CN105037161B - Continuous synthesis method of cyclohexane polyacid ester - Google Patents
Continuous synthesis method of cyclohexane polyacid ester Download PDFInfo
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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
- C07C67/00—Preparation of carboxylic acid esters
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Abstract
The invention relates to a synthesis method of cyclohexane polyacid ester. The method specifically comprises the following steps of: adding benzene polycarboxylic acid or anhydride thereof and alcohol into a stirring tank reactor; adding in an acid catalyst and raising the temperature to 200-240 DEG C; carrying out some reaction until an acid value is less than 0.2 mg KOH/g; directly adding a crude product resulting from the esterification reaction into a trickle bed reactor for hydrogenation reaction, wherein the hydrogen pressure is 40-100 bar, the temperature is 70-250 DEG C, and a catalyst is a porous oxide loaded with VIII B group metal; and after the reaction, adding in alkali for neutralization and acid removal, performing distillation or evaporation to remove alcohol, removing by-products; and performing filtration and deliming to obtain cyclohexane polyacid ester. According to the method provided by the invention, after the esterification reaction generates the crude product, no purification step is not performed; excess alcohol is used as a solvent for subsequent hydrogenation reaction; and after the hydrogenation reaction, purification steps such as alcohol removing, acid removing and filtration are performed, thereby saving time and energy. Meanwhile, according to the method provided by the invention, the alumina-magnesia composite oxide is used as the catalyst carrier, and palladium or ruthenium is selected as the metal catalyst, enabling the phenyl ring hydrogenation rate to be greater than 99.9%.
Description
Technical field
The present invention relates to a kind of method of synthesizing cyclohexane 1 alkane polybasic ester, specifically a kind of by raw material continuous esterification, reduction
The method for obtaining hexamethylene polybasic ester.
Background technology
As discovered in recent years phthalate plasticizer may be detrimental to health, its can by drinking-water, feed,
Skin is contacted and breathing enters human body, and this kind of compound of Long Term Contact can be caused to damage to peripheral nervous system, and cause multiple
The symptom such as nerve is scorching and insensitive, numb.And World Health Organization (WHO) also indicates that phthalate compound（Especially
The phthalate of short carbon chain）Hydrolysis metabolites in human body easily affect organ intracellular metabolite and reproductive function, therefore belong to
In Environmental Hormone, has bioaccumulation.Therefore many countries and regions（Comprising European Union, the U.S., Japan and Taiwan）To neighbour
The use of Phthalates plasticiser has extremely strict specification, and related specifications extensively can be seen for infant（3 years old with
Under）And anemia of pregnant woman's articles for use, food, medical supplies, it is contemplated that can get over strict.Therefore, develop and can replace traditional phthalic acid ester
The environmentally friendly and safe plasticizer of class has become the imperative trend of global related industry.
Many non-phthalic acid ester class plasticizers are had on the market, but every kind of replacement plasticizer has which to limit and lack
Point, can substitute the actually minority of phthalate plasticizer completely.The plasticizer for most substituting potentiality at present is 1,2-
Cyclohexane cyclohexanedimethanodibasic dibasic ester class plasticizer.Such plasticizer is with butadiene and maleic anhydride as raw material, via Diels-
Alder additive reaction tetrahydrobiopterin synthesis phthalic anhydrides, then synthesis hexahydrophthalic anhydride is hydrogenated, last hexahydro O-phthalic
Anhydride carries out esterification synthesis with alcohol and obtains.It is the advantage of this technology without phthalate residual, but needs to be dependent on need
The butadiene raw material that the amount of asking is big and price fluctuation is big inferior position then for this technology maximum.
At present regulation to the phthalate content specification in infant plastic be need to 1000ppm with
Under, and 30 ~ 70% estimations are accounted for general phthalate plasticiser content in PVC product, using hydrogenization method by adjacent benzene
Dioctyl phthalate makes the plasticizer for meeting regulation, and its phenyl ring hydrogenation ratio is at least needed more than 99.9%.In other words, for phthalic acid
The phenyl ring hydrogenation ratio of esters is at least needed more than 99.9%, so obtained 1,2- cyclohexane cyclohexanedimethanodibasic dibasic ester plasticizers product side
The specification of current law can be met.
DINCH（1,2- cyclohexane cyclohexanedimethanodibasic dinonyl）Be European Union forbid in the plastic with human body close contact and
Primary plasticizer first-selected after phthalic ester plasticizer used in toy for children, in nontoxic application is required,
DINCH is equally excellent universal plasticizer.Up to the present, countries in the world have been ratified it and have been contacted with food, use this product
Made by PVC toys for children and related plastic cement products meet European Union 1999/815/EC environmental protection resolutions.
Now diisononyl phthalate will be hydrogenated after purification again with technology, complex steps, energy resource consumption is big,
And the conversion ratio of diisononyl phthalate can only achieve 99%.
The content of the invention
It is an object of the invention to provide one kind is by benzene polycarboxylic acid or its anhydride continuous esterification, reduction, high conversion synthesizes ring
The method of hexane polybasic ester, its hydride conversion rate is up to more than 99.9%.
To reach above-mentioned purpose, the present invention is employed the following technical solutions：
A kind of method of synthesizing cyclohexane 1 alkane polybasic ester, by it is not post-treated after benzene polycarboxylic acid or its anhydride and alcohol esterification,
Crude product containing alcohol direct catalytic hydrogenation is obtained into hexamethylene polybasic ester.
Further, the benzene polycarboxylic acid is phthalic acid, M-phthalic acid, p-phthalic acid, 1,2,4- benzene front threes
Acid, 1,3,5- benzenetricarboxylic acids or 1,2,3- benzenetricarboxylic acids.
Further, the step of the esterification it is：It is 1 by mol ratio：2.2 ~ 3.5 benzene polycarboxylic acid or its anhydride and alcohol throw
Enter stirred tank reactor, reactor uses alcohol-water flow decker, acid catalyst post-heating added to 200 ~ 240 DEG C, instead
0.2mgKOH/g should be less than to acid value.
Further, during described alcohol is C1 ~ C30 alkylols, C3 ~ C30 cycloalkyl alcohols and C1 ~ C30 alkoxyalkyl alcohol
At least one.
C1 ~ C30 alkylols be carbon number for 1 ~ 30, carbochain for straight or branched alkylol.
C3 ~ C30 cycloalkyl alcohols are carbon numbers for 3 ~ 30, containing one or more cycloalkyl（Cyclopropyl, cyclobutyl, ring
Amyl group, cyclohexyl etc.）Alcohol, carbochain is straight or branched.
C1 ~ C30 alkoxyalkyl alcohol is carbon number for 2 ~ 30, containing one or more alkoxyls（Methoxyl group, ethyoxyl
Deng）Alcohol, carbochain is straight or branched.
Further, described alcohol is at least one in the alkylol of the straight or branched of C2 ~ C20.
Further, described alcohol is at least one in butanol, isooctanol, isononyl alcohol and isodecanol.
Further, the step of the catalytic hydrogenation it is：Esterification crude product is fed directly to into trickle bed reactor
Hydrogenation is carried out, Hydrogen Vapor Pressure is 40 ~ 100bar, and temperature is 70 ~ 250 DEG C, and catalyst is the porous oxygen for loading VIII B races metal
Compound.
Further, the VIII B races metal is at least one in ruthenium, rhodium and palladium.
Further, the porous oxides are alumina-silica Magnesium coumpoud oxides.
Further, post processing is carried out after catalytic hydrogenation：Plus remove alcohol and remove by-product with deacidification, distillation or evaporation in alkali
Thing, filtration deliming.
Further, by mol ratio be 1：During 2.2 ~ 3.5 benzene polycarboxylic acid or its anhydride and alcohol add stirred tank reactor,
Reactor uses alcohol-water flow decker, adds acid catalyst post-heating to 200 ~ 240 DEG C, reacts to acid value and be less than
0.2mgKOH/g, the esterification crude product containing alcohol is fed directly to trickle bed reactor then carries out hydrogenation, hydrogen
Atmospheric pressure is 40 ~ 100bar, and temperature is 70 ~ 250 DEG C, and catalyst is the porous oxides for loading VIII B races metal, after reaction terminates
Plus in alkali and deacidify, distill or evaporate except alcohol and except by-product, filtration deliming, obtain hexamethylene polybasic ester.
The invention has the advantages that：
The esterification of hexamethylene polybasic ester and hydrogenation process are integrated by the present invention, reduce purifying procedure that is complicated and consuming energy,
With the purpose for reaching energy-conservation with reduce production cost, first without purification step after esterification generates crude product, with excess
The solvent that alcohol is reacted as subsequent hydrogenation, is carried out except purification steps such as alcohol, deacidification, filtrations, during saving after hydrogenation again
Between and the energy.The present invention selects alumina-silica Magnesium coumpoud oxide as catalyst carrier simultaneously, from palladium or ruthenium as metal
Catalyst, makes phenyl ring hydrogenation ratio up to more than 99.9%.And the esterification plant of the present invention adopts continuously stirred tank reactor (CSTR) and alcohol water to return
Stream decker, hydrogenation equipment adopt trickle bed reactor, and occupation area of equipment is little, processing ease, alcohol-water flow decker
The water that esterification is generated can quickly be excluded by difference of specific gravity, and be reacted part alcohol reflux.
Specific embodiment
With reference to specific embodiment, the present invention is described further：
The preparation method of catalyst used by following examples is as follows：
By 420g magnesium nitrate hexahydrate [Mg（NO3）2﹒ 6H2O] and 465g ANN aluminium nitrate nonahydrate [Al（NO3）3﹒ 9H2O] it is dissolved in
In 6000mL deionized waters, add the aqueous solution containing sodium carbonate and be co-precipitated, and be thoroughly mixed at 60 DEG C, plus
Filter after entering the stirring of 300g aluminium oxidies, gained filter cake is dried at 110 DEG C after washing, obtains alumina-silica magnesium composite oxygen
Compound powder body.
300g alumina-silica Magnesium coumpoud oxide powder body and 60g forming agents and adhesive agent are taken, through mediating and being squeezed into
Type step, after calcining 4h, obtains cylindric porous oxides carrier at 450 DEG C, and wherein magnesium oxide accounts for 12wt%, by this
Cylindric porous oxides carrier is crushed, and the granulate that sieves obtains the granule of 20 ~ 30 mesh counts.
The above-mentioned granules of about 30g are taken, with containing RuCl3Impregnation solution, ruthenium metal is implanted in into carrier surface using incipient wetness method,
After 4h is calcined at 450 DEG C, X catalyst is obtained, wherein ruthenium accounts for 5wt%, and apparent density is 0.649g/cm3。
Order takes the above-mentioned granules of about 30g, with containing PdCl2Impregnation solution, palladium metal is implanted in into carrier table using incipient wetness method
Face, after calcining 4h, is obtained Y catalyst at 450 DEG C, and wherein palladium accounts for 2wt%, and apparent density is 0.546g/cm3。
Embodiment 1
It is 1 by mol ratio：During 2.5 phthalic anhydride and isononyl alcohol add stirred tank reactor, reactor uses alcohol
Water backflow decker, adding acid catalyst post-heating carries out esterification to 220 DEG C, shown in formula I, reacts to adjacent benzene two
The acid value of formic acid dinonyl crude product is less than 0.2mgKOH/g, and gained diisononyl phthalate crude product contains excessive different
Nonyl alcohol（Containing about 85% diisononyl phthalate and about 15% isononyl alcohol）.The X catalyst of 3.9g is taken, 3/8 English of diameter is filled in
As fixed bed in very little rustless steel continuous way trickle bed reactor（Filling 6mL）, then by esterification crude product without
Under purification process, being fed directly to trickle bed reactor carries out hydrogenation, and shown in formula I, Hydrogen Vapor Pressure is 50bar, temperature
For 70 DEG C, hydrogen flow rate is 100mL/min, and esterification crude product flow velocity is 4.5mL/h, two different nonyl of hydrogen and phthalic acid
The mol ratio of ester is about 28：1.After reaction terminates plus in alkali and deacidify（The acid catalyst of esterification）, distillation is except alcohol and removing
By-product, filtration deliming, obtain 1,2- cyclohexane cyclohexanedimethanodibasic dinonyls.
With remaining phenyl ring concentration in UV-visible spectroscopy assay products, phenyl ring absworption peak about in wavelength 275nm,
Diisononyl phthalate has strong absorption, and 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl prepares the adjacent benzene of variable concentrations without absorption
A calibration curve is done in dioctyl phthalate dinonyl/1,2- cyclohexane cyclohexanedimethanodibasic dinonyls, calculates diisononyl phthalate
Concentration and hydrogenation ratio（Concentration % of hydrogenation ratio=1- remnants diisononyl phthalates）.
Analysis result shows that the concentration of diisononyl phthalate is about 1000ppm, i.e. phenyl ring hydrogenation ratio up to 99.90%.
Formulas I
Embodiment 2
It is 1 by mol ratio：During 2.5 phthalic anhydride and isononyl alcohol add stirred tank reactor, reactor uses alcohol
Water backflow decker, adding acid catalyst post-heating carries out esterification to 220 DEG C, reacts to two different nonyl of phthalic acid
The acid value of ester crude product is less than 0.2mgKOH/g, and gained diisononyl phthalate crude product contains excessive isononyl alcohol.Take
The X catalyst of 3.9g, is filled in the rustless steel continuous way trickle bed reactor of 3/8 inch of diameter as fixed bed（Filling 6mL）,
Then, by esterification crude product under without purification process, being fed directly to trickle bed reactor carries out hydrogenation, hydrogen
Pressure is 50bar, and temperature is 100 DEG C, and hydrogen flow rate is 100mL/min, and esterification crude product flow velocity is 4.5mL/h, hydrogen
It is about 28 with the mol ratio of diisononyl phthalate：1.After reaction terminates plus in alkali and deacidify, distill except alcohol and except pair
Product, filtration deliming, obtain 1,2- cyclohexane cyclohexanedimethanodibasic dinonyls.
With remaining phenyl ring concentration in UV-visible spectroscopy assay products, analysis result shows phthalic acid two
The concentration of different nonyl ester is about 500ppm, i.e. phenyl ring hydrogenation ratio up to 99.95%.
Embodiment 3
It is 1 by mol ratio：During 2.5 phthalic anhydride and isononyl alcohol add stirred tank reactor, reactor uses alcohol
Water backflow decker, adding acid catalyst post-heating carries out esterification to 220 DEG C, reacts to two different nonyl of phthalic acid
The acid value of ester crude product is less than 0.2mgKOH/g, and gained diisononyl phthalate crude product contains excessive isononyl alcohol.Take
The X catalyst of 3.9g, is filled in the rustless steel continuous way trickle bed reactor of 3/8 inch of diameter as fixed bed（Filling 6mL）,
Then, by esterification crude product under without purification process, being fed directly to trickle bed reactor carries out hydrogenation, hydrogen
Pressure is 50bar, and temperature is 120 DEG C, and hydrogen flow rate is 100mL/min, and esterification crude product flow velocity is 4.5mL/h, hydrogen
It is about 28 with the mol ratio of diisononyl phthalate：1.After reaction terminates plus in alkali and deacidify, evaporate except alcohol and except pair
Product, filtration deliming, obtain 1,2- cyclohexane cyclohexanedimethanodibasic dinonyls.
With remaining phenyl ring concentration in UV-visible spectroscopy assay products, analysis result shows phthalic acid two
The concentration of different nonyl ester is about 400ppm, i.e. phenyl ring hydrogenation ratio up to 99.96%.
Embodiment 4
It is 1 by mol ratio：During 2.5 phthalic anhydride and isononyl alcohol add stirred tank reactor, reactor uses alcohol
Water backflow decker, adding acid catalyst post-heating carries out esterification to 220 DEG C, reacts to two different nonyl of phthalic acid
The acid value of ester crude product is less than 0.2mgKOH/g, and gained diisononyl phthalate crude product contains excessive isononyl alcohol.Take
The X catalyst of 3.9g, is filled in the rustless steel continuous way trickle bed reactor of 3/8 inch of diameter as fixed bed（Filling 6mL）,
Then, by esterification crude product under without purification process, being fed directly to trickle bed reactor carries out hydrogenation, hydrogen
Pressure is 100bar, and temperature is 70 DEG C, and hydrogen flow rate is 100mL/min, and esterification crude product flow velocity is 4.5mL/h, hydrogen
It is about 28 with the mol ratio of diisononyl phthalate：1.After reaction terminates plus in alkali and deacidify, evaporate except alcohol and except pair
Product, filtration deliming, obtain 1,2- cyclohexane cyclohexanedimethanodibasic dinonyls.
With remaining phenyl ring concentration in UV-visible spectroscopy assay products, analysis result shows phthalic acid two
The concentration of different nonyl ester is about 400ppm, i.e. phenyl ring hydrogenation ratio up to 99.96%.
Embodiment 5
It is 1 by mol ratio：During 2.2 phthalic acid and isononyl alcohol add stirred tank reactor, reactor uses alcohol water
Backflow decker, adding acid catalyst post-heating carries out esterification to 200 DEG C, reacts to acid value and is less than 0.2mgKOH/
g.The Y catalyst of 3.3g is taken, is filled in the rustless steel continuous way trickle bed reactor of 3/8 inch of diameter as fixed bed（Filling
6mL）, then by esterification crude product under without purification process, being fed directly to trickle bed reactor carries out hydrogenation,
Hydrogen Vapor Pressure is 50bar, and temperature is 180 DEG C, and hydrogen flow rate is 100mL/min, and esterification crude product flow velocity is 4.5mL/h,
The mol ratio of hydrogen and diisononyl phthalate is about 28：1.After reaction terminates plus in alkali and deacidification, distillation except alcohol and
Except by-product, deliming is filtered, obtain 1,2- cyclohexane cyclohexanedimethanodibasic dinonyls.
With remaining phenyl ring concentration in UV-visible spectroscopy assay products, analysis result shows phthalic acid two
The concentration of different nonyl ester is about 1000ppm, i.e. phenyl ring hydrogenation ratio up to 99.90%.
Embodiment 6
It is 1 by mol ratio：During 3 M-phthalic acid and isooctanol add stirred tank reactor, reactor is returned using alcohol water
Stream decker, adding acid catalyst post-heating carries out esterification to 240 DEG C, reacts to acid value and is less than 0.2mgKOH/g.
The Y catalyst of 3.3g is taken, is filled in the rustless steel continuous way trickle bed reactor of 3/8 inch of diameter as fixed bed（Filling
6mL）, then by esterification crude product under without purification process, being fed directly to trickle bed reactor carries out hydrogenation,
Hydrogen Vapor Pressure is 50bar, and temperature is 210 DEG C, and hydrogen flow rate is 100mL/min, and esterification crude product flow velocity is 4.5mL/h,
The mol ratio of hydrogen and diisooctyl isophthalate is about 28：1.After reaction terminates plus in alkali and deacidification, distillation except alcohol and
Except by-product, deliming is filtered, obtain 1,3- cyclohexane cyclohexanedimethanodibasic di-isooctyls.
With remaining phenyl ring concentration in UV-visible spectroscopy assay products, analysis result shows M-phthalic acid two
The concentration of different monooctyl ester is about 300ppm, i.e. phenyl ring hydrogenation ratio up to 99.97%.
Embodiment 7
It is 1 by mol ratio：During the 1 of 3.5,2,4- benzenetricarboxylic acids and butanol add stirred tank reactor, reactor uses alcohol
Water backflow decker, adding acid catalyst post-heating carries out esterification to 230 DEG C, reacts to acid value and is less than
0.2mgKOH/g.The Y catalyst of 3.3g is taken, is filled in the rustless steel continuous way trickle bed reactor of 3/8 inch of diameter as solid
Fixed bed（Filling 6mL）, then by esterification crude product under without purification process, being fed directly to trickle bed reactor is carried out
Hydrogenation, Hydrogen Vapor Pressure is 50bar, and temperature is 250 DEG C, and hydrogen flow rate is 100mL/min, and esterification crude product flow velocity is
4.5mL/h, hydrogen and 1, the mol ratio of 2,4- benzenetricarboxylic acid tributyls are about 28：1.After reaction terminates plus in alkali and deacidify, steam
Distillation alcohol and except by-product, filter deliming, obtain 1,2,4- hexamethylene tricarboxylic acid tributyls.
With remaining phenyl ring concentration in UV-visible spectroscopy assay products, analysis result shows 1,2,4- benzene front threes
The concentration of sour tributyl is about 0ppm, i.e. phenyl ring hydrogenation ratio up to 100%.
Embodiment 8
It is 1 by mol ratio：During the 1 of 3.3,3,5- benzenetricarboxylic acids and isodecanol add stirred tank reactor, reactor is used
Alcohol-water flow decker, adding acid catalyst post-heating carries out esterification to 210 DEG C, reacts to acid value and is less than
0.2mgKOH/g.The Y catalyst of 3.3g is taken, is filled in the rustless steel continuous way trickle bed reactor of 3/8 inch of diameter as solid
Fixed bed（Filling 6mL）, then by esterification crude product under without purification process, being fed directly to trickle bed reactor is carried out
Hydrogenation, Hydrogen Vapor Pressure is 70bar, and temperature is 180 DEG C, and hydrogen flow rate is 100mL/min, and esterification crude product flow velocity is
4.5mL/h, hydrogen and 1, the mol ratio of 3,5- benzenetricarboxylic acid, three isodecyl ester are about 28：1.React in adding alkali after terminating and deacidify,
Distillation obtains 1,3,5- hexamethylene tricarboxylic acid, three isodecyl ester except alcohol and except by-product, filtration deliming.
With remaining phenyl ring concentration in UV-visible spectroscopy assay products, analysis result shows 1,3,5- benzene front threes
The concentration of sour three isodecyl esters is about 700ppm, i.e. phenyl ring hydrogenation ratio up to 99.93%.
Embodiment 9
It is 1 by mol ratio：During the 1 of 3.4,2,3- benzenetricarboxylic acids and butanol add stirred tank reactor, reactor uses alcohol
Water backflow decker, adding acid catalyst post-heating carries out esterification to 220 DEG C, reacts to acid value and is less than
0.2mgKOH/g.The Y catalyst of 3.3g is taken, is filled in the rustless steel continuous way trickle bed reactor of 3/8 inch of diameter as solid
Fixed bed（Filling 6mL）, then by esterification crude product under without purification process, being fed directly to trickle bed reactor is carried out
Hydrogenation, Hydrogen Vapor Pressure 100bar, temperature are 180 DEG C, and hydrogen flow rate is 100mL/min, and esterification crude product flow velocity is
4.5mL/h, hydrogen and 1, the mol ratio of 2,3- benzenetricarboxylic acid tributyls are about 28：1.After reaction terminates plus in alkali and deacidify, steam
Distillation alcohol and except by-product, filter deliming, obtain 1,2,3- hexamethylene tricarboxylic acid tributyls.
With remaining phenyl ring concentration in UV-visible spectroscopy assay products, analysis result shows 1,2,3- benzene front threes
The concentration of sour tributyl is about 400ppm, i.e. phenyl ring hydrogenation ratio up to 99.96%.
Embodiment 10
The X catalyst of 66.5g is taken, is filled in the rustless steel continuous way trickle bed reactor of 1 inch of diameter as fixed bed
（Filling 104mL）, 1,2- cyclohexane cyclohexanedimethanodibasics dinonyl obtained by embodiment 5 is carried out into second hydrogenation, hydrogen then
Pressure is 70bar, and temperature is 85 DEG C, and hydrogen flow rate is 418mL/min, and 1,2- cyclohexane cyclohexanedimethanodibasic dinonyl flow velocity is
The mol ratio of 62.4mL/h, hydrogen and diisononyl phthalate is about 28：1.Analysis result shows that phthalic acid two is different
The concentration of nonyl ester is 100ppm, i.e. phenyl ring hydrogenation ratio up to 99.99%.
The reaction condition and testing result of embodiment 1 ~ 10 are collected, as shown in table 1：
The reaction condition and testing result of 1 embodiment 1 ~ 10 of table
| Embodiment | Catalyst | Hydrogen Vapor Pressure（bar） | Hydrogenation temperature（℃） | Phthalate concentration（ppm） | Phenyl ring hydrogenation ratio（100%） |
| 1 | X catalyst | 50 | 70 | 1000 | 99.90 |
| 2 | X catalyst | 50 | 100 | 500 | 99.95 |
| 3 | X catalyst | 50 | 120 | 400 | 99.96 |
| 4 | X catalyst | 100 | 70 | 400 | 99.96 |
| 5 | Y catalyst | 50 | 180 | 1000 | 99.90 |
| 6 | Y catalyst | 50 | 210 | 300 | 99.97 |
| 7 | Y catalyst | 50 | 250 | 0 | 100 |
| 8 | Y catalyst | 70 | 180 | 700 | 99.93 |
| 9 | Y catalyst | 100 | 180 | 400 | 99.96 |
| 10 | X catalyst | 70 | 85 | 100 | 99.99 |
By the result of embodiment 1 ~ 9 it is known that in the synthetic method of the present invention, the benzene of phthalate crude product
Hydrogenated rate is all up to more than 99.9%（99.9~100%）, can fully meet the requirement of current law（Phthalate need to be
Below 1000ppm）, meet European Union 1995/815/ with PVC toys for children made by hexamethylene polybasic ester and related plastic cement products
EC environmental protection resolutions；And by the result of embodiment 10 it is known that after second hydrogenation, two different nonyl of phthalic acid
The concentration of ester can be down to the phenyl ring hydrogenation ratio of about 100ppm, i.e. diisononyl phthalate crude product and can be promoted to 99.99%.
The above, the only specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, any
Belong to those skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in all are answered
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be defined by scope of the claims.
Claims (1)
1. a kind of method of synthesizing cyclohexane 1 alkane polybasic ester, it is characterised in that methods described is specially：It is 1 by mol ratio：3.5
1,2,4- benzenetricarboxylic acids and butanol add stirred tank reactor in, reactor use alcohol-water flow decker, add acid
Catalyst post-heating carries out esterification to 230 DEG C, reacts to acid value and is less than 0.2mgKOH/g；The Y catalyst of 3.3g is taken, is filled in
As fixed bed in the rustless steel continuous way trickle bed reactor of 3/8 inch of diameter, 6mL is filled, then esterification is slightly produced
Under without purification process, be fed directly to trickle bed reactor carries out hydrogenation to thing, and Hydrogen Vapor Pressure is 50bar, and temperature is
250 DEG C, hydrogen flow rate is 100mL/min, and esterification crude product flow velocity is 4.5mL/h, hydrogen and 1,2,4- benzenetricarboxylic acids three
The mol ratio of butyl ester is about 28: 1, after reaction terminates plus in alkali and deacidifies, distills except alcohol and except by-product, filter deliming, obtains
To 1,2,4- hexamethylene tricarboxylic acid tributyls；
The preparation method of the Y catalyst is as follows：
(1) by 420g magnesium nitrate hexahydrates [Mg (NO3)2·6H2O] and 465g ANN aluminium nitrate nonahydrates [Al (NO3)3·9H2O] it is dissolved in
In 6000mL deionized waters, add the aqueous solution containing sodium carbonate and be co-precipitated, and be thoroughly mixed at 60 DEG C, plus
Filter after entering the stirring of 300g aluminium oxidies, gained filter cake is dried at 110 DEG C after washing, obtains alumina-silica magnesium composite oxygen
Compound powder body；
(2) 300g alumina-silica Magnesium coumpoud oxide powder body and 60g forming agents and adhesive agent are taken, through mediating and being squeezed into
Type step, after calcining 4h, obtains cylindric porous oxides carrier at 450 DEG C, and wherein magnesium oxide accounts for 12wt%, by this
Cylindric porous oxides carrier is crushed, and the granulate that sieves obtains the granule of 20～30 mesh counts；
(3) the above-mentioned granules of about 30g are separately taken, with containing PdCl2Impregnation solution, palladium metal is implanted in into carrier surface using incipient wetness method,
After 4h is calcined at 450 DEG C, Y catalyst is obtained, wherein palladium accounts for 2wt%, and apparent density is 0.546g/cm3。
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| US11845849B2 (en) * | 2020-07-28 | 2023-12-19 | Evonik Operations Gmbh | Process for preparing dialkyl 1,4-cyclohexanedicarboxylates |
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| KR102496349B1 (en) * | 2017-11-29 | 2023-02-03 | 한화솔루션 주식회사 | Process for hydrogenation of phthalate compound |
| KR102458721B1 (en) * | 2017-11-29 | 2022-10-26 | 한화솔루션 주식회사 | Process for hydrogenation of phthalate compound |
| CN110437067A (en) * | 2018-05-02 | 2019-11-12 | 湖南长岭石化科技开发有限公司 | The method for preparing cyclohexane cyclohexanedimethanodibasic ester |
| WO2020091361A1 (en) | 2018-10-29 | 2020-05-07 | 주식회사 엘지화학 | Cyclohexane triester-based plasticizer composition, and resin composition containing same |
| TWI697479B (en) * | 2019-02-15 | 2020-07-01 | 台灣中油股份有限公司 | Process for making alicyclic ploycarboxylic ester |
| TWI705956B (en) * | 2019-04-15 | 2020-10-01 | 南亞塑膠工業股份有限公司 | Method preparing 1,4-cyclohexanedimethanol |
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| KR100688403B1 (en) * | 1997-12-19 | 2007-03-09 | 바스프 악티엔게젤샤프트 | Method For Hydrogenating Benzene Polycarboxylic Acids Or Derivatives Thereof By Using A Catalyst Containing Macropores |
| US8766017B2 (en) * | 2011-07-29 | 2014-07-01 | Eastman Chemical Company | Integrated process for the preparation of 1,4-cyclohexanedimethanol from terephthalic acid |
| CN104058968B (en) * | 2013-03-22 | 2016-04-06 | 长春人造树脂厂股份有限公司 | The manufacture method of terephthalic acid two (2-ethylhexyl) |
| CN103304418A (en) * | 2013-06-09 | 2013-09-18 | 中国海洋石油总公司 | Method for preparing environment-friendly plasticizer cyclohexane dicarboxylic acid ester |
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