CN108940305A - The production method and ester through hydrogenation catalyst of the preparation method and cyclohexanedimethanol of hydrogenation catalyst and cyclohexane cyclohexanedimethanodibasic dibasic ester - Google Patents

The production method and ester through hydrogenation catalyst of the preparation method and cyclohexanedimethanol of hydrogenation catalyst and cyclohexane cyclohexanedimethanodibasic dibasic ester Download PDF

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CN108940305A
CN108940305A CN201710351517.9A CN201710351517A CN108940305A CN 108940305 A CN108940305 A CN 108940305A CN 201710351517 A CN201710351517 A CN 201710351517A CN 108940305 A CN108940305 A CN 108940305A
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ester
hydrogenation
hydrogen
liquid
hydrogenation catalyst
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CN108940305B (en
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向明林
汪永军
周冬京
杜鹏
敖博
佘喜春
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Hunan Changlian New Material Technology Co ltd
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Hunan Changling Petrochemical Technology Development Co Ltd
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    • 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
    • B01J23/8926—Copper 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
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    • 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
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • 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
    • B01J23/84—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 arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a kind of hydrogenation catalyst and application, using the catalyst cyclohexane cyclohexanedimethanodibasic dibasic ester preparation method and cyclohexanedimethanol production method, the active element and auxiliary element that the catalyst contains carrier and is supported on carrier, active element is selected from one or more of Rh, Ru and Pd, auxiliary element is Cu and/or Ag, and carrier is active carbon and/or aluminium oxide.The hydrogenation catalyst has the catalytic activity significantly improved, especially has the low-temperature catalytic activity significantly improved.The invention also discloses a kind of ester through hydrogenation catalyst and preparation method and ester through hydrogenation method, which is metal composite oxide, and the metallic element in metal composite oxide contains Cu, Zn and M, and M is Zr and/or Ti.The ester through hydrogenation catalyst has the catalytic activity significantly improved, even can also obtain higher feed stock conversion at a lower temperature, while can also obtain higher selectivity of product.

Description

The preparation method and hexamethylene diformazan of hydrogenation catalyst and cyclohexane cyclohexanedimethanodibasic dibasic ester The production method and ester through hydrogenation catalyst of alcohol
Technical field
The present invention relates to a kind of hydrogenation catalyst and its applications, and the invention further relates to a kind of cyclohexane cyclohexanedimethanodibasic dibasic esters Preparation method, the invention further relates to a kind of production method of cyclohexanedimethanol, the present invention further relates to a kind of ester through hydrogenation and urges Agent and preparation method thereof and ester through hydrogenation method.
Background technique
1,4-CHDM is a kind of cycloaliphatic diols of symmetrical configuration, and it is industrial that there are two primary hydroxyls for tool The raw materials for production of important polyester, such as poly terephthalic acid Isosorbide-5-Nitrae-cyclohexane dicarboxylates (PCT), polyethylene terephthalate Ester -1,4 cyclohexane dimethanol ester (PETG) and polyethylene terephthalate -1,4 cyclohexane dimethanol ester (PCTG).With 1,4 cyclohexane dimethanol is that the saturated polyester of Material synthesis can be made into the plasticizer of high performance glaze and coating.1,4- ring Hexane dimethanol may be additionally used for being modified other unsaturated polyester resins, these polyester resin absorbabilities are extremely low, boiling water resistance energy Preferably, resistance is high, and corrosion resistance is good, can be used for making high quality mould coating, lamination and note film resin, can be widely used for production electricity Sub- product resin and insulated wire etc..The most important application of 1,4-CHDM still prepares linear polyester fibers, by Fiber relative density made of the raw material is light, fusing point is high, good electrical property, especially suitable for making electrical equipment.
Currently, industrial 1,4-CHDM is mainly used using dimethyl terephthalate (DMT) as raw material, first pass around Isosorbide-5-Nitrae-dimethyl hexahydrophthalate is made in one section of benzene ring hydrogenation, then carries out two sections of ester through hydrogenation and obtain 1,4-CHDM.
Benzene ring hydrogenation is reacted, CN1099744A discloses a kind of continuous work for producing cyclohexanedicarboxylate Skill, the technique include the following steps:
(1) by hydrogen and liquid containing cyclohexanedicarboxylate's product and corresponding rutgers reactant Body mixture is fed continuously into the hydroconversion reaction zone containing at least one carrying alumina palladium hydrogenation catalyst fixed bed；
(2) hydrogen and product liquid containing cyclohexanedicarboxylate's product are continuously removed from hydroconversion reaction zone；
Wherein, rutgers are in 10-205 bars of absolute pressure (1000-20500 kPas) and 150-230 DEG C of temperature quilt It is hydrogenated into cyclohexanedicarboxylate, and the concentration of carbon monoxide is maintained at a below from the hydrogen that hydroconversion reaction zone is shifted out 200ppm (volume).
The technique uses noble metal catalyst, includes the palladium catalyst of carrier, which has the feature that
(1) palladium content is the 0.5-2.0% of catalyst weight；
(2) dispersibility of palladium is at least 20%；
(3) at least the palladium of 90% weight is counted on aluminium oxide of its depth less than 200 microns positioned at from oxidation aluminium surface；
(4) lattice of aluminium oxide is α, θ, δ, γ, η or their mixture.
Ester through hydrogenation is reacted, CN1109859A discloses a kind of pair of dialkyl cyclohexanedicarboxylate and hydrogenated to produce The method of cyclohexanedimethanol, this method comprises:
(a) hydrogenation zone of the copper catalyst of the manganese co-catalysis containing granular reduction is provided；
(b) in the temperature that temperature range is in about 150 DEG C to about 350 DEG C and higher than feed streams dew point, feed pressure range Hydrogenatable material is formed under conditions of being about 10.34 bars to about 137.90 bars containing dialkyl cyclohexanedicarboxylate and about 0.1% (weight Amount) to the steam feed streams of about 15% (weight) acidic materials, the steam mixture has known hydrogen-containing gas and hexamethylene Dicarboxylic acid dialkyl esters ratio；
(c) steam feed is streamed into hydrogenation zone；
(d) hydrogenation conditions in hydrogenation zone is maintained to be higher than its dew point when contacting reaction mixture and catalyst；
(e) steam feed streams are passed through into hydrogenation zone；
(f) product stream containing cyclohexanedimethanol is recycled from hydrogenation zone.
Although using dimethyl terephthalate (DMT) as raw material produce 1,4 cyclohexane dimethanol have been achieved for it is some research at Fruit, still, prior art still have the space improved.For example, simplifying there is still a need for feed stock conversion is further increased Process is purified, product quality is improved；And there is still a need for the operation energy consumptions for further decreasing technique, such as reduce hydrogenation reaction Temperature.
Summary of the invention
It is an object of the present invention to improve to prepare cyclohexane cyclohexanedimethanodibasic using dimethyl terephthalate ester as raw material Feed stock conversion in the hydrogenation reaction (benzene ring hydrogenation saturated reaction) of dialkyl ester.
It is another object of the present invention to improve to carry out ester through hydrogenation reaction by raw material of cyclohexane cyclohexanedimethanodibasic dialkyl ester Prepare the feed stock conversion in the ester through hydrogenation reaction of cyclohexanedimethanol.
According to the first aspect of the invention, the present invention provides a kind of hydrogenation catalyst, the catalyst contain carrier with And load active element and auxiliary element on the carrier, the active element be selected from one of Rh, Ru and Pd or Two or more, the auxiliary element is Cu and/or Ag, and the carrier is active carbon and/or aluminium oxide.
According to the second aspect of the invention, the present invention provides hydrogenation catalysts described in first aspect according to the present invention Agent is answered as the catalyst of cyclohexane cyclohexanedimethanodibasic dibasic ester shown in phthalic acid binary ester through hydrogenation preparation formula II shown in Formulas I With,
In Formulas I and Formula II, R1And R2Respectively C1-C12Alkyl.
According to the third aspect of the present invention, the present invention provides a kind of preparation method of cyclohexane cyclohexanedimethanodibasic dibasic ester, This method is included under hydrogenation conditions, will be containing phthalic acid dibasic ester shown in hydrogen, Formulas I and optional solvent Raw mixture contacts in the reactor with the hydrogenation catalyst through reduction activation, obtains containing hexamethylene diformazan shown in Formula II The product mixtures of sour dibasic ester, wherein the hydrogenation catalyst is hydrogenation catalyst described in first aspect of the present invention,
In Formulas I and Formula II, R1And R2Respectively C1-C12Alkyl.
According to the fourth aspect of the present invention, the present invention provides a kind of production method of cyclohexanedimethanol, this method The following steps are included:
(1) using method described in third aspect of the present invention, the phthalic acid dibasic ester preparation formula II institute as shown in Formulas I The cyclohexane cyclohexanedimethanodibasic dibasic ester shown,
In Formulas I and Formula II, R1And R2Respectively C1-C12Alkyl；
It (2), will be containing cyclohexane cyclohexanedimethanodibasic dibasic ester, hydrogen shown in Formula II and optional under ester through hydrogenation reaction condition The ester through hydrogenation raw mixture of solvent contacted with the ester through hydrogenation catalyst through reduction activation, obtain hexamethylene shown in formula III Dimethanol,
Hydrogenation catalyst according to the present invention has the catalytic activity significantly improved, especially has the low temperature significantly improved Catalytic activity carries out hydrogenation reaction even if at a lower temperature contacting with hydrogen phthalic acid dibasic ester, can also obtain compared with High phthalic acid binary ester conversion rate.Hydrogenation catalyst of the invention also shows the selectivity of product significantly improved, as Phthalic acid dibasic ester is contacted to the catalyst for carrying out benzene ring hydrogenation saturated reaction with hydrogen, higher hexamethylene diformazan can be obtained Sour dibasic ester selectivity.
According to the fifth aspect of the present invention, the present invention provides a kind of ester through hydrogenation catalyst, which is compound gold Belong to oxide, the metallic element in the metal composite oxide contains Cu, Zn and M, and M is Zr and/or Ti.
6th aspect according to the present invention, the present invention provides a kind of preparation method of ester through hydrogenation catalyst, this method packets It includes following steps: the predecessor of Cu predecessor, Zn predecessor and M is co-precipitated, collect the sediment that co-precipitation obtains, And roast sediment, for the precipitating reagent used that is co-precipitated for acidic precipitation agent, M is selected from Mn, Al, Zr, Mg and Ti One or more of.
According to the seventh aspect of the present invention, the present invention provides a kind of ester through hydrogenation method, this method is included in ester through hydrogenation Under reaction condition, by the ester through hydrogenation raw material containing cyclohexane cyclohexanedimethanodibasic dibasic ester, hydrogen shown in Formula II and optional solvent Mixture is contacted with the ester through hydrogenation catalyst through reduction activation, obtains cyclohexanedimethanol shown in formula III, wherein the ester Hydrogenation catalyst is ester through hydrogenation catalyst described in the 5th aspect of the present invention or the side as described in the 6th aspect of the present invention The ester through hydrogenation catalyst of method preparation,
In Formula II, R1And R2Respectively C1-C12Alkyl；
Ester through hydrogenation catalyst according to the present invention has the catalytic activity significantly improved, even at a lower temperature It is catalyzed ester through hydrogenation reaction, can also obtain higher feed stock conversion, while higher selectivity of product can also be obtained.
Detailed description of the invention
A kind of preferred embodiment for the air and liquid mixer that Fig. 1 is used to illustrate that the present invention uses.
Fig. 2 is used to illustrate a kind of preferred embodiment party of the production method of 1,4 cyclohexane dimethanol according to the present invention Formula.
Description of symbols
A: dialkyl B: cyclohexane cyclohexanedimethanodibasic dialkyl ester C1: hydrogen
C2: 1: the first raw material of hydrogen pumps 2: the first air and liquid mixers
3: 4: the first gas-liquid separator 4A of hydrogenator: gaseous stream
4B: liquid phase stream 5: pipeline 6: pipeline
7: the second raw materials pump 8: the second air and liquid mixers 9: ester through hydrogenation reactor
10: the second gas-liquid separator 10A: gaseous stream 10B: liquid phase stream
11: the component 12 for abutting gas channel and fluid passage: shell
13: gas access 14: liquid inlet 15: liquid outlet
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more New numberical range, these numberical ranges should be considered as specific open herein.
In the present invention, " adding hydrogen " refers in the presence of hydrogen gas, and benzene ring hydrogenation is saturated as cycloaliphatic ring；" ester through hydrogenation " refers to In the presence of hydrogen gas, alcohol is converted by ester.
According to the first aspect of the invention, the present invention provides a kind of hydrogenation catalyst, the catalyst contain carrier with And the active element and auxiliary element of load on the carrier.
The active element is selected from one or more of Rh, Ru and Pd.Using the total amount of hydrogenation catalyst as base Standard, based on the element, the content of the active element can be 0.1-8 weight %, preferably 0.3-6 weight %.In the present invention, urge The type and content of active element use x-ray fluorescence spectrometry in agent.
The auxiliary element is Cu and/or Ag.On the basis of the total amount of hydrogenation catalyst, based on the element, the auxiliary agent member The content of element can be 0.1-4 weight %, preferably 0.2-2 weight %.
From the angle for the catalytic activity for further increasing hydrogenation catalyst, based on the element, the active element and institute The molar ratio for stating auxiliary element is preferably 1:0.05-1.
Hydrogenation catalyst according to the present invention, the carrier are active carbon and/or Al2O3.The active carbon and Al2O3's Source is not particularly limited, and can be the active carbon and Al of the carrier for being suitable for loaded catalyst in various sources2O3.Institute State Al2O3Lattice structure be not particularly limited, can be α-Al2O3、θ-Al2O3、δ-Al2O3、γ-Al2O3With η-Al2O3In A combination of one or more.
Hydrogenation catalyst according to the present invention can be prepared using conventional method.Specifically, the catalyst can use The combination of one or more of the precipitation method, infusion process, hydrothermal synthesis method is made.
In a preferred embodiment, the hydrogenation catalyst is prepared using dipping method, comprising the following steps:
(1) water soluble compound containing active element and the water soluble compound containing auxiliary element are dispersed in water In, form maceration extract；
(2) with the maceration extract impregnated carrier；
(3) carrier through impregnating is contacted with reducing agent, by the water soluble compound containing active element and The water soluble compound reduction containing auxiliary element.
The type of the water soluble compound containing active element is not particularly limited, specific example may include but It is not limited to: one in radium chloride, ruthenic chloride, rhodium nitrate, nitric acid ruthenium, rhodium acetate, ruthenium acetate, palladium chloride, acid chloride and palladium nitrate Kind is two or more.The water soluble compound containing auxiliary element can be conventional selection, such as can for chloride and/ Or nitrate.The dipping can carry out under normal conditions.Generally, dipping can be in environment temperature, such as 10-60 DEG C of temperature Degree is lower to carry out.
The reducing agent various can be enough the water soluble compound containing active element and institute to be common Stating the water soluble compound reduction containing auxiliary element becomes the reducing substances of corresponding metallic element.Preferably, described to go back Former agent is the combination selected from one or more of hydrazine hydrate, sodium borohydride and formaldehyde.The dosage of the reducing agent can be with For conventional selection, corresponding metallic element can be restored the compound containing active element or be reduced to substantially by being subject to.Generally, The molar ratio of reducing agent and the active element being supported on carrier can be 2-6:1.
The reduction can carry out under normal conditions, and being subject to can be such that reduction reaction carries out.Generally, the reduction can With 20-90 DEG C at a temperature of carry out, preferably 50-80 DEG C at a temperature of carry out.The duration of the reduction reaction is with energy By the water soluble compound containing active element and the water soluble compound reduction containing auxiliary element or substantially Subject to reduction.Generally, the duration of the reduction reaction can be 1-10 hours, preferably 3-6 hours.
Restoring obtained hydrogenation catalyst can be dried under normal conditions, to remove solvent therein.Generally, The drying can 40-150 DEG C at a temperature of carry out, preferably 50-120 DEG C (such as 50-100 DEG C) at a temperature of carry out.Institute Stating the dry duration can be selected according to the temperature being dried, can remove by solvent removal therein or substantially Subject to.Generally, the duration of the drying can be 8-24 hours, preferably 12-20 hours.The drying can be in sky It carries out, can also be carried out in non-oxidizing atmosphere in gas atmosphere, the non-oxidizing atmosphere such as nitrogen atmosphere and/or zero group Element atmosphere (such as argon gas).When being dried in air atmosphere, the drying preferably no more than 100 DEG C at a temperature of into Row, such as 40-80 DEG C at a temperature of carry out.The drying can carry out under normal pressure (that is, 1 standard atmospheric pressure), can also be It carries out, is not particularly limited under conditions of decompression.
Hydrogenation catalyst according to the present invention, before use, reduction activation can be carried out using conventional method.
Hydrogenation catalyst according to the present invention is particularly suitable as the catalyst for the reaction for being saturated benzene ring hydrogenation, can be obvious Reduce the reaction temperature of hydrogenation reaction, and can significantly improve phenyl ring plus hydrogen saturation factor.
As a result, according to the second aspect of the invention, the present invention provides add hydrogen to urge described in first aspect of the present invention Catalyst of the agent as cyclohexane cyclohexanedimethanodibasic dibasic ester shown in phthalic acid binary ester through hydrogenation preparation formula II shown in Formulas I Using,
In Formulas I and Formula II, R1And R2Respectively C1-C12Alkyl, as methyl, ethyl, n-propyl, isopropyl, normal-butyl, Sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, n-heptyl, different heptyl, n-octyl, iso-octyl, Positive decyl, isodecyl, n-undecane base, 1- methyldecyl, dodecyl or 1- methylundecyl.
The specific example of the phthalic acid dibasic ester can include but is not limited to: repefral, adjacent benzene two Formic acid diethylester, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, O-phthalic Sour diisodecyl ester, diisooctyl phthalate, diisononyl phthalate, dimethyl terephthalate (DMT), terephthalic acid (TPA) Diethylester, terephthalic acid (TPA) di-n-propyl ester, terephthalic acid (TPA) diisopropyl ester, di-n-butyl terephthalate, terephthalic acid (TPA) two The combination of one or more of isodecyl ester, Di-2-ethylhexyl terephthalate and terephthalic acid (TPA) dinonyl.
Preferably, the phthalic acid dibasic ester is terephthalic acid (TPA) dibasic ester.It is highly preferred that the phthalic acid binary Ester is dimethyl terephthalate (DMT).
According to the third aspect of the present invention, the present invention provides a kind of preparation method of cyclohexane cyclohexanedimethanodibasic dibasic ester, This method is included under hydrogenation conditions, will mix containing the raw material of hydrogen, phthalic acid dibasic ester and optional solvent Object contacts in the reactor with the hydrogenation catalyst through reduction activation, obtains the product mixing containing cyclohexane cyclohexanedimethanodibasic dibasic ester Object.
Method described in third aspect, the hydrogenation catalyst are described in first aspect of the present invention according to the present invention Detailed description has been carried out above for hydrogenation catalyst, the hydrogenation catalyst and its composition, and and will not be described here in detail.
Method described in third aspect, hydrogenation catalyst are handled through reduction activation according to the present invention.The reduction activation It can carry out under normal conditions.Generally, the reduction activation is using hydrogen as reducing agent.The volume space velocity of hydrogen can be with For 300-3000h-1, preferably 1000-2000h-1.The reduction activation can be in 100-400 DEG C, preferably 200-380 DEG C of temperature Degree is lower to carry out.The pressure carried out in the reactor of reduction activation can be 0-1MPa, preferably 0.2-0.8MPa, and the pressure is Gauge pressure.The duration of the reduction can be selected according to the temperature of reduction, generally can be 5-20 hours, preferably 8- 18 hours.The reduction activation can carry out in hydrogenator, can not also carry out in hydrogenator, preferably add It is carried out in hydrogen reactor.
Method described in third aspect according to the present invention by hydrogen and can contain phthalic acid two using conventional method The material liquid of first ester mixes, to obtain the raw mixture.For example, by hydrogen and benzene diformazan can be contained in a mixer The material liquid of sour dibasic ester mixes, and the mixer can be one or more of dynamic mixer, static mixer Combination.The static mixer is realized by the flow regime of change fluid and is uniformly mixed gas with liquid, specifically may be used Think but be not limited to SV type static mixer, SK type static mixer, SX type static mixer, SH type static mixer and SL type One of static mixer is a variety of.The dynamic mixer can be realized for the various movements by moving component by gas The mixing apparatus being uniformly mixed with liquid, the moving component for example can be the common various components with agitating function.
From the angle for further increasing selectivity of product and feed stock conversion, in a preferred embodiment, Hydrogen is injected in the material liquid by a kind of air and liquid mixer, so that the raw mixture is obtained, the gas-liquid mixed Device includes that at least one fluid passage for being used to accommodate the material liquid leads to at least one for accommodating gas of the hydrogen Road, adjacent by a component between the fluid passage and the gas passage, the component at least partially has porose area, institute State hydrogen has porose area to be injected in the material liquid by described.In the present invention, term " fluid passage " is to refer to accommodate liquid The space of body material (such as material liquid)；Term " gas passage " is the space for referring to accommodate gas material (such as hydrogen).
The component at least partially has a porose area, described to have porose area to extend along the length direction of the component.Preferably, It is described to there is porose area to cover entire component (that is, by with the average pore size between the fluid passage and the gas passage Component for the hole of nano-scale is adjacent, and the hydrogen is injected into the material liquid by the hole).It is described to have porose area It is the hole of nano-scale with the average pore size, so that hydrogen is infused by described with the hole that average pore size is nano-scale Enter in the material liquid.
In the preferred embodiment, the hole having in porose area can be micron openings and/or nano-pore.The present invention In, term " micron openings " refers to that average pore size is greater than the hole of 1000nm, and the average pore size of the micron openings is preferably not greater than 500 μm, more preferably not more than 400 μm.In the present invention, term " nano-pore " refers to that average pore size is not more than the hole of 1000nm, such as flat The hole that equal aperture is 1nm to 1000nm.It is highly preferred that the average pore size for having the hole in porose area is 30nm to 500 μm.More into Preferably, the average pore size for having the hole in porose area is 50nm to 400 μm to one step.The average pore size uses scanning electron microscope method Measurement.
In the preferred embodiment, the component can for one of perforated membrane, porous plate and void channels or Two or more combinations.The void channels refer to that the wall in channel is porous.The inner surface of the void channels and/or outer Surface can adhere to perforated membrane, the aperture in the hole on pipeline can be adjusted in this way, such as: the hole on the wall of the pipeline It can be micron openings, be attached to hole on the inner surface of the pipeline and/or the perforated membrane on outer surface can be nano-pore, this In invention, the pipeline that the perforated membrane that hole therein is nano-pore is attached on inner surface and/or outer surface, which is also considered as, porose area In hole be nano-pore.As an example of the pipeline with perforated membrane, the void channels can be membrane tube.It is described porous The quantity in the channel in pipeline is not particularly limited, and generally, the quantity in the channel in the void channels can be 4-20 item.
In the actual operation process, the component and a shell can be used cooperatively, to form the gas-liquid mixed Device.The shell is internally provided at least one described component, and the inner space of the shell is separated into liquid by the component Body channel and gas passage.The shell has gas access, liquid inlet and liquid outlet, the both ends point of the fluid passage It is not connected to the liquid inlet and the liquid outlet, the gas passage is connected to the gas access.Fig. 1 shows institute State a kind of preferred embodiment of air and liquid mixer.(component in Fig. 1 is void channels) can be with as shown in Figure 1, component 11 Shell 12 is used cooperatively.That is, at least one component 11 is placed in shell 12, and make the outer wall of component 11 and the inner wall of shell 12 Between there are spaces.The channel surrounded by component 11 as the fluid passage for accommodating liquid phase stream, the outer wall of component 11 with The space that the inner wall of shell 12 is formed is as the gas passage for accommodating hydrogen；Alternatively, the channel that component 11 surrounds is as use In the gas passage for accommodating hydrogen, the space that the outer wall of component 11 and the inner wall of shell 12 are formed is used as accommodating liquid phase stream Fluid passage.Preferably, the channel that component 11 surrounds is as the fluid passage for accommodating liquid phase stream, the outer wall of component 11 The space formed with the inner wall of shell 12 is as the gas passage for accommodating hydrogen.
In the channel that the component surrounds as the fluid passage for accommodating liquid phase stream, the outer wall of the component and institute When stating space that the inner wall of shell is formed as gas passage for accommodating hydrogen, as shown in Figure 1, can set on housing 12 Set gas access 13, liquid inlet 14 and liquid outlet 15, the both ends of the fluid passage respectively with liquid inlet 13 and liquid 15 connection of outlet, the gas passage are connected to gas access 13.Hydrogen is sent into shell 12 by gas access 13, by liquid Phase logistics is sent into the channel of component 11, under the action of pressure difference, hydrogen is made to enter the liquid phase object by the hole on tube wall In stream, to obtain hydrogeneous liquid phase stream.
The material for forming the component can be inorganic material (such as inorganic ceramic), or organic material, as long as shape Chemical interaction does not occur with hydrogen and liquid phase stream at the material of the component.
In the preferred embodiment, the air and liquid mixer can be arranged in the arrival end of the reactor, thus The raw mixture that air and liquid mixer exports is sent directly into reactor.
Method described in third aspect according to the present invention, the injection rate of hydrogen can be according to phthalic acid two in material liquid The content of first ester is selected, and is subject to and is enough phthalic acid binary ester hydrogenation.It is preferred above in use as an example When embodiment the method injects hydrogen in the material liquid by a kind of air and liquid mixer, the injection rate of hydrogen with it is described The molar ratio of phthalic acid dibasic ester in material liquid can be 3.5-6:1, such as 3.5:1,3.6:1,3.7:1,3.8:1,3.9: 1,4:1,4.1:1,4.2:1,4.3:1,4.4:1,4.5:1,4.6:1,4.7:1,4.8:1,4.9:1,5:1,5.1:1,5.2:1, 5.3:1,5.4:1,5.5:1,5.6:1,5.7:1,5.8:1,5.9:1 or 6:1.
Method described in third aspect according to the present invention, by using hydrogenation catalyst of the invention, even if lower At a temperature of by hydrogen and phthalic acid dibasic ester and the hydrogenation catalyst haptoreaction through reduction activation, also can be by phthalic acid Dibasic ester can significantly improve the selectivity to cyclohexane cyclohexanedimethanodibasic dibasic ester with higher conversion.Specifically, may be used With by hydrogen and phthalic acid dibasic ester and the hydrogenation catalyst through reduction activation 80-160 DEG C at a temperature of contact, such as 80℃、81℃、82℃、83℃、84℃、85℃、86℃、87℃、88℃、89℃、90℃、91℃、92℃、93℃、94℃、95 ℃、96℃、97℃、98℃、99℃、100℃、101℃、102℃、103℃、104℃、105℃、106℃、107℃、108℃、 109℃、110℃、111℃、112℃、113℃、114℃、115℃、116℃、117℃、118℃、119℃、120℃、121 ℃、122℃、123℃、124℃、125℃、126℃、127℃、128℃、129℃、130℃、131℃、132℃、133℃、 134℃、135℃、136℃、137℃、138℃、139℃、140℃、141℃、142℃、143℃、144℃、145℃、146 ℃、147℃、148℃、149℃、150℃、151℃、152℃、153℃、154℃、155℃、156℃、157℃、158℃、 159 DEG C or 160 DEG C.
Method described in third aspect according to the present invention, can be at lower pressures by hydrogen and phthalic acid binary Ester is contacted with the hydrogenation catalyst through reduction activation.Specifically, in terms of gauge pressure, the pressure in reactor can be 0.2-10MPa, Preferably 0.5-7MPa.
Method described in third aspect, the hydrogenation catalyst of use show that higher hydrogenation catalyst is living according to the present invention Property, even if at lower temperature and lower pressure, it also can be with higher feed space velocity, effectively by phthalic acid dibasic ester Hydrogenation, and obtain higher selectivity of product.Specifically, the weight (hourly) space velocity (WHSV) of the raw mixture in terms of phthalic acid dibasic ester can Think 0.5-3h-1。
Method described in third aspect according to the present invention, can be by hydrogen and phthalic acid dibasic ester and through reduction activation Hydrogenation catalyst contacted in common various reactors.In a preferred embodiment, by hydrogen and benzene two Formic acid dibasic ester is contacted in fixed bed reactors with the hydrogenation catalyst through reduction activation, described can will add hydrogen at this time Catalyst packing is in fixed bed reactors and carries out reduction activation, will mix containing the raw material of hydrogen and phthalic acid dibasic ester Object is sent into fixed bed reactors, is contacted with the hydrogenation catalyst through reduction activation.In the preferred embodiment, using Previously described air and liquid mixer the air and liquid mixer can be arranged in the fixation come when forming the raw mixture The arrival end of bed reactor.In the preferred embodiment, from the angle for further increasing hydrogenation reaction effect, preferably The raw mixture is sent into the reactor in a manner of from bottom to top.The reactor is preferably tubular reactor. The tubular reactor refers to that the draw ratio of reactor is greater than 1 reactor.By taking tubular fixed-bed reactor as an example, tubular type is fixed The ratio of height to diameter of catalyst bed in bed reactor can be 5-20:1.
Method described in third aspect according to the present invention, the phthalic acid dibasic ester can be conventional selection.Tool Body, the phthalic acid dibasic ester can be Formulas I compound represented, correspondingly, the cyclohexane cyclohexanedimethanodibasic dibasic ester of preparation For Formula II compound represented,
In Formulas I and Formula II, R1And R2Respectively C1-C12Alkyl, as methyl, ethyl, n-propyl, isopropyl, normal-butyl, Sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, n-hexyl, isohesyl, n-heptyl, different heptyl, n-octyl, iso-octyl, Positive decyl, isodecyl, n-undecane base, 1- methyldecyl, dodecyl or 1- methylundecyl.
The specific example of the phthalic acid dibasic ester can include but is not limited to: repefral, adjacent benzene two Formic acid diethylester, n-propyl phthalate, diisopropyl phthalate, n-butyl phthalate, O-phthalic Sour diisodecyl ester, diisooctyl phthalate, diisononyl phthalate, dimethyl terephthalate (DMT), terephthalic acid (TPA) Diethylester, terephthalic acid (TPA) di-n-propyl ester, terephthalic acid (TPA) diisopropyl ester, di-n-butyl terephthalate, terephthalic acid (TPA) two The combination of one or more of isodecyl ester, Di-2-ethylhexyl terephthalate and terephthalic acid (TPA) dinonyl.
Preferably, the phthalic acid dibasic ester is terephthalic acid (TPA) dibasic ester.It is highly preferred that the phthalic acid binary Ester is dimethyl terephthalate (DMT).
Method described in third aspect, the raw mixture can contain solvent, can also be free of according to the present invention There is solvent.In one embodiment, the raw mixture does not contain solvent, can effectively improve the effective of device at this time Treating capacity.In another embodiment, the raw mixture also contains at least one solvent, at this time can be to reaction rate It is adjusted.The solvent can be conventional selection.Generally, the solvent can be the benzene diformazan that can be dissolved as raw material The liquid substance of sour dibasic ester.Preferably, the solvent is cyclohexane cyclohexanedimethanodibasic dibasic ester shown in Formula II.It is highly preferred that institute Stating solvent is cyclohexane cyclohexanedimethanodibasic dibasic ester identical with the hydrogenation products of phthalic acid dibasic ester shown in Formulas I, can be exempted from this way Except subsequent separation process.The dosage of the solvent can be conventional selection.Generally, the dosage of the solvent can make institute The content for stating phthalic acid dibasic ester in raw mixture is 5-20 weight %.
Method described in third aspect according to the present invention, the product containing cyclohexane cyclohexanedimethanodibasic dibasic ester being prepared Mixed liquor can be exported directly；Can also as use cyclohexane cyclohexanedimethanodibasic dibasic ester for the reaction unit of raw material into Material, is used for example as the charging of ester through hydrogenation reaction, and further progress ester through hydrogenation reaction prepares cyclohexanedimethanol.
As a result, according to the fourth aspect of the present invention, the present invention provides a kind of production methods of cyclohexanedimethanol, should Method includes step (1) (hereinafter also referred to hydrogenation reaction step): using method described in third aspect of the present invention, by Formulas I Shown in cyclohexane cyclohexanedimethanodibasic dibasic ester shown in phthalic acid dibasic ester preparation formula II.
Cyclohexane cyclohexanedimethanodibasic dibasic ester shown in phthalic acid dibasic ester and Formula II shown in Formulas I has been carried out above Detailed description, and will not be described here in detail.Step (1) uses method described in third aspect of the present invention by phthalic acid binary Ester through hydrogenation obtains cyclohexane cyclohexanedimethanodibasic dibasic ester, and detailed description has been carried out above for specific method and condition, herein No longer it is described in detail.
Method described in 4th aspect according to the present invention, including step (2) (hereinafter also referred to ester through hydrogenation reaction step): Under ester through hydrogenation reaction condition, by the ester containing cyclohexane cyclohexanedimethanodibasic dibasic ester, hydrogen shown in Formula II and optional solvent Hydrogenating materials mixture is contacted with the ester through hydrogenation catalyst through reduction activation, obtains cyclohexanedimethanol shown in formula III,
The ester through hydrogenation raw mixture can contain solvent, can also not contain solvent.Preferably, the ester through hydrogenation is anti- Raw mixture is answered to contain at least one solvent.The solvent can be can to dissolve cyclohexane cyclohexanedimethanodibasic dibasic ester and molten Solve the liquid substance of cyclohexanedimethanol.Preferably, the solvent is selected from C1-C6One or more of alcohol.It is described The specific example of solvent can include but is not limited to one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and tert-butyl alcohol Or it is two or more.Preferably, the solvent is methanol.On the basis of the total amount of the ester through hydrogenation raw mixture, hexamethylene two The content of formic acid dibasic ester can be 10-90 weight %, and the content of solvent can be 10-90 weight %.
Conventional method can be used hydrogen and the ester through hydrogenation containing cyclohexane cyclohexanedimethanodibasic dibasic ester and optional solvent Material liquid mixing, to obtain the ester through hydrogenation raw mixture.For example, can be in a mixer by hydrogen and ester through hydrogenation raw material Liquid mixing, the mixer can be the combination of one or more of dynamic mixer, static mixer.The static state Detailed description has been carried out above for the type of mixer and the dynamic mixer, and and will not be described here in detail.
From the angle for further increasing selectivity of product and feed stock conversion, in a preferred embodiment, Hydrogen is injected in the ester through hydrogenation material liquid by previously described air and liquid mixer, so that it is mixed to obtain the ester through hydrogenation raw material Object is closed, at this point, the ester through hydrogenation material liquid is contained in the fluid passage.The structure of the air and liquid mixer and operation side Detailed description has been carried out above for formula, and and will not be described here in detail.The air and liquid mixer can be arranged anti-in ester through hydrogenation The arrival end of device is answered, so that the ester through hydrogenation raw mixture that air and liquid mixer exports is sent directly into ester through hydrogenation reactor.This When, from the angle for further increasing ester through hydrogenation reaction effect, preferably by the ester through hydrogenation raw mixture with from bottom to top Mode be sent into ester through hydrogenation reactor.
In ester through hydrogenation reaction step, the injection rate of hydrogen can be according to the cyclohexane cyclohexanedimethanodibasic dibasic in ester through hydrogenation material liquid The content of ester is selected, and is subject to and is enough to hydrogenate cyclohexane cyclohexanedimethanodibasic dibasic ester.It is excellent above in use as an example When embodiment the method being selected to inject hydrogen in the ester through hydrogenation material liquid by the air and liquid mixer, the injection of hydrogen Amount and the molar ratio of the cyclohexane cyclohexanedimethanodibasic dibasic ester in the ester through hydrogenation material liquid can be 4.5-8:1, such as 4.5:1,4.6: 1,4.7:1,4.8:1,4.9:1,5:1,5.1:1,5.2:1,5.3:1,5.4:1,5.5:1,5.6:1,5.7:1,5.8:1,5.9: 1,6:1,6.1:1,6.2:1,6.3:1,6.4:1,6.5:1,6.6:1,6.7:1,6.8:1,6.9:1,7:1,7.1:1,7.2:1, 7.3:1,7.4:1,7.5:1,7.6:1,7.7:1,7.8:1,7.9:1 or 8:1.
The ester through hydrogenation catalyst can carry out ester through hydrogenation reaction for the common cyclohexane cyclohexanedimethanodibasic dibasic ester that is enough to be catalyzed Catalyst.Such as: Cu-series catalyst.
In a preferred embodiment, the ester through hydrogenation catalyst is metal composite oxide, the composition metal Metallic element in oxide contains Cu, Zn and M, and M is selected from one or more of Mn, Al, Zr, Mg and Ti.From into The angle that one step improves the catalytic activity of ester through hydrogenation catalyst is set out, and M is preferably Zr and/or Ti.
On the basis of the total amount of metal composite oxide, in terms of oxide (oxide refers to full oxide), Cu Content can be the content of 30-60 weight %, Zn can be the content of 10-50 weight %, M can be 20-40 weight %.
The metal composite oxide can be prepared using common method.As a preferred embodiment, the compound gold Belong to oxide to prepare using coprecipitation.
The co-precipitation can carry out in alkaline medium, that is, use alkaline precipitating agent, by Cu predecessor, Zn predecessor with And the predecessor of M is co-precipitated, and collects the sediment that co-precipitation obtains, and sediment is roasted, to obtain described Metal composite oxide.The specific example of the alkaline precipitating agent can include but is not limited to: Na2CO3、NaHCO3, NaOH and ammonia One or more of water.
The present inventor has found in the course of the research, is co-precipitated in alkaline environment with using alkaline precipitating agent The metal composite oxide is prepared to compare, be co-precipitated in acidic environment using acidic precipitation agent and the compound gold for preparing Belong to oxide and show higher catalytic activity, the temperature of ester through hydrogenation reaction can be greatly reduced, moreover it is possible to obtain higher product choosing Selecting property.The acidic precipitation agent is preferably one or more of oxalic acid, propionic acid, butyric acid and succinic acid.It is highly preferred that institute Stating acidic precipitation agent is oxalic acid.
The dosage of precipitating reagent can be selected according to the dosage of metal precursor, generally, the dosage of the precipitating reagent It is 1.1-2 times of theoretical amount, preferably 1.2-1.5 times of theoretical amount.
The Cu predecessor can be that precipitation reaction can occur under the action of alkaline precipitating agent or acidic precipitation agent, Precipitating is formed, and is enough to form the substance of CuO in roasting process.The specific example of the Cu predecessor may include but unlimited In one or more of copper sulphate, copper nitrate and copper chloride.
The Zn predecessor can be that precipitation reaction can occur under the action of alkaline precipitating agent or acidic precipitation agent, Precipitating is formed, and is enough to form the substance of ZnO in roasting process.The specific example of the Zn predecessor may include but unlimited In one or more of zinc sulfate, zinc nitrate, zinc chloride and zinc acetate.
The predecessor of M can be formed for precipitation reaction can occur under the action of alkaline precipitating agent or acidic precipitation agent Precipitating, and be enough to form the substance of the oxide of M in roasting process.The specific example of the predecessor of M may include but unlimited In the one or more of sulfate, nitrate and chloride.
The co-precipitation can 40-80 DEG C at a temperature of carry out, preferably 50-70 DEG C at a temperature of carry out.
The co-precipitation can carry out in Conventional solvents.Generally, the solvent used that is co-precipitated can be water, alcohol (such as C1-C4Aliphatic alcohol, specific example can include but is not limited to one of methanol, ethyl alcohol, propyl alcohol and butanol or two Kind or more) and ketone (such as C3-C4Aliphatic ketone, specific example can include but is not limited to acetone and butanone) one of or It is two or more.Preferably, the solvent used that is co-precipitated is water.
After the completion of co-precipitation, aging 2-10 hours generally under co-precipitation temperature, the aging 4-8 preferably under co-precipitation temperature Hour.
The sediment that co-precipitation obtains can be collected using conventional method.Such as: filtering, centrifugation, sedimentation one of or Two or more combinations.
It can will be roasted after drying precipitate.The drying can 50-200 DEG C at a temperature of carry out, preferably exist It is carried out at a temperature of 80-120 DEG C.The drying can be carried out in normal pressure, can also be carried out under conditions of reducing pressure.It is described The dry duration can be selected according to dry temperature, be can remove the volatile materials in the sediment It is quasi-.Generally, the duration of the drying can be 1-12 hours, preferably 4-8 hours.
The roasting can 350-500 DEG C at a temperature of carry out, preferably 380-450 DEG C at a temperature of carry out.It is described The duration of roasting can be selected according to the temperature of roasting.Generally, the duration of the roasting can be 2-10 Hour, preferably 4-8 hours.The roasting carries out in air atmosphere.
Before use, the metal composite oxide as ester through hydrogenation catalyst is gone back using method commonly used in the art Original activation.The reduction activation can carry out in the reactor for carrying out ester through hydrogenation reaction, can not also be in ester through hydrogenation reactor Interior progress.From the angle of the terseness of operation, the reduction activation preferably carry out ester through hydrogenation reaction reactor in into Row.
The reduction activation can carry out under normal conditions.Generally, the reduction activation is using hydrogen as reduction Agent.The volume space velocity of hydrogen can be 1000-3000h-1.The reduction activation can 120-180 DEG C at a temperature of carry out.Into Pressure in the reactor of row reduction activation can be 0-7MPa, and preferably 1-5MPa, the pressure is gauge pressure.The reduction is lived The duration of change can be selected according to the temperature of reduction activation, generally can be 4-24 hours, preferably 5-20 hours.
In ester through hydrogenation reaction step, ester through hydrogenation reaction can be carried out under conventional reaction temperature and pressure.Generally, ester Hydrogenation reaction can 180-300 DEG C at a temperature of carry out, such as 180 DEG C, 185 DEG C, 190 DEG C, 195 DEG C, 200 DEG C, 250 DEG C or 300 DEG C, preferably 180-240 DEG C at a temperature of carry out.Pressure in ester through hydrogenation reactor can be 0-20MPa, preferably 1- 10MPa, more preferably 3-7MPa, the pressure are gauge pressure.The weight (hourly) space velocity (WHSV) of cyclohexane cyclohexanedimethanodibasic dibasic ester can be 0.1-2h-1, preferably 0.3-2h-1。
When using according to the ester through hydrogenation catalyst of embodiment described previously, add even carrying out ester at a lower temperature Hydrogen reaction can also obtain higher feed stock conversion and selectivity of product.Using the ester through hydrogenation of previously described preferred embodiment When catalyst (that is, previously described metal composite oxide), ester through hydrogenation reaction can 180-240 DEG C at a temperature of carry out, Such as 180 DEG C, 181 DEG C, 182 DEG C, 183 DEG C, 184 DEG C, 185 DEG C, 186 DEG C, 187 DEG C, 188 DEG C, 189 DEG C, 190 DEG C, 191 DEG C, 192 ℃、193℃、194℃、195℃、196℃、197℃、198℃、199℃、200℃、201℃、202℃、203℃、204℃、 205℃、206℃、207℃、208℃、209℃、210℃、211℃、212℃、213℃、214℃、215℃、216℃、217 ℃、218℃、219℃、220℃、221℃、222℃、223℃、224℃、225℃、226℃、227℃、228℃、229℃、 230 DEG C, 231 DEG C, 232 DEG C, 233 DEG C, 234 DEG C, 235 DEG C, 236 DEG C, 237 DEG C, 238 DEG C, 239 DEG C or 240 DEG C.At this point, ester Pressure in hydrogenator can be 3-7MPa.The weight (hourly) space velocity (WHSV) of cyclohexane cyclohexanedimethanodibasic dialkyl ester can be 0.3-2h-1.Hydrogen The molar ratio of gas and cyclohexane cyclohexanedimethanodibasic dibasic ester can be 4.5-8:1, as 4.5:1,4.6:1,4.7:1,4.8:1,4.9:1, 5:1,5.1:1,5.2:1,5.3:1,5.4:1,5.5:1,5.6:1,5.7:1,5.8:1,5.9:1,6:1,6.1:1,6.2:1, 6.3:1,6.4:1,6.5:1,6.6:1,6.7:1,6.8:1,6.9:1,7:1,7.1:1,7.2:1,7.3:1,7.4:1,7.5:1, 7.6:1,7.7:1,7.8:1,7.9:1 or 8:1.
Method described in the 4th aspect, step (1) obtain the production containing cyclohexane cyclohexanedimethanodibasic dibasic ester according to the present invention Object mixture, which can be sent directly into step (2), carries out ester through hydrogenation reaction, is sent into step (2) after can also carrying out intermediate treatment Carry out ester through hydrogenation reaction.Preferably, the product mixtures containing cyclohexane cyclohexanedimethanodibasic dibasic ester that step (1) obtains carry out gas-liquid Separation, isolates gaseous stream therein, after the liquid phase stream isolated optionally is mixed with solvent, obtains ester through hydrogenation raw material Liquid, and by the ester through hydrogenation raw mixture and hydrogen and ester through hydrogenation catalyst haptoreaction through reduction activation.The present invention for The method of gas-liquid separation is not particularly limited, and can be carried out using conventional method, such as: gas-liquid separation is carried out using condensation method.
Fig. 2 shows a kind of preferred embodiments of the production method of cyclohexanedimethanol according to the present invention.Below The preferred embodiment is described in detail in conjunction with Fig. 2.
As shown in Fig. 2, by as the dialkyl A of raw material optionally with the cyclohexane cyclohexanedimethanodibasic as solvent Dialkyl ester B (cyclohexane cyclohexanedimethanodibasic dialkyl ester preferably corresponding with the dialkyl as raw material) is mixed It closes and (preferably uses pipe-line mixer) and obtain material liquid.By the material liquid by the first raw material pump 1, it is sent into the first gas-liquid mixed In the fluid passage of device 2, while hydrogen C1 being sent into the gas passage of the first air and liquid mixer 2, thus by hydrogen injection original In feed liquid, raw mixture is obtained.The raw mixture that first air and liquid mixer 2 is exported is sent into hydrogenator 3, with dress The hydrogenation catalyst contact in hydrogenator 3 is filled out, hydrogenation reaction is carried out, dialkyl hydrogenation is become into ring Hexane dicarboxylic acid dialkyl ester.The arrival end of hydrogenator 3 is arranged in first air and liquid mixer 2.Preferably, the first gas-liquid is mixed The raw mixture that clutch 2 exports is admitted in hydrogenator 3 in a manner of flowing up.
The product mixtures containing cyclohexane cyclohexanedimethanodibasic dialkyl ester that hydrogenator 3 exports subsequently enter the first gas-liquid In separator 4, gas-liquid separation is carried out, gaseous stream 4A and liquid phase stream 4B are obtained.Gaseous stream 4A is exported into exhaust system, After being purified, it can discharge.Optionally, a part of liquid phase stream 4B gas-liquid separation obtained passes through pipe as solvent The circulation of road 5 is used for preparation raw material liquid.The remainder liquid phase stream 4B that gas-liquid separation obtains by pipeline 6 optionally with methanol D Mixing, obtains ester through hydrogenation material liquid.Ester through hydrogenation material liquid is logical by the liquid that the second raw material pump 7 enters the second air and liquid mixer 8 In road, is mixed with the hydrogen C2 for the gas passage for entering the second air and liquid mixer 8, obtain ester through hydrogenation raw mixture.
The ester through hydrogenation raw mixture of second air and liquid mixer 8 output enters in ester through hydrogenation reactor 9, adds with ester is seated in Ester through hydrogenation catalyst contact in hydrogen reactor 9, carries out ester through hydrogenation reaction, by the hexamethylene two in ester through hydrogenation raw mixture The hydrogenation of formic acid dialkyl ester becomes cyclohexanedimethanol.The product stream that ester through hydrogenation reactor 9 exports enters the second gas-liquid separation In device 10, it is separated into gaseous stream 10A and liquid phase stream 10B.Gaseous stream 10A enters in exhaust system, after being purified It can discharge.Liquid phase stream 10B is exported as product.
According to the fifth aspect of the present invention, the present invention provides a kind of ester through hydrogenation catalyst, which is Metal composite oxide, the metallic element in the metal composite oxide contain Cu, Zn and M, and M is selected from Zr and/or Ti.With It on the basis of the total amount of the ester through hydrogenation catalyst, is counted using oxide (oxide is full oxide), the content of Cu is 30- The content of 60 weight %, Zn is that the content of 10-50 weight %, M are 20-40 weight %.
Ester through hydrogenation catalyst described in 5th aspect according to the present invention, before use, using method commonly used in the art Carry out reduction activation.The reduction activation can carry out in the reactor for carrying out ester through hydrogenation reaction, can not also be in ester through hydrogenation It carries out in reactor, is preferably carried out in the reactor for carrying out ester through hydrogenation reaction.
The reduction activation can carry out under normal conditions.Generally, the reduction activation is using hydrogen as reduction Agent.The volume space velocity of hydrogen can be 1000-3000h-1.The reduction activation can 120-180 DEG C at a temperature of carry out.Into Pressure in the reactor of row reduction activation can be 0-7MPa, and preferably 1-5MPa, the pressure is gauge pressure.The reduction is lived The duration of change can be selected according to the temperature of reduction activation, generally can be 4-24 hours, preferably 5-20 hours.
According to the sixth aspect of the invention, the present invention provides a kind of preparation method of ester through hydrogenation catalyst, this method Method comprising the following steps preparation: the predecessor of Cu predecessor, Zn predecessor and M is co-precipitated, and collects co-precipitation Obtained sediment, and sediment is roasted, the precipitating reagent used that is co-precipitated for acidic precipitation agent, M for selected from Mn, One or more of Al, Zr, Mg and Ti, preferably Zr and/or Ti.
In the preparation method of the ester through hydrogenation catalyst, the dosage of the predecessor of Cu predecessor, Zn predecessor and M can To be selected according to expected forming for ester through hydrogenation catalyst.Generally, the predecessor of Cu predecessor, Zn predecessor and M Dosage make, on the basis of the total amount of the ester through hydrogenation catalyst finally prepared, in terms of oxide (for full oxide), Cu's It is the content of 10-50 weight %, M is 20-40 weight % that content, which is the content of 30-60 weight %, Zn,.
The Cu predecessor can be that can form precipitating, and be enough the shape in roasting process under acidic precipitation agent effect At the substance of CuO.The specific example of the Cu predecessor can include but is not limited to one in copper sulphate, copper nitrate and copper chloride Kind is two or more.The Zn predecessor can be that can form precipitating, and be enough in roasting process under acidic precipitation agent effect The middle substance for forming ZnO.The specific example of the Zn predecessor may include but unlimited zinc sulfate, zinc nitrate, zinc chloride and second One or more of sour zinc.The predecessor of M can be can be under acidic precipitation agent effect, and is enough in roasting process Form the substance of the oxide of M.The specific example of the predecessor of M can include but is not limited to sulfate, nitrate and chloride One or more of.
In the preparation method of the ester through hydrogenation catalyst, the acidic precipitation agent is preferably oxalic acid, propionic acid, butyric acid and fourth One or more of diacid.It is highly preferred that the acidic precipitation agent is oxalic acid.The dosage of the acidic precipitation agent can be with It is selected according to the dosage of metal precursor, generally, the dosage of the acidic precipitation agent is 1.1-2 times of theoretical amount, Preferably 1.2-1.5 times of theoretical amount.
In the preparation method of the ester through hydrogenation catalyst, the co-precipitation can 40-80 DEG C at a temperature of carry out, it is excellent It is carried out at a temperature of being selected in 50-70 DEG C.The co-precipitation can carry out in Conventional solvents.Generally, the co-precipitation uses Solvent can be water, alcohol (such as C1-C4Aliphatic alcohol, specific example can include but is not limited to methanol, ethyl alcohol, propyl alcohol and One or more of butanol) and ketone (such as C3-C4Aliphatic ketone, specific example can include but is not limited to acetone and One or more of butanone).Preferably, the solvent used that is co-precipitated is water.After the completion of co-precipitation, generally altogether Aging 2-10 hours under precipitation temperature, aging 4-8 hours preferably under co-precipitation temperature.
The sediment that co-precipitation obtains can be collected using conventional method.Such as: filtering, centrifugation, sedimentation one of or Two or more combinations.
In the preparation method of the ester through hydrogenation catalyst, roasted after sediment being dried.It is described dry It is dry can 50-200 DEG C at a temperature of carry out, preferably 80-120 DEG C at a temperature of carry out.The drying can be in normal pressure (that is, 1 normal atmosphere is depressed) carries out, and can also carry out under conditions of reducing pressure.The duration of the drying can root It is selected according to dry temperature, is subject to the volatile matter that can be removed in the sediment.Generally, the drying it is lasting when Between can be 1-12 hours, preferably 4-8 hours.In the preparation method of the ester through hydrogenation catalyst, the roasting can be Carried out at a temperature of 350-500 DEG C, preferably 380-450 DEG C at a temperature of carry out.The duration of the roasting can basis The temperature of roasting is selected.Generally, the duration of the roasting can be 2-10 hours, preferably 4-8 hours.It is described Roasting carries out in air atmosphere.
Ester through hydrogenation catalyst prepared by the method as described in the 6th aspect of the present invention, before use, normal using this field Method carries out reduction activation.The reduction activation can carry out in the reactor for carrying out ester through hydrogenation reaction, can also not It carries out in ester through hydrogenation reactor, is preferably carried out in the reactor for carrying out ester through hydrogenation reaction.
The reduction activation can carry out under normal conditions.Generally, the reduction activation is using hydrogen as reduction Agent.The volume space velocity of hydrogen can be 1000-3000h-1.The reduction activation can 120-180 DEG C at a temperature of carry out.Into Pressure in the reactor of row reduction can be 0-7MPa, and preferably 1-5MPa, the pressure is gauge pressure.The reduction activation Duration can be selected according to the temperature of reduction activation, generally can be 4-24 hours, preferably 5-20 hours.
According to the seventh aspect of the present invention, the present invention provides a kind of ester through hydrogenation method, this method is included in ester through hydrogenation Under reaction condition, by the ester through hydrogenation raw material containing cyclohexane cyclohexanedimethanodibasic dibasic ester, hydrogen shown in Formula II and optional solvent Mixture is contacted with the ester through hydrogenation catalyst through reduction activation, obtains cyclohexanedimethanol shown in formula III, wherein the ester Hydrogenation catalyst is ester through hydrogenation catalyst described in the 5th aspect of the present invention or the side as described in the 6th aspect of the present invention The ester through hydrogenation catalyst of method preparation,
In Formula II, R1And R2Respectively C1-C12Alkyl；
Detailed description has been carried out above for Formula II compound represented, and and will not be described here in detail.
The ester through hydrogenation raw mixture can contain solvent, can also not contain solvent.Preferably, the ester through hydrogenation is anti- Raw mixture is answered to contain at least one solvent.The solvent can be can to dissolve cyclohexane cyclohexanedimethanodibasic dibasic ester and molten Solve the liquid substance of cyclohexanedimethanol.Preferably, the solvent is selected from C1-C6One or more of alcohol.It is described The specific example of solvent can include but is not limited to one of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol and tert-butyl alcohol Or it is two or more.Preferably, the solvent is methanol.On the basis of the total amount of the ester through hydrogenation raw mixture, hexamethylene two The content of formic acid dibasic ester can be 10-90 weight %, and the content of solvent can be 10-90 weight %.
Conventional method can be used hydrogen and the ester through hydrogenation containing cyclohexane cyclohexanedimethanodibasic dibasic ester and optional solvent Material liquid mixing, to obtain the ester through hydrogenation raw mixture.For example, can be in a mixer by hydrogen and ester through hydrogenation raw material Liquid mixing, the mixer can be the combination of one or more of dynamic mixer, static mixer.The static state Detailed description has been carried out above for the type of mixer and the dynamic mixer, and and will not be described here in detail.
From the angle for further increasing selectivity of product and feed stock conversion, in a preferred embodiment, Hydrogen is injected in the ester through hydrogenation material liquid by previously described air and liquid mixer, so that the raw mixture is obtained, The ester through hydrogenation material liquid is contained in the fluid passage.The structure and mode of operation of the air and liquid mixer are above Through being described in detail, and will not be described here in detail.The air and liquid mixer can be arranged in the entrance of ester through hydrogenation reactor End, so that the ester through hydrogenation raw mixture that air and liquid mixer exports is sent directly into ester through hydrogenation reactor.At this point, from further The angle for improving ester through hydrogenation reaction effect is set out, and the ester through hydrogenation raw mixture is preferably sent into ester in a manner of from bottom to top In hydrogenator.
In ester through hydrogenation method, the injection rate of hydrogen can be according to the cyclohexane cyclohexanedimethanodibasic dibasic ester in ester through hydrogenation material liquid Content selected, be subject to and be enough to hydrogenate cyclohexane cyclohexanedimethanodibasic dibasic ester.It is preferred above in use as an example When embodiment the method injects hydrogen in the ester through hydrogenation material liquid by a kind of air and liquid mixer, the injection rate of hydrogen Can be 4.5-8:1 with the molar ratio of the cyclohexane cyclohexanedimethanodibasic dibasic ester in the ester through hydrogenation material liquid, as 4.5:1,4.6:1, 4.7:1,4.8:1,4.9:1,5:1,5.1:1,5.2:1,5.3:1,5.4:1,5.5:1,5.6:1,5.7:1,5.8:1,5.9:1, 6:1,6.1:1,6.2:1,6.3:1,6.4:1,6.5:1,6.6:1,6.7:1,6.8:1,6.9:1,7:1,7.1:1,7.2:1, 7.3:1,7.4:1,7.5:1,7.6:1,7.7:1,7.8:1,7.9:1 or 8:1.
In ester through hydrogenation method, ester through hydrogenation reaction can be carried out under conventional reaction temperature and pressure.According to the present invention The catalyst that uses of ester through hydrogenation method there is the catalytic activity that significantly improves, even carrying out ester under conditions of more mild Hydrogenation reaction also can effectively convert raw material, and obtain higher selectivity of product.Ester through hydrogenation method according to the present invention, Ester through hydrogenation reaction can 180-240 DEG C at a temperature of carry out, such as 180 DEG C, 181 DEG C, 182 DEG C, 183 DEG C, 184 DEG C, 185 DEG C, 186℃、187℃、188℃、189℃、190℃、191℃、192℃、193℃、194℃、195℃、196℃、197℃、198 ℃、199℃、200℃、201℃、202℃、203℃、204℃、205℃、206℃、207℃、208℃、209℃、210℃、 211℃、212℃、213℃、214℃、215℃、216℃、217℃、218℃、219℃、220℃、221℃、222℃、223 ℃、224℃、225℃、226℃、227℃、228℃、229℃、230℃、231℃、232℃、233℃、234℃、235℃、 236 DEG C, 237 DEG C, 238 DEG C, 239 DEG C or 240 DEG C.At this point, the pressure in ester through hydrogenation reactor can be 3-7MPa.Hexamethylene The weight (hourly) space velocity (WHSV) of diformazan acid dialkyl ester can be 0.3-2h-1。
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
In following embodiment and comparative example, average pore size is measured using scanning electron microscope method, pressure is in terms of gauge pressure.
In following embodiment and comparative example, the composition of the reaction solution of reactor output, and root are measured using gas chromatography Composition data according to surveying and determination is calculated using the following equation feed stock conversion and selectivity of product,
Mole of feed stock conversion=(mole of the remaining raw material of the mole-of the raw material of addition)/addition raw material Amount × 100%；
The mole for the product that selectivity of product=reaction generates/(the remaining raw material of the mole-of the raw material of addition Mole) × 100%.
In following embodiment and comparative example, the composition of catalyst uses x-ray fluorescence spectrometry.
Embodiment 1-19 is for illustrating the present invention.
Embodiment 1
In the present embodiment, hydrogenation catalyst is that Rh-Cu/C (on the basis of the total amount of catalyst, based on the element, contains 0.6 The Cu of the Rh of weight % and 0.2 weight %, carrier are active carbon), it is prepared using following methods:
(1) stoichiometrically by RhCl3And CuCl2It is dispersed in water and is made into maceration extract；
(2) 100 grams of active carbons are placed in maceration extract, saturation dipping 10 hours under environment temperature (25 DEG C)；
(3) by the active carbon through impregnating be placed in hydrazine hydrate aqueous solution (molar ratio of hydrazine hydrate and Rh be 3.5:1, Rh is with member Element meter) in, 60 DEG C at a temperature of, react 4 hours；
(4) solid matter is isolated from the reaction mixture that step (3) obtains, and be washed with deionized 3 times, 80 It is 8 hours dry in air atmosphere at a temperature of DEG C, to obtain hydrogenation catalyst.
In the present embodiment, ester through hydrogenation catalyst is CuO-ZnO-TiO2(on the basis of the total amount of catalyst, with oxide Meter, the content that the content of CuO is 40 weight %, ZnO is 40 weight %, TiO2Content be 20 weight %), using following methods Preparation:
(1) stoichiometrically by Cu (NO3)2、Zn(NO3)2With TiO (NO3)2It is dispersed in water, it is water-soluble to be made into metal salt Liquid, wherein Cu (NO3)2Mass concentration be 15.5%；
(2) oxalic acid is dissolved in deionized water, being made into precipitating reagent aqueous solution, (wherein, the mass concentration of oxalic acid is 12.5%), wherein the dosage of oxalic acid is 1.2 times of stoichiometry；
(3) 50 DEG C at a temperature of, with stirrings, aqueous metal salt and precipitating reagent aqueous solution cocurrent are instilled and react appearance In device, formed sediment, after the reaction was completed, 50 DEG C at a temperature of continue aging 4 hours；
(4) solid matter is isolated from the reaction mixture that step (3) obtains, and be washed with deionized 3 times, 80 It is 6 hours dry in air atmosphere at a temperature of DEG C, to obtain ester through hydrogenation catalyst precarsor；
(5) the ester through hydrogenation catalyst precarsor for obtaining step (4) 380 DEG C at a temperature of in air atmosphere roasting it is 5 small When, to obtain ester through hydrogenation catalyst.
Hydrogenation catalyst is seated in the tubular fixed-bed reactor as hydrogenator, ester through hydrogenation catalyst is filled It fills out in the tubular fixed-bed reactor as ester through hydrogenation reactor, forms catalyst bed, wherein hydrogenator and ester add In hydrogen reactor, the quantity of catalyst bed is 1, and the ratio of height to diameter of catalyst bed is 11.Hydrogenation catalyst is following Under the conditions of carry out reduction activation: temperature is 200 DEG C, and the volume space velocity of hydrogen is 1500h-1, the pressure in hydrogenator is 0.2MPa, duration 18h；Ester through hydrogenation catalyst carries out reduction activation under the following conditions: temperature is 130 DEG C, hydrogen Volume space velocity is 1000h-1, the pressure in ester through hydrogenation reactor is 2MPa, and the duration is 20 hours.
Using Fig. 2 shows method prepare hexamethylene-Isosorbide-5-Nitrae-dimethanol, wherein the first air and liquid mixer and the second gas-liquid Mixer for the component of abutting gas channel and fluid passage for perforated membrane as shown in Figure 1, (purchasing in the first air and liquid mixer From Jiangsu Jiuwu High-Tech Co., Ltd.), the average pore size in the hole in the perforated membrane is 100nm；Second air and liquid mixer In the component for abutting gas channel and fluid passage be perforated membrane (being purchased from Jiangsu Jiuwu High-Tech Co., Ltd.), The average pore size in the hole in the perforated membrane is 500nm.Concrete technology flow process is as follows.
(1) hydrogenation reaction
Hydrogen is sent into the gas passage of the first air and liquid mixer, by Isosorbide-5-Nitrae-hexamethylene containing dimethyl terephthalate (DMT) Alkane dicarboxylic acid dimethyl ester solution (content of dimethyl terephthalate (DMT) is 10 weight %) is sent into the liquid of the first air and liquid mixer In channel, to form raw mixture in hydrogen injection Isosorbide-5-Nitrae-dimethyl hexahydrophthalate solution.By raw mixture It is sent into hydrogenator in a manner of flowing from bottom to top, is contacted with the hydrogenation catalyst being seated in hydrogenator, and Hydrogenation products logistics is exported from hydrogenator.Wherein, hydrogenation reaction temperature is 120 DEG C, and the pressure in reactor is 3MPa, The molar ratio of hydrogen and dimethyl terephthalate (DMT) is 3.9:1, and the weight (hourly) space velocity (WHSV) of dimethyl terephthalate (DMT) is 1.1h-1.To adding Hydrogen product stream carries out composition monitoring, and calculates raw material (dimethyl terephthalate (DMT)) conversion ratio and product (Isosorbide-5-Nitrae-hexamethylene two Formic acid dimethyl ester) selectivity, as a result listed in table 1.
(2) gas-liquid separation
The product mixtures of hydrogenator output are subjected to gas-liquid separation, obtain gaseous stream and liquid phase stream.
(3) ester through hydrogenation reacts
The liquid phase stream that gas-liquid separation step obtains is mixed with methanol, forms ester through hydrogenation material liquid (wherein, Isosorbide-5-Nitrae-hexamethylene The content of alkane dicarboxylic acid dimethyl ester is 50 weight %).Hydrogen is sent into the gas passage of the second air and liquid mixer, by ester through hydrogenation Material liquid is sent into the fluid passage of the second air and liquid mixer, to form ester through hydrogenation in hydrogen injection ester through hydrogenation material liquid Raw mixture.Ester through hydrogenation raw mixture is sent into ester through hydrogenation reactor in a manner of flowing from bottom to top, and is seated in Ester through hydrogenation catalyst contact in ester through hydrogenation reactor, and ester through hydrogenation product stream is exported from ester through hydrogenation reactor.Wherein, ester Hydrogenation reaction temperature is 190 DEG C, and the pressure in reactor is 5MPa, hydrogen and Isosorbide-5-Nitrae-dimethyl hexahydrophthalate molar ratio For 6:1, Isosorbide-5-Nitrae-dimethyl hexahydrophthalate weight (hourly) space velocity (WHSV) is 0.8h-1.The composition of ester through hydrogenation product stream is monitored, And raw material (Isosorbide-5-Nitrae-dimethyl hexahydrophthalate) conversion ratio and product (1,4-CHDM) selectivity are calculated, as a result exist It is listed in table 1.
Embodiment 2
In the present embodiment, hydrogenation catalyst is that Rh-Ag/C (on the basis of the total amount of catalyst, based on the element, contains 6.0 The Ag of the Rh of weight % and 0.8 weight %, carrier are active carbon), it is prepared using following methods:
(1) stoichiometrically by Rh (NO3)3And AgNO3It is dispersed in water and is made into maceration extract；
(2) 50 grams of active carbons are placed in maceration extract, saturation dipping 10 hours under environment temperature (25 DEG C)；
(3) by the active carbon through impregnating be placed in hydrazine hydrate aqueous solution (molar ratio of hydrazine hydrate and Rh be 5:1, Rh is with element Meter) in, 60 DEG C at a temperature of, react 6 hours；
(4) solid matter is isolated from the reaction mixture that step (3) obtains, and be washed with deionized 3 times, 70 It is 15 hours dry in air atmosphere at a temperature of DEG C, to obtain hydrogenation catalyst.
In the present embodiment, ester through hydrogenation catalyst is CuO-ZnO-MnO2(on the basis of the total amount of catalyst, with oxide Meter, the content that the content of CuO is 60 weight %, ZnO is 10 weight %, MnO2Content be 30 weight %), using following methods Preparation:
(1) stoichiometrically by Cu (NO3)2、Zn(NO3)2With Mn (NO3)2It is dispersed in water, it is water-soluble to be made into metal salt Liquid, wherein Cu (NO3)2Mass concentration be 18.8%；
(2) oxalic acid is dissolved in deionized water, be made into precipitating reagent aqueous solution (wherein, the mass concentration of oxalic acid be 20%), Wherein, the dosage of oxalic acid is 1.3 times of stoichiometry；
(3) 60 DEG C at a temperature of, with stirrings, aqueous metal salt and precipitating reagent aqueous solution cocurrent are instilled and react appearance In device, formed sediment, after the reaction was completed, 60 DEG C at a temperature of continue aging 5 hours；
(4) solid matter is isolated from the reaction mixture that step (3) obtains, and be washed with deionized 3 times, It is 5 hours dry in air atmosphere at a temperature of 100 DEG C, to obtain ester through hydrogenation catalyst precarsor；
(5) the ester through hydrogenation catalyst precarsor for obtaining step (4) 400 DEG C at a temperature of in air atmosphere roasting it is 6 small When, to obtain ester through hydrogenation catalyst.Hydrogenation catalyst is seated in the tubular fixed-bed reactor as hydrogenator, By ester through hydrogenation Catalyst packing in the tubular fixed-bed reactor as ester through hydrogenation reactor, catalyst bed is formed, wherein In hydrogenator and ester through hydrogenation reactor, the quantity of catalyst bed is 1, and the ratio of height to diameter of catalyst bed is 10. Hydrogenation catalyst carries out reduction activation under the following conditions: temperature is 280 DEG C, and the volume space velocity of hydrogen is 2000h-1, add hydrogen anti- Answering the pressure in device is 0.5MPa, duration 10h；Ester through hydrogenation catalyst carries out reduction activation: temperature under the following conditions It is 180 DEG C, the volume space velocity of hydrogen is 2800h-1, the pressure in ester through hydrogenation reactor is 4MPa, and the duration is 6 hours.
Using Fig. 2 shows method prepare 1,4-CHDM, wherein the first air and liquid mixer and the second gas-liquid are mixed Clutch, should as shown in Figure 1, the component for abutting gas channel and fluid passage in the first air and liquid mixer is porous sieve plate The average pore size in the hole in porous sieve plate is 20 μm；In second air and liquid mixer for abutting gas channel and fluid passage Component is perforated membrane (being purchased from Jiangsu Jiuwu High-Tech Co., Ltd.), and the average pore size in the hole in the perforated membrane is 50nm. Concrete technology flow process is as follows.
(1) hydrogenation reaction
Hydrogen is sent into the gas passage of the first air and liquid mixer, by Isosorbide-5-Nitrae-hexamethylene containing dimethyl terephthalate (DMT) Alkane dicarboxylic acid dimethyl ester solution (dimethyl terephthalate (DMT) content is 5 weight %) is sent into the fluid passage of the first air and liquid mixer In, to form raw mixture in hydrogen injection Isosorbide-5-Nitrae-dimethyl hexahydrophthalate solution.By raw mixture with certainly The mode of lower and upper flowing is sent into hydrogenator, is contacted with the hydrogenation catalyst being seated in hydrogenator, and from adding Hydrogenation products logistics is exported in hydrogen reactor.Wherein, hydrogenation reaction temperature is 80 DEG C, and the pressure in reactor is 0.5MPa, hydrogen The molar ratio of gas and dimethyl terephthalate (DMT) is 3.5:1, and the weight (hourly) space velocity (WHSV) of dimethyl terephthalate (DMT) is 3h-1.To adding hydrogen to produce Object logistics carries out composition monitoring, and calculates raw material (dimethyl terephthalate (DMT)) conversion ratio and product (Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic Dimethyl ester) selectivity, as a result listed in table 1.
(2) gas-liquid separation
The product mixtures of hydrogenator output are subjected to gas-liquid separation, obtain gaseous stream and liquid phase stream.
(3) ester through hydrogenation reacts
The liquid phase stream that gas-liquid separation step obtains is mixed with methanol, forms ester through hydrogenation material liquid (wherein, Isosorbide-5-Nitrae-hexamethylene The content of alkane dicarboxylic acid dimethyl ester is 90 weight %).
Hydrogen is sent into the gas passage of the second air and liquid mixer, ester through hydrogenation material liquid is sent into the second air and liquid mixer Fluid passage in, thus by hydrogen injection ester through hydrogenation material liquid, form ester through hydrogenation raw mixture.Ester through hydrogenation raw material is mixed It closes object to be sent into a manner of flowing from bottom to top in ester through hydrogenation reactor, be catalyzed with the ester through hydrogenation being seated in ester through hydrogenation reactor Agent contact, and ester through hydrogenation product stream is exported from ester through hydrogenation reactor.Wherein, ester through hydrogenation reaction temperature is 205 DEG C, reactor Interior pressure is 7MPa, and hydrogen and Isosorbide-5-Nitrae-dimethyl hexahydrophthalate molar ratio are 4.5:1, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic two The weight (hourly) space velocity (WHSV) of methyl esters is 2h-1.The composition of ester through hydrogenation product stream is monitored, and calculates raw material (Isosorbide-5-Nitrae-hexamethylene diformazan Dimethyl phthalate) conversion ratio and product (1,4-CHDM) selectivity, as a result listed in table 1.
Comparative example 1
Hydrogenation reaction is carried out using method same as Example 2, unlike, the hydrogenation catalyst used is Rh/C (that is, hydrogenation catalyst is free of Ag, the content of Rh is same as Example 2).Composition monitoring is carried out to hydrogenation products logistics, and is calculated As a result feed stock conversion and selectivity of product are listed in table 1.
Comparative example 2
Hydrogenation reaction is carried out using method same as Example 2, unlike, Ag with etc. the Ni of weight replace.To adding Hydrogen product stream carries out composition monitoring, and calculates feed stock conversion and selectivity of product, as a result lists in table 1.
Comparative example 3
Hydrogenation reaction is carried out using method same as Example 2, unlike, Ag with etc. the Pd of weight replace.To adding Hydrogen product stream carries out composition monitoring, and calculates feed stock conversion and selectivity of product, as a result lists in table 1.
Embodiment 3
Ester through hydrogenation reaction is carried out using method same as Example 2, unlike, ester through hydrogenation catalyst is CuO-ZnO (that is, ester through hydrogenation catalyst is free of MnO2), in ester through hydrogenation catalyst, the relative amount of CuO and ZnO are same as Example 2.To ester The composition of hydrogenation products logistics is monitored, and calculates feed stock conversion and selectivity of product, is as a result listed in table 1.
Embodiment 4
Ester through hydrogenation reaction is carried out using method same as Example 2, unlike, the MnO in ester through hydrogenation catalyst2With Etc. weight TiO2Instead of.The composition of ester through hydrogenation product stream is monitored, and calculates feed stock conversion and selectivity of product, As a result it is listed in table 1.
Embodiment 5
Ester through hydrogenation reaction is carried out using method same as Example 2, unlike, the MnO in ester through hydrogenation catalyst2With Etc. weight ZrO2Instead of.The composition of ester through hydrogenation product stream is monitored, and calculates feed stock conversion and selectivity of product, As a result it is listed in table 1.
Embodiment 6
Ester through hydrogenation reaction is carried out using method same as Example 2, unlike, the MnO in ester through hydrogenation catalyst2With Etc. weight MgO replace.The composition of ester through hydrogenation product stream is monitored, and calculates feed stock conversion and selectivity of product, As a result it is listed in table 1.
Embodiment 7
Ester through hydrogenation reaction is carried out using method same as Example 2, unlike, the MnO in ester through hydrogenation catalyst2With Etc. weight Al2O3Instead of.The composition of ester through hydrogenation product stream is monitored, and calculates feed stock conversion and selectivity of product, As a result it is listed in table 1.
Embodiment 8
Hydrogenation reaction is carried out using method same as Example 2, unlike, by raw mixture to flow from top to bottom Dynamic mode is sent into hydrogenator, is contacted with the hydrogenation catalyst being seated in hydrogenator, and from hydrogenator Middle output hydrogenation products logistics.Composition monitoring is carried out to hydrogenation products logistics, and calculates feed stock conversion and selectivity of product, is tied Fruit is listed in table 1.
Embodiment 9
Ester through hydrogenation reaction is carried out using method same as Example 2, unlike, by ester through hydrogenation raw mixture with certainly The mode of upper and lower flowing is sent into ester through hydrogenation reactor, is contacted with the ester through hydrogenation catalyst being seated in ester through hydrogenation reactor, And hydrogenation products logistics is exported from hydrogenator.The composition of ester through hydrogenation product stream is monitored, and calculates raw material and turns As a result rate and selectivity of product are listed in table 1.
Table 1
Embodiment 10
In the present embodiment, hydrogenation catalyst Ru-Cu/Al2O3(on the basis of the total amount of catalyst, based on the element, contain The Cu of the Ru of 2.2 weight % and 2.0 weight %, carrier Al2O3), it is prepared using following methods:
(1) stoichiometrically by RuCl3And CuSO4It is dispersed in water and is made into maceration extract；
(2) by 60 grams of aluminium oxide (for γ-Al2O3) be placed in maceration extract, saturation dipping 10 is small under environment temperature (25 DEG C) When；
(3) by the aluminium oxide through impregnating be placed in hydrazine hydrate aqueous solution (molar ratio of hydrazine hydrate and Ru be 4:1, Ru is with element Meter) in, 55 DEG C at a temperature of, react 6 hours；
(4) solid matter is isolated from the reaction mixture that step (3) obtains, and be washed with deionized 3 times, It is 12 hours dry in nitrogen atmosphere at a temperature of 100 DEG C, to obtain hydrogenation catalyst.
In the present embodiment, ester through hydrogenation catalyst is CuO-ZnO-ZrO2(on the basis of the total amount of catalyst, with oxide Meter, the content that the content of CuO is 30 weight %, ZnO is 50 weight %, ZrO2Content be 20 weight %), using following methods Preparation:
(1) stoichiometrically by Cu (NO3)2、Zn(NO3)2With ZrO (NO3)2It is dispersed in water, it is water-soluble to be made into metal salt Liquid, wherein Cu (NO3)2Mass concentration be 15.0%；
(2) oxalic acid is dissolved in deionized water, being made into precipitating reagent aqueous solution, (wherein, the mass concentration of oxalic acid is 12.5%), wherein the dosage of oxalic acid is 1.2 times of stoichiometry；
(3) 55 DEG C at a temperature of, with stirring feelings, aqueous metal salt and precipitating reagent aqueous solution cocurrent are instilled and reacted In container, formed sediment, after the reaction was completed 55 DEG C at a temperature of continue aging 6 hours；
(4) solid matter is isolated from the reaction mixture that step (3) obtains, and be washed with deionized 3 times, It is 6 hours dry in air atmosphere at a temperature of 110 DEG C, to obtain ester through hydrogenation catalyst precarsor；
(5) the ester through hydrogenation catalyst precarsor for obtaining step (4) 450 DEG C at a temperature of in air atmosphere roasting it is 7 small When, to obtain ester through hydrogenation catalyst.
Hydrogenation catalyst is seated in the tubular fixed-bed reactor as hydrogenator, ester through hydrogenation catalyst is filled It fills out in the tubular fixed-bed reactor as ester through hydrogenation reactor, forms catalyst bed, wherein hydrogenator and ester add In hydrogen reactor, the quantity of catalyst bed is 1, and the ratio of height to diameter of catalyst bed is 12.Hydrogenation catalyst is following Under the conditions of carry out reduction activation: temperature is 320 DEG C, and the volume space velocity of hydrogen is 2000h-1, the pressure in hydrogenator is 0.8MPa, duration 12h；Ester through hydrogenation catalyst carries out reduction activation under the following conditions: temperature is 160 DEG C, hydrogen Volume space velocity is 1600h-1, the pressure in ester through hydrogenation reactor is 5MPa, and the duration is 10 hours.
Using Fig. 2 shows method prepare 1,4-CHDM, wherein the first air and liquid mixer and the second gas-liquid are mixed Clutch is more as shown in Figure 1, the component for abutting gas channel and fluid passage in the first air and liquid mixer is porous sieve plate The average pore size in the hole in the sieve plate of hole is 20 μm；The structure for abutting gas channel and fluid passage in second air and liquid mixer Part is porous sieve plate (being purchased from Jiangsu Jiuwu High-Tech Co., Ltd.), and the average pore size in the hole in the porous sieve plate is 400 μ m.Concrete technology flow process is as follows.
(1) hydrogenation reaction
Hydrogen is sent into the gas passage of the first air and liquid mixer, by Isosorbide-5-Nitrae-hexamethylene containing dimethyl terephthalate (DMT) Alkane dicarboxylic acid dimethyl ester solution (content of dimethyl terephthalate (DMT) is 20 weight %) is sent into the liquid of the first air and liquid mixer In channel, to form raw mixture in hydrogen injection Isosorbide-5-Nitrae-dimethyl hexahydrophthalate solution.By raw mixture It is sent into hydrogenator in a manner of flowing from bottom to top, is contacted with the hydrogenation catalyst being seated in hydrogenator, and Hydrogenation products logistics is exported from hydrogenator.Wherein, hydrogenation reaction temperature is 160 DEG C, and the pressure in reactor is 7MPa, The molar ratio of hydrogen and dimethyl terephthalate (DMT) is 6.0:1, and the weight (hourly) space velocity (WHSV) of dimethyl terephthalate (DMT) is 0.5h-1.To adding Hydrogen product stream carries out composition monitoring, and calculates raw material (dimethyl terephthalate (DMT)) conversion ratio and product (Isosorbide-5-Nitrae-hexamethylene two Formic acid dimethyl ester) selectivity, as a result listed in table 2.
(2) gas-liquid separation
The product mixtures of hydrogenator output are subjected to gas-liquid separation, obtain gaseous stream and liquid phase stream.
(3) ester through hydrogenation reacts
The liquid phase stream that gas-liquid separation step obtains is mixed with methanol, forms ester through hydrogenation material liquid (wherein, Isosorbide-5-Nitrae-hexamethylene The content of alkane dicarboxylic acid dimethyl ester is 10 weight %).Hydrogen is sent into the gas passage of the second air and liquid mixer, by ester through hydrogenation Material liquid is sent into the fluid passage of the second air and liquid mixer, to form ester through hydrogenation in hydrogen injection ester through hydrogenation material liquid Raw mixture.Ester through hydrogenation raw mixture is sent into ester through hydrogenation reactor in a manner of flowing from bottom to top, and is seated in Ester through hydrogenation catalyst contact in ester through hydrogenation reactor, and ester through hydrogenation product stream is exported from ester through hydrogenation reactor.Wherein, ester Hydrogenation reaction temperature is 180 DEG C, and the pressure in reactor is 3MPa, hydrogen and Isosorbide-5-Nitrae-dimethyl hexahydrophthalate molar ratio For 8:1, Isosorbide-5-Nitrae-dimethyl hexahydrophthalate weight (hourly) space velocity (WHSV) is 0.3h-1.The composition of ester through hydrogenation product stream is monitored, And raw material (Isosorbide-5-Nitrae-dimethyl hexahydrophthalate) conversion ratio and product (1,4-CHDM) selectivity are calculated, as a result exist It is listed in table 2.
Embodiment 11
Ester through hydrogenation reaction is carried out using method same as in Example 10, unlike, ester is prepared using alkaline precipitating agent Hydrogenation catalyst, it is specific the preparation method is as follows:
(1) stoichiometrically by Cu (NO3)2、Zn(NO3)2With ZrO (NO3)2It is dispersed in water, it is water-soluble to be made into metal salt Liquid, wherein Cu (NO3)2Mass concentration be 18.8%；
(2) by Na2CO3It is dissolved in deionized water, is made into precipitating reagent aqueous solution (wherein, Na2CO3Mass concentration be 11%), wherein Na2CO3Dosage be 1.2 times of stoichiometry；
(3) 55 DEG C at a temperature of, with stirrings, aqueous metal salt and precipitating reagent aqueous solution cocurrent are instilled and react appearance In device, formed sediment, after the reaction was completed 55 DEG C at a temperature of continue aging 6 hours；
(4) solid matter is isolated from the reaction mixture that step (3) obtains, and be washed with deionized 3 times, It is 6 hours dry in air atmosphere at a temperature of 110 DEG C, to obtain ester through hydrogenation catalyst precarsor；
(5) catalyst precarsor for obtaining step (4) 450 DEG C at a temperature of roast 7 hours in air atmosphere, thus Obtain ester through hydrogenation catalyst.
The composition of ester through hydrogenation product stream is monitored, and calculates feed stock conversion and selectivity of product, as a result in table 2 In list.
Embodiment 12
Ester through hydrogenation reaction is carried out using method same as in Example 10, unlike, the ZrO in ester through hydrogenation catalyst2 With etc. weight MnO2Instead of.The composition of ester through hydrogenation product stream is monitored, and calculates feed stock conversion and product selection Property, as a result listed in table 2.
Embodiment 13
Ester through hydrogenation reaction is carried out using method same as in Example 10, unlike, ester through hydrogenation catalyst is free of ZrO2, Relative scale in ester through hydrogenation catalyst between CuO and ZnO is same as in Example 10.The composition of ester through hydrogenation product stream is carried out Monitoring, and feed stock conversion and selectivity of product are calculated, as a result listed in table 2.
Comparative example 4
Hydrogenation reaction is carried out using method same as in Example 10, unlike, hydrogenation catalyst is free of Cu, is Ru/ Al2O3(on the basis of the total amount of catalyst, based on the element, the Ru containing 2.2 weight %, carrier Al2O3).To hydrogenation products Logistics carries out composition monitoring, and calculates feed stock conversion and selectivity of product, as a result lists in table 2.
Table 2
Embodiment 14
In the present embodiment, hydrogenation catalyst Pd-Ag/Al2O3(on the basis of the total amount of catalyst, based on the element, contain The Ag of the Pd of 0.3 weight % and 0.3 weight %, carrier Al2O3), it is prepared using following methods:
(1) stoichiometrically by Pd (NO3)2And AgNO3It is dispersed in water and is made into maceration extract；
(2) by 100 grams of aluminium oxide (for γ-Al2O3) be placed in maceration extract, the saturation dipping 10 under environment temperature (25 DEG C) Hour；
(3) by the aluminium oxide through impregnating be placed in hydrazine hydrate aqueous solution (molar ratio of hydrazine hydrate and Pd be 4:1, Rh is with element Meter) in, 80 DEG C at a temperature of, react 3 hours；
(4) solid matter is isolated from the reaction mixture that step (3) obtains, and be washed with deionized 3 times, 50 It is 20 hours dry in air atmosphere at a temperature of DEG C, to obtain hydrogenation catalyst.
In the present embodiment, ester through hydrogenation catalyst be CuO-ZnO-MgO (on the basis of the total amount of catalyst, in terms of oxide, The content of CuO is that the content that the content of 30 weight %, ZnO is 30 weight %, MgO is 40 weight %), using following methods system It is standby:
(1) stoichiometrically by Cu (NO3)2、Zn(NO3)2With Mg (NO3)2It is dispersed in water, it is water-soluble to be made into metal salt Liquid, wherein Cu (NO3)2Mass concentration be 9.4%；
(2) oxalic acid is dissolved in deionized water, be made into precipitating reagent aqueous solution (wherein, the mass concentration of oxalic acid be 25%), Wherein, the dosage of oxalic acid is 1.4 times of stoichiometry；
(3) 70 DEG C at a temperature of, with stirrings, aqueous metal salt and precipitating reagent aqueous solution cocurrent are instilled and react appearance In device, formed sediment, after the reaction was completed 70 DEG C at a temperature of continue aging 8 hours；
(4) solid matter is isolated from the reaction mixture that step (3) obtains, and be washed with deionized 3 times, It is 8 hours dry in air atmosphere at a temperature of 120 DEG C, to obtain ester through hydrogenation catalyst precarsor；
(5) the ester through hydrogenation catalyst precarsor for obtaining step (4) 390 DEG C at a temperature of in air atmosphere roasting it is 8 small When, to obtain ester through hydrogenation catalyst.
Hydrogenation catalyst is seated in the tubular fixed-bed reactor as hydrogenator, ester through hydrogenation catalyst is filled It fills out in the tubular fixed-bed reactor as ester through hydrogenation reactor, forms catalyst bed, wherein hydrogenator and ester add In hydrogen reactor, the quantity of catalyst bed is 1, and the ratio of height to diameter of catalyst bed is 13.Hydrogenation catalyst is following Under the conditions of carry out reduction activation: temperature is 360 DEG C, and the volume space velocity of hydrogen is 1800h-1, the pressure in hydrogenator is 0.3MPa, duration 8h；Ester through hydrogenation catalyst carries out reduction activation under the following conditions: temperature is 150 DEG C, the body of hydrogen Product air speed is 1200h-1, the pressure in ester through hydrogenation reactor is 1MPa, and the duration is 15 hours.
Using Fig. 2 shows method prepare 1,4-CHDM, wherein the first air and liquid mixer and the second gas-liquid are mixed For clutch as shown in Figure 1, be used for abutting gas channel and the component of fluid passage in the first air and liquid mixer are perforated membrane, this is more The average pore size in the hole in pore membrane is 50nm；The component for abutting gas channel and fluid passage in second air and liquid mixer For porous sieve plate, the average pore size in the hole in the porous sieve plate is 300 μm.Concrete technology flow process is as follows.
(1) hydrogenation reaction
Hydrogen is sent into the gas passage of the first air and liquid mixer, by Isosorbide-5-Nitrae-hexamethylene containing dimethyl terephthalate (DMT) Alkane dicarboxylic acid dimethyl ester solution (content of dimethyl terephthalate (DMT) is 12 weight %) is sent into the liquid of the first air and liquid mixer In channel, to form raw mixture in hydrogen injection Isosorbide-5-Nitrae-dimethyl hexahydrophthalate solution.By raw mixture It is sent into hydrogenator in a manner of flowing from bottom to top, is contacted with the hydrogenation catalyst being seated in hydrogenator, and Hydrogenation products logistics is exported from hydrogenator.Wherein, hydrogenation reaction temperature is 140 DEG C, and the pressure in reactor is 4MPa, The molar ratio of hydrogen and dimethyl terephthalate (DMT) is 4.3:1, and the weight (hourly) space velocity (WHSV) of dimethyl terephthalate (DMT) is 0.9h-1.To adding Hydrogen product stream carries out composition monitoring, and calculates raw material (dimethyl terephthalate (DMT)) conversion ratio and product (Isosorbide-5-Nitrae-hexamethylene two Formic acid dimethyl ester) selectivity, as a result listed in table 3.
(2) gas-liquid separation
The product mixtures of hydrogenator output are subjected to gas-liquid separation, obtain gaseous stream and liquid phase stream.
(3) ester through hydrogenation reacts
The liquid phase stream that gas-liquid separation step obtains is mixed with methanol, forms ester through hydrogenation material liquid (wherein, Isosorbide-5-Nitrae-hexamethylene The content of alkane dicarboxylic acid dimethyl ester is 40 weight %).
Hydrogen is sent into the gas passage of the second air and liquid mixer, ester through hydrogenation material liquid is sent into the second air and liquid mixer Fluid passage in, thus by hydrogen injection ester through hydrogenation material liquid, form ester through hydrogenation raw mixture.Ester through hydrogenation raw material is mixed It closes object to be sent into a manner of flowing from bottom to top in ester through hydrogenation reactor, be catalyzed with the ester through hydrogenation being seated in ester through hydrogenation reactor Agent contact, and ester through hydrogenation product stream is exported from ester through hydrogenation reactor.Wherein, ester through hydrogenation reaction temperature is 240 DEG C, reactor Interior pressure is 4MPa, and hydrogen and Isosorbide-5-Nitrae-dimethyl hexahydrophthalate molar ratio are 6:1, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic diformazan The weight (hourly) space velocity (WHSV) of ester is 1.2h-1.The composition of ester through hydrogenation product stream is monitored, and calculates raw material (Isosorbide-5-Nitrae-hexamethylene diformazan Dimethyl phthalate) conversion ratio and product (1,4-CHDM) selectivity, as a result listed in table 3.
Embodiment 15
It is reacted using ester through hydrogenation is carried out with the identical method of embodiment 14, unlike, the MgO in ester through hydrogenation catalyst is used Etc. weight TiO2Instead of.The composition of ester through hydrogenation product stream is monitored, and calculates feed stock conversion and selectivity of product, As a result it is listed in table 3.
Embodiment 16
It is reacted using ester through hydrogenation is carried out with the identical method of embodiment 15, unlike, ester is prepared using alkaline precipitating agent Hydrogenation catalyst, it is specific the preparation method is as follows:
(1) stoichiometrically by Cu (NO3)2、Zn(NO3)2And TiCl4It is dispersed in water, is made into aqueous metal salt, In, Cu (NO3)2Mass concentration be 9.4%；
(2) by NaHCO3It is dissolved in deionized water, is made into precipitating reagent aqueous solution (wherein, NaHCO3Mass concentration be 18%), wherein NaHCO3Dosage be 1.4 times of stoichiometry；
(3) 70 DEG C at a temperature of, with stirrings, aqueous metal salt and precipitating reagent aqueous solution cocurrent are instilled and react appearance In device, formed sediment, after the reaction was completed 70 DEG C at a temperature of continue aging 6 hours；
(4) solid matter is isolated from the reaction mixture that step (3) obtains, and be washed with deionized 3 times, It is 8 hours dry in air atmosphere at a temperature of 120 DEG C, to obtain ester through hydrogenation catalyst precarsor；
(5) the ester through hydrogenation catalyst precarsor for obtaining step (4) 450 DEG C at a temperature of in air atmosphere roasting it is 7 small When, to obtain ester through hydrogenation catalyst.
The composition of ester through hydrogenation product stream is monitored, and calculates feed stock conversion and selectivity of product, as a result in table 3 In list.
Table 3
Embodiment 17
In the present embodiment, hydrogenation catalyst Rh-Pd-Cu/Al2O3(on the basis of the total amount of catalyst, based on the element, contain There are the Cu, carrier Al of the Rh of 1.9 weight %, the Pd of 0.8 weight % and 0.2 weight %2O3), it is prepared using following methods:
(1) stoichiometrically by RhCl3、PdCl3And CuCl2It is dispersed in water and is made into maceration extract；
(2) by 50 grams of aluminium oxide (for γ-Al2O3) be placed in maceration extract, saturation dipping 10 is small under environment temperature (25 DEG C) When；
(3) by the aluminium oxide through impregnating be placed in hydrazine hydrate aqueous solution (molar ratio of hydrazine hydrate and Rh and Pd are 5:1, Rh and Pd is based on the element) in, 65 DEG C at a temperature of, react 6 hours；
(4) solid matter is isolated from the reaction mixture that step (3) obtains, and be washed with deionized 3 times, 70 It is 15 hours dry in air atmosphere at a temperature of DEG C, to obtain hydrogenation catalyst.
In the present embodiment, ester through hydrogenation catalyst is CuO-ZnO-MnO2(on the basis of the total amount of catalyst, with oxide Meter, the content that the content of CuO is 50 weight %, ZnO is 20 weight %, MnO2Content be 30 weight %), using following methods Preparation:
(1) stoichiometrically by Cu (NO3)2、Zn(NO3)2With Mn (NO3)2It is dispersed in water, it is water-soluble to be made into metal salt Liquid, wherein Cu (NO3)2Mass concentration be 24.6%；
(2) oxalic acid is dissolved in deionized water, being made into precipitating reagent aqueous solution, (wherein, the mass concentration of oxalic acid is 18.5%), wherein the dosage of oxalic acid is 1.3 times of stoichiometry；
(3) 70 DEG C at a temperature of, with stirrings, aqueous metal salt and precipitating reagent aqueous solution cocurrent are instilled and react appearance In device, formed sediment, after the reaction was completed 70 DEG C at a temperature of continue aging 8 hours；
(4) solid matter is isolated from the reaction mixture that step (3) obtains, and be washed with deionized 3 times, It is 8 hours dry in air atmosphere at a temperature of 120 DEG C, to obtain ester through hydrogenation catalyst precarsor；
(5) catalyst precarsor for obtaining step (4) 400 DEG C at a temperature of roast 6 hours in air atmosphere, thus Obtain ester through hydrogenation catalyst.
Hydrogenation catalyst is seated in the tubular fixed-bed reactor as hydrogenator, ester through hydrogenation catalyst is filled It fills out in the tubular fixed-bed reactor as ester through hydrogenation reactor, forms catalyst bed, wherein hydrogenator and ester add In hydrogen reactor, the quantity of catalyst bed is 1, and the ratio of height to diameter of catalyst bed is 7.Hydrogenation catalyst is in following item Reduction activation is carried out under part: temperature is 260 DEG C, and the volume space velocity of hydrogen is 1000h-1, the pressure in hydrogenator is 0.6MPa, duration 14h；Ester through hydrogenation catalyst carries out reduction activation under the following conditions: temperature is 160 DEG C, hydrogen Volume space velocity is 2200h-1, the pressure in ester through hydrogenation reactor is 2.8MPa, and the duration is 16 hours.
Using Fig. 2 shows method prepare 1,4-CHDM, wherein the first air and liquid mixer and the second gas-liquid are mixed For clutch as shown in Figure 1, be used for abutting gas channel and the component of fluid passage in the first air and liquid mixer are perforated membrane, this is more The average pore size in the hole in pore membrane is 100nm；The structure for abutting gas channel and fluid passage in second air and liquid mixer Part is perforated membrane (being purchased from Jiangsu Jiuwu High-Tech Co., Ltd.), and the average pore size in the hole in the perforated membrane is 1200nm. Concrete technology flow process is as follows.
(1) hydrogenation reaction
Hydrogen is sent into the gas passage of the first air and liquid mixer, by Isosorbide-5-Nitrae-hexamethylene containing dimethyl terephthalate (DMT) The liquid that alkane dicarboxylic acid dimethyl ester solution (content of dimethyl terephthalate (DMT) is 7 weight %) is sent into the first air and liquid mixer is logical In road, to form raw mixture in hydrogen injection Isosorbide-5-Nitrae-dimethyl hexahydrophthalate solution.By raw mixture with The mode flowed from bottom to top is sent into hydrogenator, is contacted with the hydrogenation catalyst being seated in hydrogenator, and from Hydrogenation products logistics is exported in hydrogenator.Wherein, hydrogenation reaction temperature is 135 DEG C, and the pressure in reactor is 6MPa, hydrogen The molar ratio of gas and dimethyl terephthalate (DMT) is 4.5:1, and the weight (hourly) space velocity (WHSV) of dimethyl terephthalate (DMT) is 2.1h-1.To adding hydrogen Product stream carries out composition monitoring, and calculates raw material (dimethyl terephthalate (DMT)) conversion ratio and product (Isosorbide-5-Nitrae-hexamethylene diformazan Dimethyl phthalate) selectivity, as a result list in table 4.
(2) gas-liquid separation
The product mixtures of hydrogenator output are subjected to gas-liquid separation, obtain gaseous stream and liquid phase stream.
(3) ester through hydrogenation reacts
The liquid phase stream that gas-liquid separation step obtains is mixed with methanol, forms ester through hydrogenation material liquid (wherein, Isosorbide-5-Nitrae-hexamethylene The content of alkane dicarboxylic acid dimethyl ester is 60 weight %).
Hydrogen is sent into the gas passage of the second air and liquid mixer, ester through hydrogenation material liquid is sent into the second air and liquid mixer Fluid passage in, thus by hydrogen injection ester through hydrogenation material liquid, form ester through hydrogenation raw mixture.Ester through hydrogenation raw material is mixed It closes object to be sent into a manner of flowing from bottom to top in ester through hydrogenation reactor, be catalyzed with the ester through hydrogenation being seated in ester through hydrogenation reactor Agent contact, and ester through hydrogenation product stream is exported from ester through hydrogenation reactor.Wherein, ester through hydrogenation reaction temperature is 210 DEG C, reactor Interior pressure is 6MPa, and hydrogen and Isosorbide-5-Nitrae-dimethyl hexahydrophthalate molar ratio are 6.4:1, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic two The weight (hourly) space velocity (WHSV) of methyl esters is 1.3h-1.The composition of ester through hydrogenation product stream is monitored, and calculates feed stock conversion and product choosing As a result selecting property is listed in table 4.
Embodiment 18
It is reacted using ester through hydrogenation is carried out with the identical method of embodiment 17, unlike, the MnO in ester through hydrogenation catalyst2 Use ZrO2Instead of.The composition of ester through hydrogenation product stream is monitored, and calculates feed stock conversion and selectivity of product, is as a result existed It is listed in table 4.
Embodiment 19
It is reacted using ester through hydrogenation is carried out with the identical method of embodiment 17, unlike, ester is prepared using alkaline precipitating agent Hydrogenation catalyst, it is specific the preparation method is as follows:
(1) stoichiometrically by Cu (NO3)2、Zn(NO3)2With Mn (NO3)2It is dispersed in water, it is water-soluble to be made into metal salt Liquid, wherein Cu (NO3)2Mass concentration be 24.6%；
(2) NaOH is dissolved in deionized water, be made into precipitating reagent aqueous solution (wherein, the mass concentration of NaOH be 5.5%), Wherein, the dosage of NaOH is 1.3 times of stoichiometry；
(3) 70 DEG C at a temperature of, with stirrings, aqueous metal salt and precipitating reagent aqueous solution cocurrent are instilled and react appearance In device, formed sediment, after the reaction was completed 70 DEG C at a temperature of continue aging 8 hours；
(4) solid matter is isolated from the reaction mixture that step (3) obtains, and be washed with deionized 3 times, It is 8 hours dry in air atmosphere at a temperature of 120 DEG C, to obtain ester through hydrogenation catalyst precarsor；
(5) catalyst precarsor for obtaining step (4) 400 DEG C at a temperature of roast 6 hours in air atmosphere, thus Obtain ester through hydrogenation catalyst.
The composition of ester through hydrogenation product stream is monitored, and calculates feed stock conversion and selectivity of product, as a result in table 4 In list.
Table 4
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to Protection scope of the present invention.

Claims (31)

1. a kind of hydrogenation catalyst, which contains carrier and loads active element on the carrier and auxiliary agent member Element, the active element are selected from one of Rh, Ru and Pd or two or more, and the auxiliary element is Cu and/or Ag, institute Stating carrier is active carbon and/or aluminium oxide.
2. hydrogenation catalyst according to claim 1, wherein based on the element, described on the basis of the total amount of the catalyst The content of active element is 0.1-8 weight %, and preferably 0.3-6 weight %, the content of the auxiliary element is 0.1-4 weight Measure %, preferably 0.2-2 weight %；
Preferably, based on the element, the molar ratio of the active element and the auxiliary element is 1:0.05-1.
3. hydrogenation catalyst of any of claims 1 or 2 is as shown in phthalic acid binary ester through hydrogenation preparation formula II shown in Formulas I Cyclohexane cyclohexanedimethanodibasic dibasic ester catalyst application,
In Formulas I and Formula II, R1And R2Respectively C1-C12Alkyl；
Preferably, phthalic acid dibasic ester shown in Formulas I is terephthalic acid (TPA) dibasic ester, preferably dimethyl terephthalate (DMT).
4. a kind of preparation method of cyclohexane cyclohexanedimethanodibasic dibasic ester, this method are included under hydrogenation conditions, will containing hydrogen, The raw mixture of phthalic acid dibasic ester and optional solvent shown in Formulas I is with the hydrogenation catalyst through reduction activation anti- It answers in device and contacts, obtain the product mixtures containing cyclohexane cyclohexanedimethanodibasic dibasic ester shown in Formula II, which is characterized in that is described to add Hydrogen catalyst is the hydrogenation catalyst of any of claims 1 or 2 through restoring,
In Formulas I and Formula II, R1And R2Respectively C1-C12Alkyl.
5. according to the method described in claim 4, wherein, the molar ratio of hydrogen and phthalic acid dibasic ester is 3.5-6:1.
6. method according to claim 4 or 5, wherein the solvent is cyclohexane cyclohexanedimethanodibasic dibasic ester shown in Formula II, Cyclohexane cyclohexanedimethanodibasic dibasic ester preferably identical with the hydrogenation products of phthalic acid dibasic ester shown in Formulas I.
7. method according to any one of claims 4 to 6, wherein this method further includes providing the raw mixture The step of, in material liquid that hydrogen injection is contained to phthalic acid dibasic ester and optional solvent, obtain the raw material mixing Object；
Preferably, hydrogen is injected in the material liquid by a kind of air and liquid mixer, so that the raw mixture is obtained, institute Stating air and liquid mixer includes that at least one fluid passage for being used to accommodate the material liquid is used to accommodate the hydrogen at least one The gas passage of gas, adjacent by a component between the fluid passage and the gas passage, the component is at least partly To there is porose area, the hydrogen has porose area to be injected in the material liquid by described；
The hole having in porose area is preferably micron openings and/or nano-pore；
The component is preferably the combination of one or more of perforated membrane, porous plate and void channels；
It is highly preferred that the air and liquid mixer further includes shell, the shell has gas access, liquid inlet and liquid discharge Mouthful, the shell is internally provided at least one described component, and the inner space of the shell is separated into liquid by the component Body channel and gas passage, the both ends of the fluid passage are connected to the liquid inlet and the liquid outlet respectively, described Gas passage is connected to the gas access.
8. the method according to any one of claim 4-7, wherein the hydrogenation reaction in fixed bed reactors into Row；
Preferably, in terms of phthalic acid dibasic ester, the weight (hourly) space velocity (WHSV) of the raw mixture is 0.5-3h-1。
9. the method according to any one of claim 4-8, wherein the hydrogenation reaction 80-160 DEG C at a temperature of It carries out；
Preferably, carrying out the pressure in the reactor of hydrogenation reaction is 0.5-7MPa, and the pressure is gauge pressure.
10. the method according to any one of claim 4-9, wherein the reducing agent used that restores is hydrogen, hydrogen The volume space velocity of gas is preferably 300-3000h-1；
Preferably, the reduction activation 100-400 DEG C at a temperature of carry out；
It is highly preferred that the pressure in the reactor restored is 0-1MPa, the pressure is gauge pressure.
11. the method according to any one of claim 4-10, wherein the phthalic acid dibasic ester is terephthaldehyde Sour dibasic ester, preferably dimethyl terephthalate (DMT).
12. a kind of production method of cyclohexanedimethanol, method includes the following steps:
(1) using method described in any one of claim 4-10, the phthalic acid dibasic ester preparation formula II as shown in Formulas I Shown in cyclohexane cyclohexanedimethanodibasic dibasic ester,
In Formulas I and Formula II, R1And R2Respectively C1-C12Alkyl；
It (2), will be containing cyclohexane cyclohexanedimethanodibasic dibasic ester, hydrogen shown in Formula II and optional molten under ester through hydrogenation reaction condition The ester through hydrogenation raw mixture of agent is contacted with the ester through hydrogenation catalyst through reduction activation, obtains hexamethylene diformazan shown in formula III Alcohol,
13. according to the method for claim 12, wherein in step (2), the ester through hydrogenation catalyst is composition metal oxidation Object, the metallic element in the metal composite oxide contain Cu, Zn and M, and M is selected from one of Mn, Al, Zr, Mg and Ti Or two or more, preferably Zr and/or Ti.
14. according to the method for claim 13, wherein on the basis of the total amount of the metal composite oxide, with oxidation Object meter, it be the content of 10-50 weight %, M is 20-40 weight % that the content of Cu, which is the content of 30-60 weight %, Zn,.
15. method described in 3 or 14 according to claim 1, wherein what the metal composite oxide use included the following steps Method preparation: the predecessor of Cu predecessor, Zn predecessor and M is co-precipitated, and collects the sediment that co-precipitation obtains, and Sediment is roasted, the precipitating reagent used that is co-precipitated is acidic precipitation agent, preferably oxalic acid；
Preferably, the co-precipitation carries out under conditions of temperature is 40-80 DEG C.
16. method described in any one of 2-15 according to claim 1, wherein restore the reduction of use described in step (2) Agent is hydrogen, and the volume space velocity of hydrogen is preferably 1000-3000h-1；
Preferably, the reduction activation 120-180 DEG C at a temperature of carry out；
It is highly preferred that the pressure in the reactor restored is 0-7MPa, the pressure is gauge pressure.
17. method described in any one of 2-16 according to claim 1, wherein solvent described in step (2) is selected from C1-C6 One or more of alcohol, preferably methanol.
18. method described in any one of 2-17 according to claim 1, wherein this method further includes providing the ester through hydrogenation The step of raw mixture: hydrogen injection is contained to the ester through hydrogenation material liquid of cyclohexane cyclohexanedimethanodibasic dibasic ester and optional solvent In, obtain the ester through hydrogenation raw mixture；
Preferably, hydrogen is injected in the ester through hydrogenation material liquid by a kind of air and liquid mixer, to obtain the ester through hydrogenation Raw mixture, the air and liquid mixer include the fluid passage and at least that at least one is used to accommodate the ester through hydrogenation material liquid One passes through component adjoining for accommodating the gas passage of the hydrogen, between the fluid passage and the gas passage, The component at least partially has porose area, and the hydrogen has porose area to be injected in the ester through hydrogenation material liquid by described；
The hole having in porose area is preferably micron openings and/or nano-pore；
The component is preferably the combination of one or more of perforated membrane, porous plate and void channels；
It is highly preferred that the air and liquid mixer further includes shell, the shell has gas access, liquid inlet and liquid discharge Mouthful, the shell is internally provided at least one described component, and the inner space of the shell is separated into liquid by the component Body channel and gas passage, the both ends of the fluid passage are connected to the liquid inlet and the liquid outlet respectively, described Gas passage is connected to the gas access.
19. method described in any one of 2-18 according to claim 1, wherein in step (2), the ester through hydrogenation reaction exists It is carried out in fixed bed reactors；
Preferably, the molar ratio of hydrogen and cyclohexane cyclohexanedimethanodibasic dibasic ester is 4.5-8:1.
20. method described in any one of 2-19 according to claim 1, wherein ester through hydrogenation reaction 180-300 DEG C, It is preferred that being carried out at a temperature of 180-240 DEG C；
Preferably, carrying out the pressure in the reactor of ester through hydrogenation reaction is 0-20MPa, preferably 3-7MPa；
Preferably, the weight (hourly) space velocity (WHSV) of cyclohexane cyclohexanedimethanodibasic dialkyl ester is 0.3-2h-1。
21. a kind of ester through hydrogenation catalyst, which is metal composite oxide, the metal member in the metal composite oxide Element contains Cu, Zn and M, and M is selected from Zr and/or Ti.
22. ester through hydrogenation catalyst according to claim 21, wherein on the basis of the total amount of the ester through hydrogenation catalyst, In terms of oxide, it be the content of 10-50 weight %, M is 20-40 weight % that the content of Cu, which is the content of 30-60 weight %, Zn,.
23. a kind of preparation method of ester through hydrogenation catalyst, the method that this approach includes the following steps: by Cu predecessor, Zn forerunner The predecessor of object and M are co-precipitated, and collect the sediment that co-precipitation obtains, and sediment is roasted, described coprecipitated The precipitating reagent that uses form sediment for acidic precipitation agent, preferably oxalic acid, M for selected from one or both of Mn, Al, Zr, Mg and Ti with On, preferably Zr and/or Ti.
24. according to the method for claim 23, wherein the co-precipitation carries out under conditions of temperature is 40-80 DEG C.
25. the method according to claim 23 or 24, wherein the dosage of the predecessor of Cu predecessor, Zn predecessor and M So that in terms of oxide, the content of Cu is 30-60 weight %, Zn on the basis of the total amount of the ester through hydrogenation catalyst finally prepared Content be the content of 10-50 weight %, M be 20-40 weight %.
26. a kind of ester through hydrogenation method, this method are included under ester through hydrogenation reaction condition, hexamethylene diformazan shown in Formula II will be contained The ester through hydrogenation raw mixture of sour dibasic ester, hydrogen and optional solvent is contacted with the ester through hydrogenation catalyst through restoring, and is obtained Cyclohexanedimethanol shown in formula III, which is characterized in that the ester through hydrogenation catalyst is any one of claim 21-22 The ester through hydrogenation catalyst or the ester through hydrogenation catalyst of the preparation of the method as described in any one of claim 23-25,
In Formula II, R1And R2Respectively C1-C12Alkyl, preferably respectively C4-C10Alkyl, more preferably respectively C6-C10Alkane Base, further preferably respectively C7-C10Alkyl；
27. according to the method for claim 26, wherein the reducing agent that the reduction activation uses is hydrogen, the body of hydrogen Product air speed is preferably 1000-3000h-1；
Preferably, the reduction activation 120-180 DEG C at a temperature of carry out；
It is highly preferred that the pressure in the reactor restored is 0-7MPa, the pressure is gauge pressure.
28. the method according to claim 26 or 27, wherein the solvent is selected from C1-C6One or both of alcohol More than, preferably methanol.
29. the method according to any one of claim 26-28, wherein this method further includes providing the ester through hydrogenation The step of raw mixture: hydrogen injection is contained to the ester through hydrogenation material liquid of cyclohexane cyclohexanedimethanodibasic dibasic ester and optional solvent In, obtain the ester through hydrogenation raw mixture；
Preferably, hydrogen is injected in the ester through hydrogenation material liquid by a kind of air and liquid mixer, to obtain the ester through hydrogenation Raw mixture, the air and liquid mixer include the fluid passage and at least that at least one is used to accommodate the ester through hydrogenation material liquid One passes through component adjoining for accommodating the gas passage of the hydrogen, between the fluid passage and the gas passage, The component at least partially has porose area, and the hydrogen has porose area to be injected in the ester through hydrogenation material liquid by described；
The hole having in porose area is preferably micron openings and/or nano-pore；
The component is preferably the combination of one or more of perforated membrane, porous plate and void channels；
It is highly preferred that the air and liquid mixer further includes shell, the shell has gas access, liquid inlet and liquid discharge Mouthful, the shell is internally provided at least one described component, and the inner space of the shell is separated into liquid by the component Body channel and gas passage, the both ends of the fluid passage are connected to the liquid inlet and the liquid outlet respectively, described Gas passage is connected to the gas access.
30. the method according to any one of claim 26-29, wherein the ester through hydrogenation reaction is in fixed bed reaction It is carried out in device；
Preferably, the molar ratio of hydrogen and cyclohexane cyclohexanedimethanodibasic dibasic ester is 4.5-8:1.
31. the method according to any one of claim 26-30, wherein the ester through hydrogenation reaction is at 180-240 DEG C At a temperature of carry out；
Preferably, carrying out the pressure in the reactor of ester through hydrogenation reaction is 3-7MPa；
Preferably, the weight (hourly) space velocity (WHSV) of cyclohexane cyclohexanedimethanodibasic dialkyl ester is 0.3-2h-1。
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