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CN104829431B - Application of catalyst in improving proportion of trans-1, 4-cyclohexanedimethanol - Google Patents

Application of catalyst in improving proportion of trans-1, 4-cyclohexanedimethanol Download PDF

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Publication number
CN104829431B
CN104829431B CN201510261405.5A CN201510261405A CN104829431B CN 104829431 B CN104829431 B CN 104829431B CN 201510261405 A CN201510261405 A CN 201510261405A CN 104829431 B CN104829431 B CN 104829431B
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solution
catalyst
nitrate
catalyst precursor
crystallization
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CN104829431A (en
Inventor
宋金文
臧涵
朱天松
潘少明
朱小方
申卫卫
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Lianyungang Industrial Investment Group Co Ltd
High-Tech Research Institute Nanjing University Lianyungang
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Lianyungang Industrial Investment Group Co Ltd
High-Tech Research Institute Nanjing University Lianyungang
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
    • B01J2523/17—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
    • B01J2523/27—Zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
    • B01J2523/31—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/09—Geometrical isomers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses application of a catalyst in improving the proportion of trans-1, 4-cyclohexanedimethanol. The catalyst is prepared by virtue of methods of fractional precipitation and dynamic crystallization by taking copper, zinc and aluminum as active ingredients and Mg, Ba, Mn and the like as auxiliaries. The catalyst is reduced in hydrogen before use, is heated to 220 DEG C at a rate of 10 DEG C/min and is maintained to be reduced for 2-10 hours. The catalyst prepared has a high specific surface area and uniform grain size and has high activity and high selectivity if being used for hydrogenating dimethyl 1,4-cyclohexane dicarboxylate to prepare 1,4-cyclohexanedimethanol, and the effect that the cis/trans ratio is adjustable is achieved.

Description

A kind of application of catalyst in the ratio for improving trans 1,4-CHDM
Technical field
The present invention relates to a kind of application of catalyst, particularly a kind of catalyst is in the trans 1,4-CHDM of raising Ratio on application, belong to the technical field of catalytic hydrogenation.
Background technology
1,4-CHDM (CHDM), white waxy solid.There are two kinds of different structural formulas, it is trans and cis, melt 43 DEG C (cis) of point, 70 DEG C (trans), 286 DEG C of boiling point.Relative density 1.150 (20/4 DEG C).160 DEG C of sublimation temperature, with water, alcohol It is miscible, ketone is dissolved in, aliphatic hydrocarbon, ether is practically insoluble in.
1,4-CHDM is the upgraded product of the production polyester for substituting ethylene glycol or other polyhydric alcohol Raw material, has more preferable heat stability and chemical stability good by materials such as its high-performance polyesters for synthesizing, without phenyl ring, nothing Poison, is a kind of environmental protection plasticizer and green chemical.The high polymer fusing point 260 of cis -1,4-CHDM synthesis ～267 DEG C, anti-form-1,4- cyclohexanedimethanols synthesis high polymer 315～320 DEG C of fusing point, combination property show it is trans- CHDM performances are better than cis-CHDM.Presently commercially available CHDM is that suitable, back mixing is fit, anti-along than being usually 1.0～2.5:1.
At present, industrial production 1,4-CHDM is hydrogenated with by raw material of dimethyl terephthalate (DMT) through two steps Method production is obtained, and Yi Si Man of the U.S. is to apply for Patents earliest, and Yi Si Man produces work in CHDM so far Maintain the leading position in terms of skill.CN102795965A discloses the technique that two step method produces 1,4-CHDM, using solid Fixed bed reacts, with dimethyl terephthalate (DMT) as raw material, a step benzene ring hydrogenation Ru/Al2O3For catalyst, condition is 140 DEG C, 4.0Mpa.Two step ester through hydrogenation are 180 DEG C with modified Cu-Cr catalyst, condition, 5.0Mpa.1,4-CHDM it is total Yield is 94.3%.U.S.'s Yi Si Man patent US6600080 prepares 1,4-CHDM using a step hydrogenation method, with Terephthalyl alcohol is raw material, and using 5%Ru/C catalyst, condition is 100 DEG C, 4.9Mpa, but 1,4-CHDM Yield is 76%.One step hydrogenation method is high to equipment requirements, and product purity is low, and later separation is more complicated.Only describe in patent The yield of product 1,4-CHDM, but and in undeclared product trans, cis-isomer composition because it is suitable, Both crystal structures anti-are different, so as to the melt temperature and density of polyester are also different.
The content of the invention
It is an object of the invention to provide a kind of application of catalyst, the catalysis can be used to adjust 1,4-CHDM Middle anti-form-1, the ratio of 4- cyclohexanedimethanols, so that improve the performance of product.
The technical scheme for realizing the object of the invention is：A kind of catalyst for preparing 1,4-CHDM, it is described Catalyst by following steps prepare：
(1) zinc nitrate, aluminum nitrate are dissolved in the water containing 1～2wt% Polyethylene Glycol, are configured to solution A；By nitric acid Copper and promoter metal nitrate are configured to B solution；Precipitant is configured to into C solution；
(2) solution A and C solution are poured in colloid mill simultaneously, high-speed stirred 2-10min obtains catalyst precursor 1；
(3) B solution is slowly added to in catalyst precursor 1, and high-speed stirred 10-30min obtains catalyst precursor 2；
(4) catalyst precursor 2 is washed to without Cl-, crystallization is carried out in being transferred to rotation crystallization instrument, after natural cooling simultaneously Washing, obtains catalyst precursor 3；
(5) catalyst precursor 3 is dried into the roasting at 200～700 DEG C DEG C；
(6) it is standby after tabletting screening.
In step (1), described Polyethylene Glycol adopts Macrogol 2000～12000；Described promoter metal nitric acid Salt is one or more in magnesium nitrate, manganese nitrate and barium nitrate；During precipitant is sodium hydroxide, sodium carbonate and sodium bicarbonate One or more, precipitant is 1.2～1.5 with the mol ratio of each metal nitrate summation:1.
In step (2) and (3), the rotating speed of colloid mill high-speed stirred is 2000-5000r/min.
In step (4), the condition of crystallization is：Rotating speed 30-100r/min, temperature 50-80 DEG C, crystallization time 12-24h.
In step (5), baking temperature is 80～120 DEG C, and drying time is 2～24h；Roasting time is 2h～24h.
Anti-form-1,4- hexamethylene are adjusted when being applied to prepare 1,4-CHDM by catalyst prepared by said method The ratio of dimethanol, described catalyst face hydrogen reduction before the use, with 10 DEG C/min ramps to 220 DEG C, keep also Former 2-10h.
Compared with prior art, beneficial effects of the present invention are：(1) by composition and the preparation of change CuZnAl catalyst Method, the specific surface area of catalyst of preparation are big, and active constituent is evenly distributed, and aperture even.(2) the CuZnAl catalyst application In 1,4-CHDM is prepared, feed stock conversion is high, and target product selectivity is good, while anti-form-1 can be adjusted, 4- rings The ratio of hexane dimethanol, so that improve the performance of product.
Specific embodiment
In following embodiments, using 7820 analytical reactions thing conversion ratios of gas chromatograph Agilent, yield, selectivity； The full-automatic specific surface area produced using Beijing Jin Aipu Science and Technology Ltd.s and Porosimetry V-Sorb 2800P are determined and are urged Agent specific surface area, pore volume and aperture.
The catalyst for evaluating present invention preparation is carried out in 50ml high pressure fixed beds.Constant temperature portion in portion's adds one in the reactor Quantitative catalyst, upper-lower section are filled with quartz sand.After with hydrogen exchange device, catalyst is reduced.The system for the treatment of reaches During the temperature and pressure of setting, the boosting of raw material Jing pumps is mixed with hydrogen, into hydrogenation reactor, adjusts reaction bar as needed Part (such as pressure, temperature, hydrogen-oil ratio etc.).Product Jing heat exchangers are cooled down, and enter high-pressure separator gas-liquid separation, the High Pressure Hydrogen isolated Gas Jing recycle compressors are sent into reactor cycles and are used, and the highly pressurised liquid containing a small amount of gas enters low pressure separator and further enters circulation of qi promoting Liquid is separated, and is isolated a gas part and is discharged response system, and a part is entered on-line chromatograph and analyzes its composition；Separate the liquid after gas Body enters fractional distillation refining plant, carries out refinement treatment, and the qualified products of acquisition enter products pot.
Embodiment 1
According to Cu contents 40wt% in catalyst, Zn contents 20wt%, Al content 40wt% accurately measure corresponding copper nitrate, Zinc nitrate, aluminum nitrate.2g PEG20000 heating for dissolving is weighed in deionized water, zinc nitrate, aluminum nitrate is configured to molten Liquid A, copper nitrate are configured to solution B.The sodium bicarbonate of accurate measurement is configured to into C solution.Solution A and B solution are poured into simultaneously In colloid mill, with 3000r/min high-speed stirred 10min, catalyst precursor 1 is obtained.B solution is slowly added into before catalyst Body 1 is driven, 3000r/min high-speed stirred 15min obtains catalyst precursor 2, washing is washed with deionized to without Cl-After turn Move on in rotation crystallization instrument, rotating speed 50r/min, 80 DEG C, crystallization 12h obtains catalyst precursor 3.Presoma 3 is used into deionization 80 DEG C of vacuum drying oven is put into after water washing 2 times and is dried 24h.With the ramp of 5 DEG C/min to 600 DEG C, roasting in Muffle furnace 12h.Obtain catalyst CAT-1.
Embodiment 2
According to Cu contents 50wt% in catalyst, Zn contents 25wt%, Al content 25wt% accurately measure corresponding copper nitrate, Zinc nitrate, aluminum nitrate.2g PEG 20000 heating for dissolving is weighed in deionized water, zinc nitrate, aluminum nitrate is configured to molten Liquid A, copper nitrate are configured to solution B.The sodium hydroxide of accurate measurement is configured to into C solution.Solution A and B solution are poured into simultaneously In colloid mill, with 4000r/min high-speed stirred 10min, catalyst precursor 1 is obtained.B solution is slowly added into before catalyst Body Isosorbide-5-Nitrae 000r/min high-speed stirred 20min is driven, catalyst precursor 2 is obtained, and washing is washed with deionized to without after Cl- turns Move on in rotation crystallization instrument, rotating speed 50r/min, 80 DEG C, crystallization 16h obtains catalyst precursor 3.Presoma 3 is used into deionization 80 DEG C of vacuum drying oven is put into after water washing 2 times and is dried 8h.With the ramp of 5 DEG C/min to 550 DEG C, roasting in Muffle furnace 24h.Obtain catalyst CAT-2.
Embodiment 3
A, B, C solution preparation are poured in colloid mill simultaneously with embodiment 2, solution A and B solution, with 3000r/min high-speed stirrings 5min is mixed, catalyst precursor 1 is obtained.B solution is slowly added into into catalyst precursor 1,3000r/min high-speed stirred 15min, obtains catalyst precursor 2.The other the same as in Example 2, obtains catalyst CAT-3.
Embodiment 4
In 2 solution B of embodiment, add auxiliary agent magnesium nitrate, wherein, content of magnesium replaces 2% copper content.A, B, C solution Preparation is poured in colloid mill simultaneously with embodiment 2, solution A and B solution, with 5000r/min high-speed stirred 5min, obtains catalyst Presoma 1.B solution is slowly added into into catalyst precursor 1,5000r/min high-speed stirred 10min obtains complex catalyst precursor Body 2.The other the same as in Example 2, obtains catalyst CAT-4.
Embodiment 5
In example 2, the condition for changing dynamic crystallization is rotating speed 30r/min, and 80 DEG C, crystallization 24h, before obtaining catalyst Drive body 3.80 DEG C of vacuum drying oven is put into after presoma 3 is washed with deionized 2 times is dried 12h.With 8 DEG C/min in Muffle furnace Ramp to 650 DEG C, roasting 8h.Obtain catalyst CAT-5.
Embodiment 6
In example 2, the condition for changing dynamic crystallization is rotating speed 80r/min, and 50 DEG C, crystallization 18h, before obtaining catalyst Drive body 3.80 DEG C of vacuum drying oven is put into after presoma 3 is washed with deionized 2 times is dried 12h.With 6 DEG C/min in Muffle furnace Ramp to 650 DEG C, roasting 12h.Obtain catalyst CAT-6.
Comparative example 1
Weigh quality copper nitrate same as Example 2, zinc nitrate, aluminum nitrate and be configured to solution A.Weigh quality and enforcement 2 identical sodium hydroxide of example is configured to B solution.A, B are added in 80 DEG C of deionized waters with stirring simultaneously, 15min is reacted Post curing 8h.With pure water washing to without Cl-, 120 DEG C are dried 12h.80 DEG C of vacuum drying oven is dried 24h.With 5 in Muffle furnace DEG C/ramp to 600 DEG C of min, catalyst PAT-1 is obtained after roasting 8h.
Comparative example 2
Weigh quality copper nitrate same as Example 2, zinc nitrate, aluminum nitrate and be configured to solution A.Weigh quality and enforcement 2 identical sodium hydroxide of example is configured to B solution.A, B are added in 80 DEG C of deionized waters with stirring simultaneously, 15min is reacted Post curing 8h.Washing is washed with deionized to without Cl-After be transferred to rotation crystallization instrument in, rotating speed 40r/min, 80 DEG C, crystallization 12h, obtains catalyst precursor.80 DEG C of vacuum drying oven is put into after presoma is washed with deionized 2 times is dried 24h.Horse Not with the ramp of 5 DEG C/min to 600 DEG C, roasting 12h in stove.Obtain catalyst PAT-2.
Comparative example 3
A, B, C solution preparation are poured in colloid mill simultaneously with embodiment 2, solution A and B solution, with 4000r/min high-speed stirrings 5min is mixed, catalyst precursor 1 is obtained.B solution is slowly added into into catalyst precursor Isosorbide-5-Nitrae 000r/min high-speed stirred 15min, obtains catalyst precursor 2.80 DEG C of vacuum drying oven is put into after 2 times are washed with deionized after 2 ripening 8h of presoma It is dried 24h.With the ramp of 5 DEG C/min to 600 DEG C, roasting 12h in Muffle furnace.Obtain catalyst PAT-3.
Above-mentioned catalyst is used for DMCD Hydrogenations to react for CHDM, activity is carried out to which using 50ml fixed beds and is commented Valency, the results are shown in Table 1.
1 different catalysts conversion ratio of table, selectivity and it is anti-along than

Claims (5)

1. application of a kind of catalyst in the ratio for improving trans 1,4-CHDM, it is characterised in that described urges Agent faces hydrogen reduction before the use, with 10 DEG C/min ramps to 220 DEG C, keeps reductase 12-10h, and wherein, described urges Agent is prepared by following steps：
(1) zinc nitrate, aluminum nitrate are dissolved in the water containing 1 ~ 2wt% Polyethylene Glycol, are configured to solution A；By copper nitrate and Promoter metal nitrate is configured to B solution；Precipitant is configured to into C solution；
(2) solution A and C solution are poured in colloid mill simultaneously, high-speed stirred 2-10min obtains catalyst precursor 1；
(3) B solution is slowly added to in catalyst precursor 1, and high-speed stirred 10-30min obtains catalyst precursor 2；
(4) catalyst precursor 2 is washed to without Cl-, crystallization is carried out in being transferred to rotation crystallization instrument, after natural cooling and wash, Obtain catalyst precursor 3；
(5) catalyst precursor 3 is dried and is obtained after roasting at 200 ~ 700 DEG C DEG C.
2. it is as claimed in claim 1 to apply, it is characterised in that in step (1), Polyethylene Glycol using Macrogol 2000 ~ 12000；Promoter metal nitrate is one or more in magnesium nitrate, manganese nitrate and barium nitrate；Precipitant is sodium hydroxide, carbon One or more in sour sodium and sodium bicarbonate；Precipitant is 1.2 ~ 1.5 with the mol ratio of each metal nitrate summation:1.
3. it is as claimed in claim 1 to apply, it is characterised in that step (2) and（3）In, the rotating speed of high-speed stirred is 2000- 5000 r/min。
4. it is as claimed in claim 1 to apply, it is characterised in that in step (4), the condition of crystallization is：Rotating speed 30-100r/ Min, temperature 50-80 DEG C, crystallization time 12-24h.
5. as claimed in claim 1 to apply, it is characterised in that in step (5), baking temperature is 80 ~ 120 DEG C, drying time For 2 ~ 24h；Roasting time is 2h ~ 24h.
CN201510261405.5A 2015-05-20 2015-05-20 Application of catalyst in improving proportion of trans-1, 4-cyclohexanedimethanol Expired - Fee Related CN104829431B (en)

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TWI554544B (en) * 2015-10-26 2016-10-21 財團法人工業技術研究院 Polyester, methods for manufacturing the same and methods for manufacturing a polyester sheet
CN107188782B (en) * 2017-06-22 2021-01-08 江苏飞翔化工股份有限公司 Method for preparing 1, 4-cyclohexanedimethanol by hydrogenating dimethyl 1, 4-cyclohexanedicarboxylate
CN112264025B (en) * 2020-11-18 2021-10-15 西南化工研究设计院有限公司 Simple, energy-saving and environment-friendly preparation method of methanol synthesis catalyst

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CN1164548C (en) * 2001-04-13 2004-09-01 中国石化集团天津石油化工公司 A catalyst for hydrogenation of 1,4-cyclohexanedicarboxylate to produce 1,4-cyclohexanedimethanol and its preparation method
CN101096332A (en) * 2006-06-30 2008-01-02 中国石化上海石油化工股份有限公司 Method for preparing 1,4-cyclohexane dimethanol by hydrogenation of terephthalyl alcohol
CN102380392A (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-cyclohexanedimethanol
US8410318B2 (en) * 2011-07-29 2013-04-02 Eastman Chemical Company Process for the preparation of 1,4-cyclohexanedimethanol from terephthalic acid
CN103877991B (en) * 2012-12-19 2015-12-09 中国石油化工股份有限公司 Anti-form-1, the production method of 4-cyclohexanedimethanol and used catalyst thereof
CN103878003B (en) * 2012-12-19 2016-01-13 中国石油化工股份有限公司 Produce anti-form-1, the Catalysts and its preparation method of 4-cyclohexanedimethanol

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