and reaction pressure is 6.0MPa, DMT conversion ratio 98～100%, DMCD selective 96～99%.The features such as this catalyst composition is simple, and preparation easily, in the reaction at dimethyl terephthalate (DMT) Hydrogenation for Isosorbide-5-Nitrae-dimethyl hexahydrophthalate, has hydrogenation reaction pressure low, and catalytic activity is high, and accessory substance is few.
Detailed description of the invention:
1, the preparation of catalyst:
Embodiment 1
Configure respectively 20 milliliters containing 0.45 gram of PdCl
2the aqueous solution, 20 milliliters containing 0.068 gram of SnCl
22H
2the aqueous solution of O, take 17.7 gram of 10～20 object alumina carrier, first will flood above-mentioned alumina carrier containing the Sn aqueous solution, leave standstill aging, natural drying after, to add in the alumina carrier that has flooded Sn containing the Pd aqueous solution again, continuation leaves standstill aging, natural drying, 120 DEG C of oven dryings, then 420 DEG C of roastings four hours in Muffle furnace, obtain catalyst precursor.Before evaluation experimental, 10 milliliters of catalyst precursors are placed in to tubular reactor, in this reactor, pass into hydrogen, hydrogen flowing quantity is controlled at 30～50ml/min, under 300 DEG C of conditions of temperature, reduce 3 hours, in prepared catalyst, tenor is 1.5%Pd and 0.2%Sn.Catalyst is labeled as 1
#.
Embodiment 2-9
According to the method in embodiment 1, change PdCl
2and SnCl
22H
2the consumption of O, prepares other catalyst.
Pd in catalyst prepared by each embodiment and Sn content are in table 1.
Table 1. catalyst composition
Embodiment 10
Configure respectively 20 milliliters containing 0.58 gram of Pd (NO
3)
2the aqueous solution, 20 milliliters containing 0.105 gram of SnCl
45H
2the aqueous solution of O, takes 17.7 gram of 10～20 object alumina carrier, according to the preparation method in embodiment 1, Kaolinite Preparation of Catalyst.In prepared catalyst, tenor is 1.5%Pd and 0.2%Sn.Catalyst is labeled as 10
#.
2, DMT Hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate:
Embodiment 11
The catalyst 1 that embodiment 1 is obtained
#, on fixed bed reactors, test.Loaded catalyst is 10 milliliters, reaction pressure is adjusted to 6.0MPa, temperature maintains 190 DEG C, reaction raw materials is the DMT/DMCD solution of 10% (weight), and charging rate is 30ml/h, and amounts of hydrogen is 300ml/min, after reaction smooth running, sampling, through gas chromatographic analysis, normalization method calculates that reaction conversion ratio is 99.6%, product D MCD is selectively 99.0%.
Embodiment 12-20
Successively by catalyst 2
#～10
#for embodiment 12～20, carry out evaluation experimental according to the method for embodiment 11.
Result of the test is listed in table 2.
Table 2. evaluation test result
Comparative example 1
Configure 20 milliliters containing 0.45 gram of PdCl
2the aqueous solution, take 17.7 gram of 10～20 object alumina carrier, will add in alumina carrier containing the Pd aqueous solution, standing aging, natural drying, 120 DEG C of oven dryings, then 420 DEG C of roastings four hours in Muffle furnace, obtain catalyst precursor, and catalyst consists of 1.5%Pd.Before evaluation experimental, 10 milliliters of catalyst precursors are placed in to tubular reactor, in this reactor, pass into hydrogen, hydrogen flowing quantity is controlled at 30～50ml/min, under 300 DEG C of conditions of temperature, reduces 3 hours.Carry out evaluation experimental according to the method for embodiment 11 again.Result of the test shows that reaction conversion ratio is 98.5%, product D MCD is selectively 94.2%.
Comparative example 2
Configure 20 milliliters containing 0.34 gram of SnCl
22H
2the aqueous solution of O, takes 17.7 gram of 10～20 object alumina carrier, will flood above-mentioned alumina carrier containing the Sn aqueous solution, standing aging, natural drying, 120 DEG C of oven dryings, then 420 DEG C of roastings four hours in Muffle furnace, obtain catalyst precursor, and catalyst consists of 1%Sn.Before evaluation experimental, 10 milliliters of catalyst precursors are placed in to tubular reactor, in this reactor, pass into hydrogen, hydrogen flowing quantity is controlled at 30～50ml/min, under 300 DEG C of conditions of temperature, reduces 3 hours.Carry out evaluation experimental according to the method for embodiment 11 again.
Result of the test shows that catalyst is to this reaction non-activity.
Claims (4)
1. prepare the catalyst of 1,4 ?dimethyl hexahydrophthalate for one kind, it is characterized in that: catalyst is made up of main activity component metal palladium, promoter metal tin and alumina catalyst support three parts, and component and percentage by weight are as follows:
Metal Palladium: 1.5 ?2.0%,
Promoter metal tin: 0.2 ?0.5%,
Surplus is carrier γ type aluminium oxide.
2. described in claim 11,4 ?the method for preparing catalyst of dimethyl hexahydrophthalate, it is characterized in that: respectively by the solubility salt of Metal Palladium and metallic tin, be mixed with the aqueous solution, then will pour in catalyst carrier containing the aqueous solution of Sn, leave standstill aging, dry after, again the aqueous solution containing Pd is poured in gained solid, standing aging, after drying, roasting, obtain catalyst precursor, finally with obtaining required catalyst after hydrogen reducing precursor.
3. method as claimed in claim 2, is characterized in that the solubility salt of described Metal Palladium is PdCl
2or Pd (NO
3)
2.
4. method as claimed in claim 2, is characterized in that the solubility salt of described metallic tin is SnCl
22H
2o or SnCl
45H
2o.
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| CN201210451214.1A CN102935365B (en) | 2012-11-12 | 2012-11-12 | Catalyst and method for preparing 1,4-cyclohexane dimethyl isophthalate |
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| CN201210451214.1A CN102935365B (en) | 2012-11-12 | 2012-11-12 | Catalyst and method for preparing 1,4-cyclohexane dimethyl isophthalate |
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| KR101883993B1 (en) * | 2016-09-29 | 2018-07-31 | 롯데케미칼 주식회사 | Preparation method of 1,3-cyclohexanedicarboxylic acid |
| CN111569926B (en) * | 2020-04-23 | 2023-03-24 | 台州学院 | Boron nitride loaded palladium-gold-tin liquid alloy catalyst and preparation method and application thereof |
| CN111672508B (en) * | 2020-06-23 | 2023-03-14 | 中国天辰工程有限公司 | Preparation and application of catalyst for preparing 1,4-dimethyl cyclohexanedicarboxylate through dimethyl terephthalate hydrogenation |
| CN113680351A (en) * | 2021-09-10 | 2021-11-23 | 润泰化学（泰兴）有限公司 | Preparation method and application of dioctyl phthalate prepared dioctyl p-cyclohexanedicarboxylate bimetallic indium oxide catalyst |
| CN114789056A (en) * | 2022-04-26 | 2022-07-26 | 中国科学院过程工程研究所 | Hydrogenation catalyst, preparation method and application thereof |
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|---|---|---|---|---|
| US5286898A (en) * | 1993-06-15 | 1994-02-15 | Eastman Kodak Company | Low pressure process for the hydrogenation of dimethyl benzenedicarboxylates to the corresponding dimethyl cyclohexanedicarboxlates |
| US5399742A (en) * | 1993-06-15 | 1995-03-21 | Eastman Chemical Company | Low pressure process for the manufacture of cyclohexanedicarboxylate esters |
| CN1772377A (en) * | 2005-10-25 | 2006-05-17 | 中国石油天然气股份有限公司 | Catalyst for eliminating hydrocarbon impurity from CO2 and its prepn and application |
| CN102380373A (en) * | 2010-09-01 | 2012-03-21 | 中国石油天然气股份有限公司 | Catalyst for preparing 1,4-cyclohexane dicarboxylic acid dimethyl ester |
-
2012
- 2012-11-12 CN CN201210451214.1A patent/CN102935365B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5286898A (en) * | 1993-06-15 | 1994-02-15 | Eastman Kodak Company | Low pressure process for the hydrogenation of dimethyl benzenedicarboxylates to the corresponding dimethyl cyclohexanedicarboxlates |
| US5399742A (en) * | 1993-06-15 | 1995-03-21 | Eastman Chemical Company | Low pressure process for the manufacture of cyclohexanedicarboxylate esters |
| CN1772377A (en) * | 2005-10-25 | 2006-05-17 | 中国石油天然气股份有限公司 | Catalyst for eliminating hydrocarbon impurity from CO2 and its prepn and application |
| CN102380373A (en) * | 2010-09-01 | 2012-03-21 | 中国石油天然气股份有限公司 | Catalyst for preparing 1,4-cyclohexane dicarboxylic acid dimethyl ester |
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