CN105056996B - Catalyst for selectively hydrogenating dimethyl terephthalate to prepare 1,4-cyclohexane dimethyl isophthalate and preparation method and use method of catalyst - Google Patents
Catalyst for selectively hydrogenating dimethyl terephthalate to prepare 1,4-cyclohexane dimethyl isophthalate and preparation method and use method of catalyst Download PDFInfo
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Abstract
The invention belongs to the field of chemistry and chemical engineering, and particularly discloses a catalyst for selectively hydrogenating dimethyl terephthalate to prepare 1,4-cyclohexane dimethyl isophthalate and a preparation method and use method of the catalyst. The catalyst is Ru particles, and the surfaces of the Ru particles are modified with Ru-S and Ru-O coordinate bonds. The preparation method comprises the steps of solution preparation, a reduction reaction, sedimentation and washing, molecular modification and aftertreatment. Compared with the prior art, the catalyst is used for selectively hydrogenating dimethyl terephthalate to prepare 1,4-cyclohexane dimethyl isophthalate, better catalytic activity and target product selectivity are achieved, hydrogenation conditions are mild, and reaction time is shorter.
Description
Technical field
The invention belongs to chemical field, and in particular to a kind of dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-ring
Hexane dicarboxylic acid dimethyl ester catalyst and preparation method thereof, using method.
Background technology
1,4 cyclohexanedicarboxylic acid dimethyl ester（DMCD）Important Organic Chemicals, can Hydrogenation get everything ready and have many excellent
The saturation type of good characteristic or the monomer 1,4 cyclohexane dimethanol of insatiable hunger type polyester（CHDM）, it has symmetrical structure so that poly-
The arrangement of compound chain is tight, this symmetry and is closely spaced and is conducive to forming hydrogen bond between polymer chain, and then limits polymerization
The motion of thing, improves the hardness of polymer, and the crystallinity that can also make polyester resin is improved, and makes the stability of powdery paints, resistance to
Agglutinating property is improved.CHDM is the important monomer of modified resin and polyester, is widely paid attention to by more and more, it is contemplated that from now on
The demand of CHDM will further be increased.DMCD is extremely urgent as CHDM intermediates, industrialized production is prepared.Key is asked
Topic is to improve catalyst, reduce operating pressure, select suitable solvent, improve yield, is finally reached the purpose of reduces cost.
By dimethyl terephthalate (DMT)（DMT）Hydrogenation is for DMCD, existing more than 30 years history, using Pd/Al2O3Or Ni/
Diatomite catalyst, operating pressure is higher than 34MPa.The nineties in 20th century, Yi Si Man of the U.S. in order to improve hydrogenation activity,
Pd/Al2O3The second component is added in catalyst（VIII race's metal such as Ni, Ru, Pt）.Calendar year 2001, Nanjing Chemical Industrial group company
Production NCG-2 hydrogenation catalysts, it is activity Al that Ni mass fractions are 40%, carrier2O3, reduce operating pressure, but DMCD yields
It is relatively low.2003, Yi Si Man of the U.S. using Ni mass fractions 20% ~ 60% loaded catalyst, operating pressure 8MPa,
140 DEG C of temperature, the said firm in 2005 is used for Ni catalyst in the preparation technology of DMCD, and operating pressure is still higher.Make in recent years
With modified Pd supported catalysts and load Ru catalyst, DMCD yields are unsatisfactory.
The dimethyl terephthalate (DMT) of disclosed patent of invention US 3,334,149 makees raw material and prepares 1,4- hexamethylene diformazans
Dimethyl phthalate and 1,4-CHDM, operating pressure is higher than 34MPa.
Disclosed patent of invention CN1380282A adopts active component is used for terephthalic acid (TPA) two for the catalyst of metal Pd
Methyl esters selective hydrogenation Isosorbide-5-Nitrae dimethyl hexahydrophthalate, introduces two kinds of metallic elements in catalyst（IIth A and the VIIIth race）
For auxiliary agent, but Pd is used as a kind of noble metal, expensive, and catalyst preparation and technique for applying flow process be not complicated easy to operate.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of dimethyl terephthalate (DMT) selective hydrogenation
1,4 cyclohexanedicarboxylic acid dimethyl ester catalyst processed and preparation method thereof, using method.
For achieving the above object, the technical scheme that the present invention takes is as follows：
A kind of dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate catalyst, the catalysis
Agent is Ru particles, and Ru particle surfaces are modified with Ru-S and Ru-O coordinate bonds.
Preparation method：The method is with RuCl3·xH2O is active component precursors, and polyethylene glycol is stabilizer, thiophene dicarboxylic acid
For dressing agent, sodium borohydride or hydrogen are reducing agent, and preparation process is：
1. solution is prepared：Prepare RuCl3·xH2O mass fractions be 5 ~ 10%, polyethylene glycol mass fraction for 2 ~ 6% it is mixed
Close solution；
2. reduction reaction：Mixed solution is transferred in autoclave, 80 ~ 150 DEG C, 3 ~ 5 MPa hydrogen pressures, 800 ~
2 ~ 8h of reduction reaction under 1200 r/min speeds of agitator；Or under 20 ~ 40 DEG C, normal pressure, 300-800r/min speeds of agitator,
Reducing agent is done using the aqueous solution of the sodium borohydride of mass fraction 0.4 ~ 1%, solution is dropped in colourless（When solution is in colourless, table
Show reduction reaction completely, this process takes around 1 ~ 2h）；
3. washing of precipitate：After reduction reaction terminates, supernatant is removed, precipitum is Ru particles, Ru particles rinsed with water
To neutrality, without chlorion；
4. molecular modification：It is that 0.05 ~ 0.5%, NaOH mass fraction is 0.01 to prepare thiophene dicarboxylic acid's mass fraction
~ 0.3% mixed solution, in being transferred to autoclave, adds the Ru particles for having washed to its quality in the mixed solution point
Number is 1 ~ 5%, and 1 ~ 4h is reacted under 130 ~ 150 DEG C, 4 ~ 5MPa hydrogen pressures, 800 ~ 1000r/min speeds of agitator to Ru particle surfaces
Carry out molecular modification；
5. post-process：The Ru particles Jing after molecular modification are isolated, is washed to neutrality, be dried, obtain final product final catalyst.
Further, the molecular weight of polyethylene glycol is preferably 2000 ~ 10000.
Using method：With methyl alcohol as solvent, dimethyl terephthalate (DMT) and catalyst are in 150 ~ 250 DEG C, 4.0 ~ 6.0 MPa
1 ~ 4h is reacted under hydrogen pressure, 1000 ~ 1200r/min speeds of agitator, Isosorbide-5-Nitrae-dimethyl hexahydrophthalate is obtained；Catalyst with to benzene
The mass ratio 1 of dicarboxylic acid dimethyl ester:(20 ~ 100), terephthalic acid (TPA) is 1 with the mass ratio of methyl alcohol:(10~30 ).
The reaction equation of dimethyl terephthalate (DMT) selective hydrogenation 1,4 cyclohexanedicarboxylic acid dimethyl ester is as follows：
The good effect that the present invention is produced：
Compared with prior art, catalyst of the present invention is used for dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-hexamethylene
Dicarboxylic acid dimethyl ester, with more preferable catalysis activity and target product selectivity, and hydroconversion condition is gentle, and the reaction time is shorter.
Description of the drawings
Fig. 1：The transmission electron microscope of catalyst prepared by embodiment 1（TEM）Photo.
Fig. 2：X-ray photoelectron power spectrum O1 of catalyst prepared by embodiment 1s（d）, S2p（c）, Ru3d 5/2（b）, finely
Spectrum and full spectrum（a）.
Specific embodiment
With reference to specific embodiment, the invention will be further described, but does not limit protection scope of the present invention.
Embodiment 1
A kind of preparation of dimethyl terephthalate (DMT) selective hydrogenation 1,4 cyclohexanedicarboxylic acid dimethyl ester catalyst
Method, comprises the following steps that：
1. solution is prepared：Prepare RuCl3·3H2O mass fractions are 5%, polyethylene glycol（PEG-2000）Mass fraction is
2% mixed solution, stirs 0.5h；
2. reduction reaction：Above-mentioned mixed solution is transferred in liner polytetrafluoro autoclave, 80 DEG C, 3MPa hydrogen pressures,
Under 800 r/min speeds of agitator, reduction reaction 3h；
3. washing of precipitate：After reduction reaction terminates, supernatant, sediment are removed（That is Ru particles）It is washed with deionized
To neutrality, without chlorion；
4. molecular modification：It is 0.05% that preparation thiophene dicarboxylic acid's mass fraction is 0.09%, NaOH mass fraction
Mixed solution, in being transferred to autoclave, the Ru particles for adding above-mentioned washing good are to its mass fraction in the mixed solution
1%, react 2h under 130 DEG C, 4MPa hydrogen pressures, 800r/min speeds of agitator carries out molecular modification to Ru particle surfaces；
5. post-process：The Ru particle centrifugations of Jing molecular modifications are washed to neutrality, freeze-drying, obtain final product target and urge
Agent.
Fig. 1 is the transmission electron microscope of the final catalyst of the present embodiment 1（TEM）Photo, it can be seen that the catalyst be diameter 2 ~
The spheroid of 5nm, wherein 0.21nm are 101 interplanar distances of Ru.
Fig. 2 is x-ray photoelectron power spectrum O1s of the final catalyst of the present embodiment 1（d）, S2p（c）, Ru3d5/2（b）Finely
Spectrum and full spectrum（a）, may determine that the catalyst surface forms Ru-S and Ru-O coordinations according to the chemical shift of electron binding energy
Key.
Embodiment 2
A kind of preparation of dimethyl terephthalate (DMT) selective hydrogenation 1,4 cyclohexanedicarboxylic acid dimethyl ester catalyst
Method, comprises the following steps that：
1. solution is prepared：Prepare RuCl3·5H2O mass fractions are 10%, polyethylene glycol（PEG-10000）Mass fraction
For 6% mixed solution, 1h is stirred；
2. reduction reaction：Above-mentioned mixed solution is transferred in liner C276 Hastelloy autoclaves, in 150 DEG C, 5MPa
Under hydrogen pressure, 1200 r/min speeds of agitator, reduction reaction 5h；
3. washing of precipitate：After reduction reaction terminates, supernatant, sediment are removed（That is Ru particles）With pure water into
Property, without chlorion；
4. molecular modification：Prepare thiophene dicarboxylic acid's mass fraction be 0.2%, NaOH mass fraction be 0.09% it is mixed
Solution is closed, in being transferred to autoclave, adds the good Ru particles of above-mentioned washing to its mass fraction in the mixed solution to be 5%,
React 3 h under 150 DEG C, 5MPa hydrogen pressures, 1000r/min speeds of agitator carries out molecular modification to Ru particle surfaces；
5. post-process：The Ru particle centrifugations of Jing molecular modifications are washed to neutrality, vacuum drying, obtain final product target and urge
Agent.
Transmission electron microscope（TEM）Photo and x-ray photoelectron power spectrum O1s, S2p, Ru3d5/2The sign knot of fine spectrum and full spectrum
Fruit is with embodiment 1.
Embodiment 3
A kind of preparation of dimethyl terephthalate (DMT) selective hydrogenation 1,4 cyclohexanedicarboxylic acid dimethyl ester catalyst
Method, comprises the following steps that：
1. solution is prepared：Prepare RuCl3·3H2O mass fractions are 5%, polyethylene glycol（PEG-2000）Mass fraction is
2% mixed solution, stirs 0.5h；
2. reduction reaction：Under 25 DEG C, normal pressure, 500r/min speeds of agitator, using the sodium borohydride of mass fraction 0.5%
The aqueous solution make reducing agent, dropwise drop to solution in colourless；
3. washing of precipitate：After reduction terminates, supernatant, sediment are removed（That is Ru particles）It is washed with deionized into
Property, without chlorion；
4. molecular modification：Prepare thiophene dicarboxylic acid's mass fraction be 0.3%, NaOH mass fraction be 0.14% it is mixed
Solution is closed, in being transferred to autoclave, adds the good Ru particles of above-mentioned washing to its mass fraction in the mixed solution to be 1%,
2h is reacted under 130 DEG C, 4MPa hydrogen pressures, 800r/min speeds of agitator carries out molecular modification to Ru particle surfaces；
5. post-process：The Ru particle centrifugations of Jing molecular modifications are washed to neutrality, vacuum drying, obtain final product target and urge
Agent, Average crystallite particle diameter 3nm.
Transmission electron microscope（TEM）Photo and x-ray photoelectron power spectrum O1s, S2p, Ru3d5/2The sign knot of fine spectrum and full spectrum
Fruit is with embodiment 1.
Embodiment 4
A kind of preparation of dimethyl terephthalate (DMT) selective hydrogenation 1,4 cyclohexanedicarboxylic acid dimethyl ester catalyst
Method, comprises the following steps that：
1. solution is prepared：Prepare RuCl3·5H2O mass fractions are 10%, polyethylene glycol（PEG-10000）Mass fraction
For 6% mixed solution, 1h is stirred；
2. reduction reaction：Under 40 DEG C, normal pressure, 800r/min speeds of agitator, using the sodium borohydride of mass fraction 0.5%
The aqueous solution make reducing agent, dropwise drop to solution in colourless；
3. washing of precipitate：After reduction terminates, supernatant, sediment are removed（That is Ru particles）With pure water to neutral, nothing
Chlorion；
4. molecular modification：Preparation thiophene dicarboxylic acid's mass fraction is 0.5%, the mixing that NaOH mass fraction is 0.3%
Solution, in being transferred to autoclave, adds the good Ru particles of above-mentioned washing to its mass fraction in the mixed solution to be 5%,
150 DEG C, 5MPa hydrogen pressures, react 3 h under 1000r/min speeds of agitator molecular modification carried out to Ru particle surfaces；
5. post-process：The Ru particle centrifugations of Jing molecular modifications are washed to neutrality, freeze-drying, obtain final product target and urge
Agent.
Transmission electron microscope（TEM）Photo and x-ray photoelectron power spectrum O1s, the sign knot that S2p, Ru3d5/2 are finely composed and composed entirely
Fruit is with embodiment 1.
Embodiment 5
A kind of use of dimethyl terephthalate (DMT) selective hydrogenation 1,4 cyclohexanedicarboxylic acid dimethyl ester catalyst
Method：
With 50mL methyl alcohol as solvent, dimethyl terephthalate (DMT) 2g, the catalyst 0.03g of embodiment 1, in 150 DEG C, 4MPa
Under hydrogen pressure, 1000r/min speeds of agitator, 1.0 h are reacted, constituted using gas chromatographic detection product, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic
Dimethyl ester selective 98.56%.
Embodiment 6
A kind of use of dimethyl terephthalate (DMT) selective hydrogenation 1,4 cyclohexanedicarboxylic acid dimethyl ester catalyst
Method：
With 50mL methyl alcohol as solvent, dimethyl terephthalate (DMT) 2g, the catalyst 0.03g of embodiment 2, in 150 DEG C, 6MPa
Under hydrogen pressure, 1200r/min speeds of agitator, 1.0 h are reacted, constituted using gas chromatographic detection product, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic
Dimethyl ester selective 98.99%.
Embodiment 7
A kind of use of dimethyl terephthalate (DMT) selective hydrogenation 1,4 cyclohexanedicarboxylic acid dimethyl ester catalyst
Method：
With 50mL methyl alcohol as solvent, dimethyl terephthalate (DMT) 2g, the catalyst 0.03g of embodiment 3, in 210 DEG C, 4MPa
Under hydrogen pressure, 1000r/min speeds of agitator, 1.0 h are reacted, constituted using gas chromatographic detection product, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic
Dimethyl ester selective 99.42%.
Embodiment 8
A kind of use of dimethyl terephthalate (DMT) selective hydrogenation 1,4 cyclohexanedicarboxylic acid dimethyl ester catalyst
Method：
With 50mL methyl alcohol as solvent, dimethyl terephthalate (DMT) 2g, the catalyst 0.03g of embodiment 4, in 210 DEG C, 6MPa
Under hydrogen pressure, 1200r/min speeds of agitator, 1.0 h are reacted, constituted using gas chromatographic detection product, Isosorbide-5-Nitrae-cyclohexane cyclohexanedimethanodibasic
Dimethyl ester selective 99.50%.
The result of embodiment 5 ~ 8 is listed in table 1：
Presently preferred embodiments of the present invention has been described in detail above, but the content is only the preferable enforcement of the present invention
Example, it is impossible to be considered as the practical range for limiting the present invention.All impartial changes made according to the present patent application scope and improvement
Deng all should still belong within the protection domain of patent of the present invention.
Claims (3)
1. a kind of side for preparing dimethyl terephthalate (DMT) selective hydrogenation 1,4 cyclohexanedicarboxylic acid dimethyl ester catalyst
Method, it is characterised in that：The catalyst is Ru particles, and Ru particle surfaces are modified with Ru-S and Ru-O coordinate bonds；The method with
RuCl3·xH2O is active component precursors, and polyethylene glycol is stabilizer, and thiophene dicarboxylic acid is dressing agent, sodium borohydride or hydrogen
For reducing agent, preparation process is：
1. solution is prepared：Prepare RuCl3·xH2O mass fractions are that the mixing that 5 ~ 10%, polyethylene glycol mass fraction is 2 ~ 6% is molten
Liquid；
2. reduction reaction：Mixed solution is transferred in autoclave, 80 ~ 150 DEG C, 3 ~ 5 MPa hydrogen pressures, 800 ~ 1200 r/
2 ~ 8h of reduction reaction under min speeds of agitator；Or under 20 ~ 40 DEG C, normal pressure, 300-800r/min speeds of agitator, using quality
The aqueous solution of the sodium borohydride of fraction 0.4 ~ 1% makees reducing agent, drops to solution in colourless；
3. washing of precipitate：After reduction reaction terminates, supernatant is removed, precipitum is Ru particles, and Ru particles rinsed with water is into
Property, without chlorion；
4. molecular modification：It is that 0.05 ~ 0.5%, NaOH mass fraction is 0.01 ~ 0.3% to prepare thiophene dicarboxylic acid's mass fraction
Mixed solution, in being transferred to autoclave, add the Ru particles that washs to its mass fraction in the mixed solution for 1 ~
5%, react 1 ~ 4h under 130 ~ 150 DEG C, 4 ~ 5MPa hydrogen pressures, 800 ~ 1000r/min speeds of agitator is carried out point to Ru particle surfaces
Son modification；
5. post-process：The Ru particles Jing after molecular modification are isolated, is washed to neutrality, be dried, obtain final product final catalyst.
2. the method for claim 1, it is characterised in that：The molecular weight of polyethylene glycol is 2000 ~ 10000.
3. the using method of catalyst prepared by a kind of method as claimed in claim 1 or 2, it is characterised in that：With methyl alcohol as molten
Agent, dimethyl terephthalate (DMT) and catalyst 150 ~ 250 DEG C, 4.0 ~ 6.0 MPa hydrogen pressures, 1000 ~ 1200r/min speeds of agitator
1 ~ 4h of lower reaction, is obtained Isosorbide-5-Nitrae-dimethyl hexahydrophthalate；The mass ratio 1 of catalyst and dimethyl terephthalate (DMT):(20~
100), dimethyl terephthalate (DMT) and the mass ratio of methyl alcohol are 1:(10~30 ).
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| CN105056997B (en) * | 2015-08-20 | 2017-08-11 | 郑州大学 | A kind of cyclohexane cyclohexanedimethanodibasic catalyst of terephthalic acid (TPA) selective hydrogenation system 1,4 and preparation method thereof, application method |
| CN108187675A (en) * | 2017-12-01 | 2018-06-22 | 中海油天津化工研究设计院有限公司 | A kind of preparation method of noble metal catalyst for benzene ring hydrogenation saturation |
| CN109896958B (en) * | 2017-12-07 | 2021-06-01 | 中国科学院大连化学物理研究所 | Synthesis method of 1,2,4, 5-cyclohexane tetracarboxylate |
| CN111672508B (en) * | 2020-06-23 | 2023-03-14 | 中国天辰工程有限公司 | Preparation and application of catalyst for preparing 1,4-dimethyl cyclohexanedicarboxylate through dimethyl terephthalate hydrogenation |
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