CN110090647A - A kind of catalyst and preparation method preparing 1,4- cyclohexane dicarboxylic acid di-isooctyl - Google Patents
A kind of catalyst and preparation method preparing 1,4- cyclohexane dicarboxylic acid di-isooctyl Download PDFInfo
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- CN110090647A CN110090647A CN201910206896.1A CN201910206896A CN110090647A CN 110090647 A CN110090647 A CN 110090647A CN 201910206896 A CN201910206896 A CN 201910206896A CN 110090647 A CN110090647 A CN 110090647A
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- catalyst
- carrier
- auxiliary agent
- isooctyl
- dicarboxylic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 title description 4
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 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 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 8
- 239000011777 magnesium Substances 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 8
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 10
- -1 phthalic acids ester Chemical class 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Chemical class 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical class [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 description 1
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical class CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010019695 Hepatic neoplasm Diseases 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- BYGQIUHOWVUUPS-UHFFFAOYSA-N dioctyl cyclohexane-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1CCC(C(=O)OCCCCCCCC)CC1 BYGQIUHOWVUUPS-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 230000001738 genotoxic effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 206010020718 hyperplasia Diseases 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- 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
- 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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
-
- 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)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Catalysts (AREA)
Abstract
1 is prepared the invention discloses a kind of, the catalyst and preparation method of 4- cyclohexane dicarboxylic acid di-isooctyl, its main feature is that including carrier, main active component and auxiliary agent, carrier is one of activated alumina, silica, diatomite, main active component is ruthenium, and auxiliary agent is the one or more of nickel, palladium, magnesium.The beneficial effects of the present invention are: the present invention use using ruthenium as main active component, the catalyst that nickel, palladium, magnesium are prepared as auxiliary agent, preparation process is simple, production cost is low, catalyst is used to prepare Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid di-isooctyl conversion ratio and selectivity is high, is suitable for large-scale production.
Description
Technical field
The invention belongs to catalyst technical fields, more particularly to one kind is for adding hydrogen to produce Isosorbide-5-Nitrae-benzene dicarboxylic acid dioctyl ester
The catalyst and preparation method thereof of cyclohexane dicarboxylic acid di-isooctyl.
Background technique
The phthalic acids ester plasticizers such as dioctyl phthalate (DOP), dioctyl terephthalate (DOTP), solely with it
Special excellent properties play significant role in polyvinyl chloride plastic material products and its application, and production capacity increases year by year at present, such as 2018
Annual capacity is up to 1,800,000 tons.A large amount of zooperies prove, Long Term Contact phthalic acid esters energy initiated oxidation object enzyme body hyperplasia, in turn
Induce liver tumour.Therefore many countries have started to limit or have forbidden directly connecing in medical instrument, food, toy for children etc. with human body
These phthalic acid ester plasticizers are used in the plastic products of touching.Cyclohexanedicarboxyester ester class compound, such as Isosorbide-5-Nitrae-hexamethylene two
Carboxylic acid di-isooctyl, the polyvinyl chloride (PVC) for being proved not only to make it to be plasticized have better properties, and do not present toxicity or
Genotoxicity, cyclohexanedicarboxyester ester class compound is not only suitable for food fresh keeping membrane, pad, sports and leisure product etc. in seal food
Sensitive soft PVC (PVC) product, it can also be used to produce children under three years of age's toy, domestic food contact gloves, environmental protection
Wallpaper, decorative sheets of material, intravenous blood transfusion tube and medical blood bag etc. in type room.Due to its wide application prospect, hexamethylene two
The synthesis of carboxylic acid ester compound receives significant attention.
In the prior art, Chinese patent application, application number 201610061045.9, the applying date 20160128, Shen Qing Publication
Number CN105732370A, data of publication of application 20160706 disclose " a kind of to prepare Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dioctyl ester side
Method ", including using Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and octanol as raw material, under the action of acidic molecular sieve or acid salt are catalyst,
Lactate synthesis 1,4 cyclohexanedicarboxylic acid dioctyl ester under conditions of 120~200 DEG C of reaction temperature；Octanol be n-octyl alcohol and/or
Isooctanol, acid salt are selected from sodium bisulfate and potassium acid sulfate.The present invention is using specific catalyst and in specific reaction temperature
The lower esterification for completing Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic and octanol, obtains Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dioctyl ester.But the technology
Scheme high production cost, yield are low, are not suitable for industrial mass production, the catalyst that acidic molecular sieve or acid salt are made into
Because technical limitation development is restricted.
Chinese patent application, application number CN201310015626.5, the applying date 20130116, Authorization Notice No.
CN103130648B, authorized announcement date 20150107, disclose " it is a kind of prepare Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dioctyl ester device and
Its method ", including by terephthalic acid (TPA) and octanol to carry out esterification acquisition terephthalic acid (TPA) two at 220~230 DEG C pungent
Ester, then add the obtained Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic two of hydrogen pungent at 12.9MPa and 200 DEG C the dioctyl terephthalate of acquisition
Ester.1,4 cyclohexanedicarboxylic acid two is prepared using the relatively simple and safe method for being first esterified back end hydrogenation in the technical solution
Monooctyl ester, but do not disclose using catalyst, and esterification products add the pressure condition requirement of hydrogen high, and use program product 1,
The conversion per pass and yield of 4- cyclohexane cyclohexanedimethanodibasic dioctyl ester are by larger limitation, while aftertreatment technology is cumbersome, and has useless
Water generates.
Summary of the invention
In the present invention, unless otherwise stated, Science and Technology noun used herein has art technology
The normally understood meaning of personnel institute.For a better understanding of the present invention, the definition and explanation of relational language is provided below.
As used in this article, catalyst, according to International Federation of Pure Chemical and Applied Chemistry (IUPAC) 1981
Definition: catalyst is a kind of change reaction rate but does not change the substance for reacting total standard Gibbs free energy.Catalyst is being changed
It learns caused effect in reaction and cries catalytic action.Catalyst is industrially also referred to as catalyst.The composition of catalyst itself, chemically
Matter and quality before the reaction after do not change.
As used in this article, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid di-isooctyl, alias: Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dioctyl ester,
Molecular formula: C24H44O4, molecular weight: 396.6, No. CAS: 84731-70-4, chemical structural formula is
As used in this article, dioctyl terephthalate (DOTP), molecular formula: C24H38O4, No. CAS: 6422-86-2,
Molecular weight: 390.5, structural formula:Appearance is in pale yellow transparent oily liquids or colorless and transparent oily liquid
Body.- 48 DEG C of freezing point, 383 DEG C of boiling point (0.1) MPa.s (0 DEG C), 399 DEG C of ignition point, be the master of polyvinyl chloride (PVC) plastics
Plasticizer.It has heat-resisting, cold-resistant, difficult volatilization, anti-extraction, flexibility and electricity compared with diisooctyl phthalate (DOP)
The advantages that good insulation preformance, shows that excellent persistence, resistance to soap be aqueous and low-temperature pliability in product.
As used in this article, term " adding hydrogen " is used interchangeably with " hydrogenation reaction ", refers to that hydrogen and other compounds are mutual
The reaction process of effect usually carries out in the presence of a catalyst.
In order to overcome the deficiencies of the prior art, the purpose of the present invention is to provide one kind adds hydrogen for dioctyl terephthalate
Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid di-isooctyl catalyst and preparation method thereof is produced, is used using ruthenium as main active component, selection
The catalyst of suitable auxiliary agents preparation carries out catalysis reaction, and preparation process is simple, and at low cost, hydrogenation selectivity is higher.
To achieve the above object, the present invention adopts the following technical scheme:
It is a kind of to prepare Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid di-isooctyl catalyst, its main feature is that, catalyst be include carrier, master
Active component and auxiliary agent are wanted, the carrier is one of activated alumina, silica, diatomite or several, the main work
Property group be divided into ruthenium, the auxiliary agent is the one or more of nickel, palladium, magnesium, the main active component content is 0.4 by mass~
1.5%, the auxiliary agent content is 0.04~0.1% by mass.
Further, the auxiliary agent is nickel, palladium, magnesium a period of time, and auxiliary agent content is 0.04~0.1% by mass.
Further, the carrier is activated alumina, and 0.5~0.8ml/g of Kong Rongwei of the activated alumina compares table
150~350m of area2/g。
The present invention also provides a kind of methods for preparing above-mentioned catalyst, its main feature is that, carrier is immersed in the water, unit is measured
Quality carrier can absorb the volume of water, and caning absorb the equal principle of liquor capacity according to unit mass carrier can show that metal salt is molten
Liquid product, is then calculated the quality that unit mass carrier needs metal salt solution according to content of metal, then according to gold
The quality and volume for belonging to salting liquid prepare corresponding solution, then immerse in the solution carrier and stand, dry, then calcine,
400~500 DEG C of calcination temperature, 4~8h of calcination time, last 8~14h of reduction activation in the hydrogen gas atmosphere.
Further, the metal salt solution is one of chloride, nitrate.
The beneficial effects of the present invention are: the present invention use using ruthenium as main active component, nickel, palladium, magnesium are as auxiliary agent system
Standby catalyst, preparation process is simple, and production cost is low, and catalyst is used to prepare Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid di-isooctyl conversion
Rate and selectivity are high, are suitable for large-scale production.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
It can be with conventional products that are commercially available.
Embodiment
The present invention, which provides, a kind of prepares Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid di-isooctyl catalyst, including carrier, chief active
Component and auxiliary agent, carrier are activated alumina, and main active component is ruthenium, and auxiliary agent is the one or more of nickel, palladium, magnesium, mainly
Active component content is 0.4~1.5% by mass, and auxiliary agent content is 0.04~0.1% by mass；The hole of activated alumina
Hold is 0.5~0.8ml/g, 150~350m of specific surface area2/g。
Ruthenium catalyst is prepared by the following method, activated alumina is immersed in the water, and measures unit mass active oxidation
Aluminium can absorb the volume of water, and caning absorb the equal principle of liquor capacity according to unit mass activated alumina can show that metal salt is molten
Liquid product, is then calculated the quality that unit mass activated alumina needs metal salt solution according to the load capacity of metal, so
Corresponding solution is prepared according to the quality of metal salt solution and volume afterwards, then activated alumina is immersed in the solution and is stood,
It is dry, it then calcines, calcination temperature, calcination time, finally 8~14h of reduction activation in the hydrogen gas atmosphere.
Above-mentioned metal salt solution is one of nitrate solution, chloride brine solution.
Catalyst prepared by the above method is prepared into 1,4- cyclohexane dicarboxylic acid di-isooctyl by the following method: in fixation
Catalyst is used in bed hydroprocessing device, DOTP is inputted by pump and entered fixed bed reaction after the hydrogen that hydrogen compressor inputs mixes
Device, the material after reaction, which enters after cooler, to be entered back into gas-liquid separator and is separated, and product is mainly Isosorbide-5-Nitrae-hexamethylene after reaction
Alkane 2-dicarboxylic acid diethylhexyl ester；Reaction condition: 140 DEG C of temperature, pressure 8Mpa, air speed 1h-1, hydrogen ester molar ratio 100:1 obtains such as table
1 illustrated embodiment 1-5.
Table 1
| Embodiment | Ruthenium | Nickel | Magnesium | Palladium | Calcination temperature DEG C | Calcination time h | Conversion ratio | Selectivity |
| 1 | 0.5 | 0.05 | 0 | 0 | 430 | 6 | 97.6% | 96.4% |
| 2 | 0.5 | 0.08 | 0 | 0 | 460 | 8 | 98.9% | 95.8% |
| 3 | 0.8 | 0.05 | 0 | 0 | 430 | 6 | 99.7% | 97.1% |
| 4 | 0.8 | 0 | 0 | 0.05 | 430 | 6 | 99.8% | 96.8% |
| 5 | 0.8 | 0 | 0.05 | 0 | 430 | 6 | 99.3% | 97.3% |
Although a specific embodiment of the invention has obtained detailed description, those skilled in the art will appreciate that root
According to all technical data having disclosed, details can be carry out various modifications and be changed, and these change in the present invention
Protection scope within.Full scope of the invention is as given by appended claims and its any equivalent.
Claims (5)
1. a kind of prepare Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid di-isooctyl catalyst, it is characterised in that: catalyst be include carrier, master
Active component and auxiliary agent are wanted, the carrier is one of activated alumina, silica, diatomite or several, the main work
Property group be divided into ruthenium, the auxiliary agent is the one or more of nickel, palladium, magnesium, the main active component content is 0.4 by mass~
1.5%, the auxiliary agent content is 0.04~0.1% by mass.
2. a kind of according to claim 1 prepare Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid di-isooctyl catalyst, it is characterised in that: institute
Stating auxiliary agent is nickel, palladium, magnesium a period of time, and auxiliary agent content is 0.04~0.1% by mass.
3. a kind of according to claim 1 prepare Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid di-isooctyl catalyst, it is characterised in that: institute
Stating carrier is activated alumina, 0.5~0.8ml/g of Kong Rongwei of the activated alumina, 150~350m of specific surface area2/g。
4. a kind of preparation method of the catalyst as described in claim any one of 1-2, it is characterised in that: carrier is immersed in the water,
The volume that unit mass carrier can absorb water is measured, caning absorb the equal principle of liquor capacity according to unit mass carrier can obtain
Then the quality that unit mass carrier needs metal salt solution is calculated according to content of metal, so in metal salt solution volume
Corresponding solution is prepared according to the quality of metal salt solution and volume afterwards, then carrier is immersed in the solution and is stood, it is dry, so
After calcine, 400~500 DEG C of calcination temperature, 4~8h of calcination time, last 8~14h of reduction activation in the hydrogen gas atmosphere.
5. a kind of preparation method of catalyst according to claim 4, it is characterised in that: the metal salt solution is chlorination
One of object, nitrate.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476052A (en) * | 2010-11-29 | 2012-05-30 | 中国石油化工股份有限公司 | Supported ruthenium catalyst and preparation method thereof |
| WO2015057311A1 (en) * | 2013-10-18 | 2015-04-23 | Exxonmobile Chemical Patents Inc. | A hydrogenation catalyst, its method of preparation and use |
| CN105688915A (en) * | 2016-04-13 | 2016-06-22 | 凯凌化工(张家港)有限公司 | Dual-function catalyst for hydrogenating benzene rings and reducing carbonyl, preparation of dual-function catalyst and application thereof |
| CN105727995A (en) * | 2016-03-22 | 2016-07-06 | 凯凌化工(张家港)有限公司 | Catalyst capable of preparing cyclohexane organic matters by hydrogenating benzene ring organic matters and preparation method and application of catalyst |
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2019
- 2019-03-19 CN CN201910206896.1A patent/CN110090647A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102476052A (en) * | 2010-11-29 | 2012-05-30 | 中国石油化工股份有限公司 | Supported ruthenium catalyst and preparation method thereof |
| WO2015057311A1 (en) * | 2013-10-18 | 2015-04-23 | Exxonmobile Chemical Patents Inc. | A hydrogenation catalyst, its method of preparation and use |
| CN105727995A (en) * | 2016-03-22 | 2016-07-06 | 凯凌化工(张家港)有限公司 | Catalyst capable of preparing cyclohexane organic matters by hydrogenating benzene ring organic matters and preparation method and application of catalyst |
| CN105688915A (en) * | 2016-04-13 | 2016-06-22 | 凯凌化工(张家港)有限公司 | Dual-function catalyst for hydrogenating benzene rings and reducing carbonyl, preparation of dual-function catalyst and application thereof |
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