CN110437033A - The method for producing 1,4 cyclohexane dimethanol - Google Patents
The method for producing 1,4 cyclohexane dimethanol Download PDFInfo
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- CN110437033A CN110437033A CN201810409497.0A CN201810409497A CN110437033A CN 110437033 A CN110437033 A CN 110437033A CN 201810409497 A CN201810409497 A CN 201810409497A CN 110437033 A CN110437033 A CN 110437033A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—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
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The present invention relates to productions 1, the method of 4- cyclohexanedimethanol, more particularly to by terephthalic acid (TPA) dibasic ester production 1, the method of 4- cyclohexanedimethanol, method includes the following steps: terephthalic acid (TPA) dibasic ester shown in formula (I) and hydrogen are carried out hydrogenation reaction by (1) in the presence of the first catalyst, obtain Isosorbide-5-Nitrae cyclohexane cyclohexanedimethanodibasic dibasic esterIn formula (I), R1And R2It is identical or different, it is each independently selected from the alkyl of C4-C12；(2) Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dibasic ester obtained by step (1) and hydrogen are subjected in the presence of the second catalyst hydrogenation reaction, obtain the product stream containing 1,4-CHDM；(3) the resulting product stream containing 1,4-CHDM of step (2) is separated, obtains 1,4-CHDM product.The method of the invention using under room temperature be liquid reaction raw materials solve the problems, such as circulation solvent energy consumption is high, catalyst activity is given full play to, and product separating technique is simple, particularly suitable for industrial production.
Description
Technical field
The present invention relates to the methods of production 1,4-CHDM, and in particular to 1 is produced by terephthalic acid (TPA) dibasic ester,
The method of 4- cyclohexanedimethanol.
Background technique
1,4-CHDM (abbreviation CHDM) is a kind of cycloaliphatic diols of symmetrical configuration, containing there are two primary hydroxyls
Base is industrial important polyester (poly terephthalic acid 1,4-CHDM ester PCT；Terephthalic acid (TPA), ethylene glycol and small
In the copolymer p ETG of 50% 1,4 cyclohexane dimethanol；Terephthalic acid (TPA), ethylene glycol and the 1,4- hexamethylene greater than 50%
The copolymer p CTG of dimethanol) raw materials for production, be the improvement product of existing dihydric alcohol such as ethylene glycol, neopentyl glycol.With 1,4- ring
Hexane dimethanol is that the saturated polyester of Material synthesis can be made into the plasticizer of high performance glaze and coating, Isosorbide-5-Nitrae-hexamethylene two
Methanol may be additionally used for being modified other unsaturated polyester resins.And the most important application of 1,4 cyclohexane dimethanol or preparation line
Property polyester fiber, the fiber relative density made of the raw material is light, fusing point is high, good electrical property, especially suitable for production electric appliance set
It is standby.Monopolization of the Eastman company, the U.S. to CHDM product and production technology decades, seriously constrains China's polyester new material
Industrialization process.
Currently, the preparation route of 1,4-CHDM mainly include the following types: (1) by dimethyl terephthalate (DMT)
(DMT) CHDM is prepared through first step benzene ring hydrogenation and second step ester through hydrogenation；(2) by dimethyl terephthalate (DMT) (DMT) through a step
Hydrogenation reaction prepares CHDM；(3) hydrogen is added to prepare through first step benzene ring hydrogenation and second step carboxyl by terephthalic acid (TPA) (PTA)
CHDM；(4) hydrogen is added to prepare CHDM by terephthalic acid (TPA) (PTA) step；(5) CHDM is hydrogenated to by one step of terephthalaldehyde.But
It is that currently the only industrialized method is that dimethyl terephthalate (DMT) (DMT) two-step method adds hydrogen to prepare CHDM, i.e. DMT is passed through first
Isosorbide-5-Nitrae-dimethyl hexahydrophthalate is made in one section of benzene ring hydrogenation, then carries out the production method of two sections of ester through hydrogenation and product purification.
(1) for one section of benzene ring hydrogenation process, CN1099745A discloses a kind of dimethyl terephthalate (DMT) (DMT) plus hydrogen
The Catalyst And Method for preparing Isosorbide-5-Nitrae-dimethyl hexahydrophthalate (DMCD), uses Pd/Al2O3Catalyst, and auxiliary agent is added
Second of VIII B metals of or mixtures thereof Ni, Ru, Pt, in 140-250 DEG C of reaction temperature, pressure 5-17MPa, liquid air speed
0.5-5h-1And under the conditions of the mass ratio of DMT and DMCD is 30: 70, the DMT for being dissolved in DMCD is contacted with hydrogen, using fixation
Bed hydroprocessing prepares 1,4 cyclohexanedicarboxylic acid dimethyl ester.CN1058959C, which is disclosed, becomes rutgers catalytic hydrogenation
The technique of corresponding cyclohexanedicarboxylate, uses Pd/Al2O3Catalyst, in actual operation, 80-95% (weight)
Hydrogenation products need to be recycled back to reactor inlet, and need to be arranged in series two hydroconversion reaction zones, can just make turning for DMT raw material
It is the disadvantages of rate reaches 99% or so, and there are hydrogen consumptions for this method greatly, product circulation energy consumption is high, process flow is complicated, inevitable
Bring the problem that production is at high cost.CN1089082C discloses a kind of in the Ru catalyst presence of load and gas-liquid mixed
In the case where, by aromatic dicarboxylic acid dialkyl ester (Arrcostab of 1-4 carbon atom) the hydrogenated method for preparing DMCD, reaction temperature
120-180 DEG C, pressure 3-10MPa are spent, in order to control hydrogenation reaction heat release using Multi-row-tube voltage-resistant reactor form, this method is deposited
In the defects such as device fabrication difficulty is big, at high cost and corresponding hydrotreating ability is low.
(2) for two sections of ester through hydrogenation processes, CN1060153C is disclosed two-in the presence of the copper catalyst of manganese co-catalysis
Dicarboxylic ester (preferably DMCD) plus hydrogen prepare the technique of CHDM, 200-260 DEG C of reaction temperature, pressure to (C1-C4 alkyl) ring
The molar ratio of 1-13.7MPa, hydrogen and hydrogenating materials is up to 200:1-1000:1, feed stock conversion 98%, purpose product selection
Property 96%, and using a large amount of methanol as retarder thinner, that there are hydrogen consumptions is big for this method, solvent separation circulating consumption is high and raw
Produce the problems such as at high cost.CN1089082C discloses one kind in the presence of copper chromite catalyst, under the conditions of gas-liquid mixed phase
The method that continuous hydrogenation DMCD prepares CHDM, 220-280 DEG C of reaction temperature, pressure 18.5-30MPa, this method not only equally need
The Multi-row-tube voltage-resistant reactor equipment that use production is complicated, operation difficulty is high is wanted, while hydrogenating materials are DMCD and 1-4 carbon is former
The additional amount of the mixture of sub- fatty alcohol, fatty alcohol is calculated as 10-80 weight % by DMCD, increases production run cost.
Furthermore it is noted that being solid under dimethyl terephthalate (DMT) (DMT) room temperature, fusing point is up to 140 DEG C, In
Solubility in various organic solvents is all very small, even if the solubility of DMT is generally smaller than 10% under the high temperature conditions, this is just
It determines that one section of benzene ring hydrogenation needs a large amount of solvent in the process, directly results in high circulation energy consumption, and during secondary hydrogenation
Methanol loop solvent is largely used, subsequent separating methanol energy consumption is also quite high.
Summary of the invention
The purpose of the invention is to overcome raw materials used dimethyl terephthalate (DMT) fusing point of the existing technology high, molten
The problems such as Xie Du is low provides the method for production 1,4-CHDM.
To achieve the goals above, one aspect of the present invention provides a kind of method for producing 1,4-CHDM, the party
Method the following steps are included:
(1) terephthalic acid (TPA) dibasic ester shown in formula (I) and hydrogen are subjected to hydrogenation reaction in the presence of the first catalyst,
Isosorbide-5-Nitrae cyclohexane cyclohexanedimethanodibasic dibasic ester is obtained,
In formula (I), R1And R2It is identical or different, it is each independently selected from the alkyl of C4-C12；
(2) 1,4 cyclohexanedicarboxylic acid dibasic ester obtained by step (1) and hydrogen are added in the presence of the second catalyst
Hydrogen reaction, obtains the product stream containing 1,4-CHDM；
(3) the resulting product stream containing 1,4-CHDM of step (2) is separated, obtains Isosorbide-5-Nitrae-hexamethylene
Dimethanol product.
The method of the invention has the advantage that
(1) replace traditional dimethyl terephthalate (DMT) as raw material using terephthalic acid (TPA) dibasic ester (alkyl of C4-C12),
Raw material is changed to liquid by solid, solves the problems, such as that dissolution of raw material degree is small, to fundamentally solve circulation solvent, energy consumption is high
The problem of；
(2) since phenyl ring hydrogenation and ester group hydrogenation belong to exothermic reaction, raw material by macromolecule terephthalic acid (TPA)
Dibasic ester replaces the dimethyl terephthalate (DMT) of traditional small-molecular-weight, and quality hydrogen consumption reduces about 30% (or 50%), thermal discharge
Also it is greatly lowered, catalyst activity can be given full play to, raw material remnants are low in product, and product selectivity is high；
(3) reaction temperature and reaction pressure are low, and hydrogen ester molar ratio is small, compared to traditional gas phase hydrogenation technique, using liquid
Its hydrogen circulating consumption of phase hydrogenation technique can be greatly reduced；
(4) separating technology is simple, particularly suitable for industrial production, good product quality.
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.
The present invention provides a kind of methods for producing 1,4-CHDM, method includes the following steps:
(1) terephthalic acid (TPA) dibasic ester shown in formula (I) and hydrogen are subjected to hydrogenation reaction in the presence of the first catalyst,
Isosorbide-5-Nitrae cyclohexane cyclohexanedimethanodibasic dibasic ester is obtained,
In formula (I), R1And R2It is identical or different, it is each independently selected from the alkyl of C4-C12；
(2) 1,4 cyclohexanedicarboxylic acid dibasic ester obtained by step (1) and hydrogen are added in the presence of the second catalyst
Hydrogen reaction, obtains the product stream containing 1,4-CHDM；
(3) the resulting product stream containing 1,4-CHDM of step (2) is separated, obtains Isosorbide-5-Nitrae-hexamethylene
Dimethanol product.
In the present invention, the terephthalic acid (TPA) dibasic ester has structure shown in formula (I), R1And R2It is identical or different, often
Lower temperature is liquid, it is preferable that R1And R2Be each independently selected from normal-butyl, isobutyl group, n-pentyl, isopentyl, neopentyl, just oneself
Base, isohesyl, n-heptyl, different heptyl, n-octyl, iso-octyl, n-nonyl, isononyl, positive decyl, isodecyl, undecyl and
Dodecyl；Preferably R1And R2It is all normal-butyl, isobutyl group, n-octyl or iso-octyl；More preferably R1And R2It is all n-octyl
Or iso-octyl.
In the present invention, the terephthalic acid (TPA) dibasic ester can be the mixture of above-mentioned a variety of esters, such as described to benzene
Cyclohexanedimethanodibasic dibasic ester is the mixture of dibutyl terephthalate and dioctyl terephthalate.
In the present invention, step (1), which is realized, is reduced to hexamethylene ring for the benzene ring hydrogenation in terephthalic acid (TPA) dibasic ester.Institute
The catalyst that the first catalyst can be commonly used in the art used in hydrogenation process is stated, as long as hexamethylene can be reduced into phenyl ring
Ring.Preferably, the active component on first catalyst containing carrier and load on the carrier, the active component
For one of Ni, Rh, Ru and Pd or a variety of, the carrier is selected from Al2O3、SiO2、TiO2With one of active carbon or more
Kind.On the basis of the total weight of first catalyst, the content of the active component is 0.05-10 weight %, preferably
0.3-5 weight %.
It in the present invention, the use of the terephthalic acid (TPA) dibasic ester for being liquid is reaction raw materials under room temperature as described above, step
Suddenly the hydrogenation reaction of (1) can carry out at a lower temperature, for example, hydrogenation reaction condition may include: temperature be 60-160
DEG C, pressure 0.1-10MPa, H2Molar ratio with phthalic acid dibasic ester is 3.5-100, the weight of terephthalic acid (TPA) dibasic ester
Air speed is 0.2-3h-1。
In the present invention, step (2) realizes that by Isosorbide-5-Nitrae-cyclohexane dicarboxylic ester ester group hydrogenating reduction be alcohol.In described plus hydrogen
Used in the process of the second catalyst can be catalyst commonly used in the art, such as the catalyst containing Cu, preferably CuO-AO-
One or more of BO, A Zn, Mn, Cr, one or more of B Al, Zr, Mg, Ti.With second catalyst
On the basis of total weight, the content of CuO in the catalyst is that the content of 30-60 weight %, AO in the catalyst is 20-50 weight
% is measured, the content of BO in the catalyst is 0-30 weight %.
In the present invention, in step (2), the condition of the hydrogenation reaction includes: that temperature is 180-260 DEG C, and pressure is
0.1-10MPa, H2It is 5-100, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dibasic ester with Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dibasic ester molar ratio
Weight space velocity is 0.2-3h-1。
In the present invention, the hydrogenation reaction in the hydrogenation reaction and step (2) of the step (1) adds hydrogen list in level-one respectively
It is carried out in member and secondary hydrogenation unit, the level-one hydrogenation unit and secondary hydrogenation unit can be two portions of same reactor
Point, or be located in two reactors.Preferably, the reactor is fixed bed reactors.
For example, hydrogen is micro-nano by average pore size when realizing dispersion process as dispersed components thereof using micro-nano pore membrane
The hole of size is injected into hydrogenating materials, forms the gas-liquid mixture fluid containing micro-bubble.In another example when with micro-nano hole
When sieve plate is that dispersed components thereof realizes dispersion process, after hydrogen passes through micro-nano hole sieve plate, adding for flowing is distributed to from vertical direction
In hydrogen feedstock, hydrogen and hydrogenating materials cross-flow passes, hydrogen cut into micro-bubble by the hydrogenating materials of cross-flow passes, and bubble is flat
Equal diameter can be controlled by bore dia on micro-nano hole sieve plate and hydrogen flow rate.For another example when with micro-nano
When grade channel is that dispersed components thereof realizes dispersion process, using arrangement of microspheres when in reaction channel, micron order and nanoscale are formed
The microchannel coexisted, each reactant form turbulent flow in microchannel, reach efficient mixed effect.
In the present invention, above-mentioned micro-nano hole, which refers to, had not only contained nano-pore but also had contained micron openings in dispersed components thereof structure, institute
The average diameter for stating nano-pore is 1-100nm, and the average diameter of the micron openings is 100nm-2000 μm.Above-mentioned micro/nano level is logical
In road, the average diameter of Nanoscale channels is 1-100nm, and the average diameter of micro scale channel is 100nm-2000 μm.
In the present invention, after the liquid material and hydrogen mix, enter preferably in a manner of from bottom to top plus hydrogen is anti-
Device is answered to be reacted.
In the present invention, in step (3) by the resulting product stream containing 1,4-CHDM separate with
Obtain 1,4 cyclohexane dimethanol product and alcohols byproduct.In the present invention, the separation carries out in separative unit, preferably
Ground, the separative unit include at least two knockout towers, one of knockout tower for obtain alcohols byproduct (such as butanol or
Octanol), another knockout tower is for obtaining 1,4-CHDM product.
In the present invention, the knockout tower can realize separation by this field conventional technology, such as pass through
Decompression operation realizes that vacuum degree 3KPa-90KPa, temperature is 100-250 DEG C.
The method of production 1,4-CHDM of the present invention, uses the terephthalate energy under room temperature being liquid
Enough solve the problems, such as that energy consumption is high for circulation solvent；And use the terephthalate of larger molecular weight, unit mass hydrogen consumption drop
Low, thermal discharge is also greatly lowered, and can give full play to catalyst activity, and product selectivity is high；Hydrogen is made using liquid-phase hydrogenatin technique
Gas circulating consumption is greatly reduced；Separating technology is simple, is suitable for production.
The present invention will be described in detail by way of examples below.
Embodiment 1
Level-one hydrogenation unit: by dioctyl terephthalate and H2Pass through fixed bed reactors (wherein from bottom to top together
The catalyst of filling is Pd-Rh/Al2O3(0.3 weight %Pd, 0.3 weight %Rh), the catalyst is in H2Atmosphere, 150 DEG C of items
Reduction activation 6 hours under part) hydrogenation reaction is carried out, micro-nano pore membrane is provided with before fixed bed reactors, and (nano-pore is averaged
Diameter is 20nm, 800 μm of the average diameter of micron openings), hydrogen high degree of dispersion or is dissolved in terephthaldehyde by micro-nano pore membrane
In dioctyl phthalate.Hydrogenation conditions are as follows: temperature is 110 DEG C, pressure 3MPa, H2With the molar ratio of dioctyl terephthalate
It is 10, the weight space velocity of dioctyl terephthalate is 0.9h-1.It is computed, it is pungent that level-one hydrogenation unit exports terephthalic acid (TPA) two
The conversion ratio of ester is 99.9%, and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dioctyl ester is selectively 99.8%.
Secondary hydrogenation unit: hydrogen is added to produce the level-one of the resulting dioctyl ester containing 1,4 cyclohexanedicarboxylic acid of level-one hydrogenation unit
Object and H2By fixed bed reactors, (catalyst of filling is CuO-ZnO-TiO from bottom to top together2(40 weight %CuO, 40 weights
Measure %ZnO, 20 weight %TiO2), the catalyst is in H2Atmosphere, reduction activation 10 hours under the conditions of 240 DEG C) it carries out plus hydrogen is anti-
It answers, micro-nano hole channel is provided with before fixed bed reactors, and (average diameter of Nanoscale channels is 50nm, micro scale channel
Average diameter is 1000 μm), hydrogen high degree of dispersion or is dissolved in level-one hydrogenation products by micro-nano pore membrane.Hydrogenation reaction
Condition are as follows: temperature is 195 DEG C, pressure 5MPa, H2It is 15 with Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dioctyl ester molar ratio, Isosorbide-5-Nitrae-hexamethylene
The weight space velocity of alkane diformazan dioctyl phthalate is 0.8h-1.It is computed, secondary hydrogenation unit exports Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dioctyl ester
Conversion ratio be 99.9%, 1,4-CHDM is selectively 98.7%.
Separative unit: secondary hydrogenation product is sent into the first decompression separation tower: 140 DEG C of vacuum degree 90KPa, temperature, tower top
It can get the octanol byproduct of purity 99.2%, materials at bottom of tower is sent into the second decompression separation tower: vacuum degree 25KPa, temperature 200
DEG C, tower top can get the 1,4-CHDM product that purity is greater than 99.6%, and materials at bottom of tower is recycled into hydrogenation unit.
Embodiment 2
Level-one hydrogenation unit: by dibutyl terephthalate and H2Pass through the fixed bed reactors (catalyst of filling together
For Ru/SiO2(2.3 weight %Ru), the catalyst is in H2Atmosphere, reduction activation 10 hours under the conditions of 120 DEG C) it carries out plus hydrogen is anti-
It answers, hydrogenation conditions are as follows: temperature is 60 DEG C, pressure 10MPa, H2Molar ratio with dibutyl terephthalate is 3.5, right
The weight space velocity of dibatyl phithalate is 1.3h-1.It is computed, level-one hydrogenation unit exports the conversion of dibutyl terephthalate
Rate is 99.8%, and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dibutyl ester is selectively 100%.
Secondary hydrogenation unit: hydrogen is added to produce the level-one of the resulting dibutyl ester containing 1,4 cyclohexanedicarboxylic acid of level-one hydrogenation unit
Object and H2By fixed bed reactors, (catalyst of filling is CuO-MnO together2-ZrO2(60 weight %CuO, 35 weight %
MnO2, 5 weight %ZrO2), the catalyst is in H2Atmosphere, reduction activation 15 hours under the conditions of 180 DEG C) hydrogenation reaction is carried out, instead
Answer condition are as follows: temperature is 210 DEG C, pressure 10MPa, H2It is 5 with Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dibutyl ester molar ratio, Isosorbide-5-Nitrae-ring
The weight space velocity of hexane dicarboxylic acid dibutyl ester is 1.2h-1.It is computed secondary hydrogenation unit outlet two fourth of 1,4 cyclohexanedicarboxylic acid
The conversion ratio of ester is 99.9%, and 1,4-CHDM is selectively 98.3%.
Separative unit: secondary hydrogenation product is sent into the first decompression separation tower: 115 DEG C of vacuum degree 80KPa, temperature, tower top can
The butanol byproduct of purity 98.5% is obtained, materials at bottom of tower is sent into the second decompression separation tower: 170 DEG C of vacuum degree 3KPa, temperature, tower
It pushes up and can get the 1,4-CHDM product that purity is greater than 99.9%, materials at bottom of tower is recycled into hydrogenation unit.
Embodiment 3
Level-one hydrogenation unit: by dioctyl terephthalate and H2Pass through the fixed bed reactors (catalyst of filling together
For Rh-Pd/C (0.3 weight %Rh, 0.2 weight %Pd), the catalyst is in H2Atmosphere, reduction activation 5 is small under the conditions of 180 DEG C
When) carrying out hydrogenation reaction, reaction condition are as follows: temperature is 160 DEG C, pressure 0.1MPa, H2With rubbing for dioctyl terephthalate
, than being 100, the weight space velocity of dioctyl terephthalate is 3h for you-1.It is computed, level-one hydrogenator exports terephthalic acid (TPA)
The conversion ratio of dioctyl ester is 99.6%, and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dioctyl ester is selectively 99.1%.
Secondary hydrogenation unit: hydrogen is added to produce the level-one of the resulting dioctyl ester containing 1,4 cyclohexanedicarboxylic acid of level-one hydrogenation unit
Object and H2By fixed bed reactors, (catalyst of filling is CuO-ZnO-Al together2O3(42 weight %CuO, 38 weight %
ZnO, 20 weight %Al2O3), the catalyst is in H2Atmosphere, reduction activation 15 hours under the conditions of 210 DEG C) hydrogenation reaction is carried out,
Reaction condition are as follows: temperature is 220 DEG C, pressure 5MPa, H2It is 50 with Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dioctyl ester molar ratio, Isosorbide-5-Nitrae-
The weight space velocity of cyclohexane cyclohexanedimethanodibasic dioctyl ester is 0.6h-1.It is computed, secondary hydrogenation reactor outlet Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic
The conversion ratio of dioctyl ester is 99.9%, and 1,4-CHDM is selectively 99.0%.
Separative unit: secondary hydrogenation product is sent into the first decompression separation tower: 155 DEG C of vacuum degree 54KPa, temperature, tower top can
The octanol byproduct of purity 99.1% is obtained, materials at bottom of tower is sent into the second decompression separation tower: 198 DEG C of vacuum degree 15KPa, temperature,
Tower top can get the 1,4-CHDM product that purity is greater than 99.9%, and materials at bottom of tower is recycled into hydrogenation unit.
Embodiment 4
Level-one hydrogenation unit: by dibutyl terephthalate and H2Pass through the fixed bed reactors (catalyst of filling together
For Ru/C (2.5 weight %Ru), the catalyst is in H2Atmosphere, reduction activation 9 hours under the conditions of 170 DEG C) it carries out plus hydrogen is anti-
It answers, hydrogenation conditions are as follows: temperature is 130 DEG C, pressure 1.5MPa, H2Molar ratio with dibutyl terephthalate is 17,
The weight space velocity of dibutyl terephthalate is 1.6h-1.It is computed, level-one hydrogenator exports dibutyl terephthalate
Conversion ratio is 99.7%, and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dibutyl ester is selectively 99.7%.
Secondary hydrogenation unit: hydrogen is added to produce the level-one of the resulting dibutyl ester containing 1,4 cyclohexanedicarboxylic acid of level-one hydrogenation unit
Object and H2By fixed bed reactors, (catalyst of filling is CuO-CrO together3- MgO (30 weight %CuO, 40 weight %
CrO3, 30 weight %MgO), the catalyst is in H2Atmosphere, reduction activation 12 hours under the conditions of 260 DEG C) carry out hydrogenation reaction,
Reaction condition are as follows: temperature is 260 DEG C, pressure 4MPa, H2It is 100,1 with Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic dibutyl ester molar ratio,
The weight space velocity of 4- cyclohexane cyclohexanedimethanodibasic dibutyl ester is 3h-1.It is computed, secondary hydrogenation reactor outlet Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic
The conversion ratio of dibutyl ester is 99.4%, and 1,4-CHDM is selectively 98.6%.
Separative unit: secondary hydrogenation product is sent into the first decompression separation tower: 145 DEG C of vacuum degree 67KPa, temperature, tower top can
The butanol byproduct of purity 99.2% is obtained, materials at bottom of tower is sent into the second decompression separation tower: 190 DEG C of vacuum degree 11KPa, temperature,
Tower top can get the 1,4-CHDM product that purity is greater than 99.8%, and materials at bottom of tower is recycled into hydrogenation unit.
Embodiment 5
Level-one hydrogenation unit: by terephthalic acid (TPA) didecyl and H2Pass through the fixed bed reactors (catalyst of filling together
For Ru/SiO2-Al2O3(2.5 weight %Ru), the catalyst is in H2Atmosphere, reduction activation 9 hours under the conditions of 160 DEG C) into
Row hydrogenation reaction, hydrogenation conditions are as follows: temperature is 140 DEG C, pressure 3.0MPa, H2With mole of terephthalic acid (TPA) didecyl
Than being 3.8, the weight space velocity of terephthalic acid (TPA) didecyl is 0.98h-1.It is computed, level-one hydrogenator exports terephthaldehyde
The conversion ratio of sour didecyl is 99.9%, and Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic didecyl is selectively 99.7%.
Secondary hydrogenation unit: hydrogen is added to produce the level-one of the resulting didecyl containing 1,4 cyclohexanedicarboxylic acid of level-one hydrogenation unit
Object and H2By fixed bed reactors, (catalyst of filling is CuO-CrO together3- MgO (40 weight %CuO, 40 weight %
CrO3, 20 weight %MgO), the catalyst is in H2Atmosphere, reduction activation 12 hours under the conditions of 270 DEG C) carry out hydrogenation reaction,
Reaction condition are as follows: temperature is 250 DEG C, pressure 5MPa, H2It is 100,1 with Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic didecyl molar ratio,
The weight space velocity of 4- cyclohexane cyclohexanedimethanodibasic didecyl is 2.8h-1.It is computed, secondary hydrogenation reactor outlet Isosorbide-5-Nitrae-hexamethylene diformazan
The conversion ratio of sour didecyl is 99.6%, and 1,4-CHDM is selectively 98.7%.
Separative unit: secondary hydrogenation product is sent into the first decompression separation tower: 150 DEG C of vacuum degree 70KPa, temperature, tower top can
The decyl alcohol byproduct of purity 99.5% is obtained, materials at bottom of tower is sent into the second decompression separation tower: 180 DEG C of vacuum degree 10KPa, temperature,
Tower top can get the 1,4-CHDM product that purity is greater than 99.8%, and materials at bottom of tower is recycled into hydrogenation unit.
Embodiment 6
Level-one hydrogenation unit: by (dodecane) ester of terephthalic acid (TPA) two and H2Together by fixed bed reactors (filling
Catalyst is Ru/Al2O3-TiO2(2.5 weight %Ru), the catalyst is in H2Atmosphere, reduction activation 14 under the conditions of 150 DEG C
Hour) carrying out hydrogenation reaction, hydrogenation conditions are as follows: temperature is 120 DEG C, pressure 6.0MPa, H2With terephthalic acid (TPA) two (ten
Dioxane) molar ratio of ester is 4.0, the weight space velocity of terephthalic acid (TPA) two (dodecane) ester is 0.97h-1.It is computed, level-one adds hydrogen
The conversion ratio of reactor outlet terephthalic acid (TPA) two (dodecane) ester is 99.9%, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic two (dodecane) ester
Selectivity is 99.7%.
Secondary hydrogenation unit: by the resulting level-one containing 1,4 cyclohexanedicarboxylic acid two (dodecane) ester of level-one hydrogenation unit
Hydrogenation products and H2By fixed bed reactors, (catalyst of filling is CuO-ZrO together2- ZnO (40 weight %CuO, 20 weights
Measure %ZrO2, 40 weight %ZnO), the catalyst is in H2Atmosphere, reduction activation 12 hours under the conditions of 270 DEG C) it carries out plus hydrogen
Reaction, reaction condition are as follows: temperature is 260 DEG C, pressure 6MPa, H2With mole of 1,4 cyclohexanedicarboxylic acid two (dodecane) ester
Than being 120, the weight space velocity of Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic two (dodecane) ester is 3.6h-1.It is computed, secondary hydrogenation reactor goes out
The conversion ratio of mouth Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic two (dodecane) ester is 99.6%, and 1,4-CHDM is selectively
98.7%.
Separative unit: secondary hydrogenation product is sent into the first decompression separation tower: 170 DEG C of vacuum degree 60KPa, temperature, tower top can
The dodecanol byproduct of purity 99.5% is obtained, materials at bottom of tower is sent into the second decompression separation tower: vacuum degree 12KPa, temperature 190
DEG C, tower top can get the 1,4-CHDM product that purity is greater than 99.8%, and materials at bottom of tower is recycled into hydrogenation unit.
From above-described embodiment it is found that the method for the invention uses the terephthalic acid (TPA) under the larger room temperature of molecular weight being liquid
Diester be reaction raw materials solve the problems, such as circulation solvent energy consumption is high, while allow hydrogenation reaction at a lower temperature into
Row, and the selectivity of 1,4-CHDM is preferable, and by-product is less, and the separating treatment technique of products therefrom is simpler,
Good product quality.
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 (10)
1. a kind of method for producing 1,4-CHDM, method includes the following steps:
(1) terephthalic acid (TPA) dibasic ester shown in formula (I) and hydrogen are subjected in the presence of the first catalyst hydrogenation reaction, obtained
Isosorbide-5-Nitrae cyclohexane cyclohexanedimethanodibasic dibasic ester,
In formula (I), R1And R2It is identical or different, it is each independently selected from the alkyl of C4-C12；
(2) 1,4 cyclohexanedicarboxylic acid dibasic ester obtained by step (1) and hydrogen are carried out in the presence of the second catalyst plus hydrogen is anti-
It answers, obtains the product stream containing 1,4-CHDM；
(3) the resulting product stream containing 1,4-CHDM of step (2) is separated, obtains Isosorbide-5-Nitrae-hexamethylene diformazan
Alcohol product.
2. according to the method described in claim 1, wherein, the terephthalic acid (TPA) dibasic ester be dibutyl terephthalate and/
Or dioctyl terephthalate.
3. method according to claim 1 or 2, wherein first catalyst contains carrier and is supported on the load
Active component on body, the active component are one of Ni, Rh, Ru and Pd or a variety of, and the carrier is selected from Al2O3、
SiO2、TiO2With one of active carbon or a variety of.
4. method according to claim 1 or 2, wherein on the basis of the total weight of first catalyst, the activity
The content of component is 0.05-10 weight %, preferably 0.3-5 weight %.
5. method according to claim 1 or 2, wherein in step (1), the condition of the hydrogenation reaction includes: temperature
It is 60-160 DEG C, pressure 0.1-10MPa, H2Molar ratio with phthalic acid dibasic ester is 3.5-100.
6. method according to claim 1 or 2, wherein second catalyst is the catalyst containing Cu, preferably CuO-
One or more of AO-BO, A Zn, Mn, Cr, one or more of B Al, Zr, Mg, Ti.
7. according to the method described in claim 6, on the basis of the total weight of second catalyst, CuO is in the catalyst
Content be the content of 30-60 weight %, AO in the catalyst be the content of 20-50 weight %, BO in the catalyst be 0-30 weight
Measure %.
8. method according to claim 1 or 2, wherein in step (2), the condition of the hydrogenation reaction includes: temperature
It is 180-260 DEG C, pressure 0.1-10MPa, H2Molar ratio with 1,4 cyclohexanedicarboxylic acid dibasic ester is 5-100.
9. method according to claim 1 or 2, wherein hydrogenation reaction described in step (1) and (2) is in fixed bed reaction
It is carried out in device.
10. method according to claim 1 or 2, the separation is realized by decompression operation, vacuum degree 3KPa-
90KPa, temperature are 100-250 DEG C.
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| CN114436770A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Method for preparing cyclohexanedimethanol by hydrogenation of cyclohexanedicarboxylic acid dibasic ester |
| CN114929657A (en) * | 2019-12-27 | 2022-08-19 | 韩华思路信(株) | Process for preparing 1, 4-cyclohexanedicarboxylic acid |
| CN114984989A (en) * | 2022-05-11 | 2022-09-02 | 润泰化学（泰兴）有限公司 | Preparation method and application of catalyst for generating 1,4 cyclohexanedimethanol from diethylene glycol terephthalate by one-step method |
| CN115368210A (en) * | 2022-09-06 | 2022-11-22 | 浙江清和新材料科技有限公司 | Method for treating tail gas hydrogen of hydrogenation reaction |
| CN116444343A (en) * | 2023-04-11 | 2023-07-18 | 浙江大学 | Method for preparing 1, 4-cyclohexanedimethanol from waste polyester |
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| CN114929657A (en) * | 2019-12-27 | 2022-08-19 | 韩华思路信(株) | Process for preparing 1, 4-cyclohexanedicarboxylic acid |
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| CN114984989A (en) * | 2022-05-11 | 2022-09-02 | 润泰化学（泰兴）有限公司 | Preparation method and application of catalyst for generating 1,4 cyclohexanedimethanol from diethylene glycol terephthalate by one-step method |
| CN115368210A (en) * | 2022-09-06 | 2022-11-22 | 浙江清和新材料科技有限公司 | Method for treating tail gas hydrogen of hydrogenation reaction |
| CN115368210B (en) * | 2022-09-06 | 2024-04-30 | 浙江清和新材料科技有限公司 | Treatment method of tail gas hydrogen of hydrogenation reaction |
| CN116444343A (en) * | 2023-04-11 | 2023-07-18 | 浙江大学 | Method for preparing 1, 4-cyclohexanedimethanol from waste polyester |
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