CN105056996A - 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 PDF

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CN105056996A
CN105056996A CN201510513293.8A CN201510513293A CN105056996A CN 105056996 A CN105056996 A CN 105056996A CN 201510513293 A CN201510513293 A CN 201510513293A CN 105056996 A CN105056996 A CN 105056996A
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CN105056996B (en
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刘仲毅
韩舒伊
李保军
李中军
刘寿长
彭智昆
李帅辉
李卫东
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Zhengzhou University
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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

Dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate Catalysts and its preparation method, using method
Technical field
The invention belongs to chemical field, be specifically related to a kind of dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate Catalysts and its preparation method, using method.
Background technology
1,4-dimethyl hexahydrophthalate (DMCD) is important Organic Chemicals, can to get everything ready the saturation type of a lot of good characteristic or the monomer 1 of insatiable hunger type polyester by Hydrogenation, 4-cyclohexanedimethanol (CHDM), it has symmetrical structure, make polymer chain tight, this symmetry and be arranged with closely to be beneficial between polymer chain and form hydrogen bond, and then limit the motion of polymer, improve the hardness of polymer, the crystallinity of mylar also can be made to improve, make the stability of powdery paints, sintering resistance improves.CHDM is the important monomer of modified resin and polyester, has been subject to paying attention to more and more widely, and estimating will increase further to the demand of CHDM from now on.DMCD is as preparation CHDM intermediate, and suitability for industrialized production is extremely urgent.Key issue is to improve catalyst, reduces operating pressure, selects suitable solvent, improves productive rate, finally reaches the object reduced costs.
By dimethyl terephthalate (DMT) (DMT) Hydrogenation for DMCD, the history of existing more than 30 year, adopts Pd/Al 2o 3or 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, at Pd/Al 2o 3second component (VIII race's metal is as Ni, Ru, Pt) is added in catalyst.Calendar year 2001, Nanjing Chemical Industrial group company produces NCG-2 hydrogenation catalyst, and Ni mass fraction is 40%, carrier is active A l 2o 3, reduce operating pressure, but DMCD yield is lower.2003, Yi Si Man of the U.S. adopted the loaded catalyst of Ni mass fraction 20% ~ 60%, and operating pressure 8MPa, temperature 140 DEG C, within 2005, Ni catalyst is used in the preparation technology of DMCD by the said firm, and operating pressure is still higher.Use Pd supported catalyst and the load Ru catalyst of modification in recent years, DMCD yield is unsatisfactory.
Openly patent of invention US3,334,149 prepare Isosorbide-5-Nitrae-dimethyl hexahydrophthalate and 1,4-CHDM with dimethyl terephthalate (DMT) as raw material, and operating pressure is higher than 34MPa.
Openly patent of invention CN1380282A adopts active component to be that the catalyst of metal Pd is for dimethyl terephthalate (DMT) selective hydrogenation system 1,4 dimethyl hexahydrophthalates, introducing two kinds of metallic elements (the IIth A and the VIIIth race) in catalyst is auxiliary agent, but Pd is as a kind of noble metal, expensive, and catalyst preparing and technique for applying flow process complexity not easy to operate.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide a kind of dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate Catalysts and its preparation method, using method.
For achieving the above object, the technical scheme taked of the present invention is as follows:
A kind of dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate catalyst, this catalyst is Ru particle, and Ru particle surface is modified with Ru-S and Ru-O coordinate bond.
Preparation method: the method is with RuCl 3xH 2o is active component precursors, and polyethylene glycol is stabilizing agent, and thiophene dicarboxylic acid is dressing agent, and sodium borohydride or hydrogen are reducing agent, and preparation process is:
1. solution preparation: preparation RuCl 3xH 2o mass fraction is 5 ~ 10%, polyethylene glycol mass fraction is the mixed solution of 2 ~ 6%;
2. reduction reaction: mixed solution is transferred in autoclave, 80 ~ 150 DEG C, 3 ~ 5MPa hydrogen pressure, reduction reaction 2 ~ 8h under 800 ~ 1200r/min speed of agitator; Or 20 ~ 40 DEG C, normal pressure, under 300-800r/min speed of agitator, the aqueous solution of the sodium borohydride of mass fraction 0.4 ~ 1% is adopted to make reducing agent, dropping to solution is colourless (when solution is colourless, represent that reduction reaction is complete, this process approximately needs 1 ~ 2h);
3. washing of precipitate: after reduction reaction terminates, shifts out supernatant, and precipitum is Ru particle, and Ru particles rinsed with water is to neutrality, without chlorion;
4. molecular modification: preparation thiophene dicarboxylic acid mass fraction is 0.05 ~ 0.5%, NaOH mass fraction is the mixed solution of 0.01 ~ 0.3%, be transferred in autoclave, adding the Ru particle that washed to its mass fraction in this mixed solution is 1 ~ 5%, 130 ~ 150 DEG C, 4 ~ 5MPa hydrogen pressure, reaction 1 ~ 4h carries out molecular modification to Ru particle surface under 800 ~ 1000r/min speed of agitator;
5. post processing: isolate the Ru particle after molecular modification, washing is to neutral, dry, obtains final catalyst.
Further, the molecular weight of polyethylene glycol is preferably 2000 ~ 10000.
Using method: take methyl alcohol as solvent, dimethyl terephthalate (DMT) and catalyst 150 ~ 250 DEG C, 4.0 ~ 6.0MPa hydrogen pressure, reaction 1 ~ 4h under 1000 ~ 1200r/min speed of agitator, obtained Isosorbide-5-Nitrae-dimethyl hexahydrophthalate; Mass ratio 1:(20 ~ 100 of catalyst and dimethyl terephthalate (DMT)), the mass ratio of terephthalic acid (TPA) and methyl alcohol is 1:(10 ~ 30).
The reaction equation of dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate is as follows:
The good effect that the present invention produces:
Compared with prior art, catalyst of the present invention is used for dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate, and have better catalytic activity and target product selectivity, and hydroconversion condition is gentle, the reaction time is shorter.
Accompanying drawing explanation
Fig. 1: transmission electron microscope (TEM) photo of catalyst prepared by embodiment 1.
Fig. 2: the x-ray photoelectron power spectrum O1 of catalyst prepared by embodiment 1 s(d), S2 p(c), Ru3 d 5/2(b), meticulous spectrum and full spectrum (a).
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described, but do not limit protection scope of the present invention.
Embodiment 1
A preparation method for dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate catalyst, concrete steps are as follows:
1. solution preparation: preparation RuCl 33H 2o mass fraction is 5%, polyethylene glycol (PEG-2000) mass fraction is the mixed solution of 2%, stirs 0.5h;
2. reduction reaction: above-mentioned mixed solution is transferred in liner polytetrafluoro autoclave, 80 DEG C, 3MPa hydrogen pressure, under 800r/min speed of agitator, reduction reaction 3h;
3. washing of precipitate: after reduction reaction terminates, shifts out supernatant, and sediment (i.e. Ru particle) spends deionized water to neutrality, without chlorion;
4. molecular modification: preparation thiophene dicarboxylic acid mass fraction is 0.09%, NaOH mass fraction is the mixed solution of 0.05%, be transferred in autoclave, adding the good Ru particle of above-mentioned washing to its mass fraction in this mixed solution is 1%, 130 DEG C, 4MPa hydrogen pressure, react 2h under 800r/min speed of agitator molecular modification carried out to Ru particle surface;
5. post processing: by the Ru particle centrifugation through molecular modification, washing is to neutral, and freeze drying, obtains final catalyst.
Fig. 1 is transmission electron microscope (TEM) photo of the present embodiment 1 final catalyst, can find out that this catalyst is the spheroid of diameter 2 ~ 5nm, and wherein 0.21nm is 101 interplanar distances of Ru.
Fig. 2 is the x-ray photoelectron power spectrum O1s(d of the present embodiment 1 final catalyst), S2p(c), Ru3d 5/2b according to the chemical shift of electron binding energy, () meticulous spectrum and full spectrum (a), can judge that this catalyst surface forms Ru-S and Ru-O coordinate bond.
Embodiment 2
A preparation method for dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate catalyst, concrete steps are as follows:
1. solution preparation: preparation RuCl 35H 2o mass fraction is 10%, polyethylene glycol (PEG-10000) mass fraction is the mixed solution of 6%, stirs 1h;
2. reduction reaction: above-mentioned mixed solution is transferred in liner C276 Hastelloy autoclave, 150 DEG C, 5MPa hydrogen pressure, under 1200r/min speed of agitator, reduction reaction 5h;
3. washing of precipitate: after reduction reaction terminates, shifts out supernatant, sediment (i.e. Ru particle) with pure water to neutral, without chlorion;
4. molecular modification: preparation thiophene dicarboxylic acid mass fraction is 0.2%, NaOH mass fraction is the mixed solution of 0.09%, be transferred in autoclave, adding the good Ru particle of above-mentioned washing to its mass fraction in this mixed solution is 5%, 150 DEG C, 5MPa hydrogen pressure, react 3h under 1000r/min speed of agitator molecular modification carried out to Ru particle surface;
5. post processing: by the Ru particle centrifugation through molecular modification, washing is to neutral, and vacuum drying, obtains final catalyst.
Transmission electron microscope (TEM) photo and x-ray photoelectron power spectrum O1s, S2p, Ru3d 5/2the characterization result of meticulous spectrum and full spectrum is with embodiment 1.
Embodiment 3
A preparation method for dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate catalyst, concrete steps are as follows:
1. solution preparation: preparation RuCl 33H 2o mass fraction is 5%, polyethylene glycol (PEG-2000) mass fraction is the mixed solution of 2%, stirs 0.5h;
2. reduction reaction: 25 DEG C, normal pressure, under 500r/min speed of agitator, adopt the aqueous solution of the sodium borohydride of mass fraction 0.5% to make reducing agent, it is colourless for dropwise dropping to solution;
3. washing of precipitate: after reduction terminates, shift out supernatant, sediment (i.e. Ru particle) spends deionized water to neutrality, without chlorion;
4. molecular modification: preparation thiophene dicarboxylic acid mass fraction is 0.3%, NaOH mass fraction is the mixed solution of 0.14%, be transferred in autoclave, adding the good Ru particle of above-mentioned washing to its mass fraction in this mixed solution is 1%, 130 DEG C, 4MPa hydrogen pressure, react 2h under 800r/min speed of agitator molecular modification carried out to Ru particle surface;
5. post processing: by the Ru particle centrifugation through molecular modification, washing is to neutral, and vacuum drying, obtains final catalyst, Average crystallite particle diameter 3nm.
Transmission electron microscope (TEM) photo and x-ray photoelectron power spectrum O1s, S2p, Ru3d 5/2the characterization result of meticulous spectrum and full spectrum is with embodiment 1.
Embodiment 4
A preparation method for dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate catalyst, concrete steps are as follows:
1. solution preparation: preparation RuCl 35H 2o mass fraction is 10%, polyethylene glycol (PEG-10000) mass fraction is the mixed solution of 6%, stirs 1h;
2. reduction reaction: 40 DEG C, normal pressure, under 800r/min speed of agitator, adopt the aqueous solution of the sodium borohydride of mass fraction 0.5% to make reducing agent, it is colourless for dropwise dropping to solution;
3. washing of precipitate: reduction terminate after, shift out supernatant, sediment (i.e. Ru particle) with pure water to neutrality, without chlorion;
4. molecular modification: preparation thiophene dicarboxylic acid mass fraction is 0.5%, NaOH mass fraction is the mixed solution of 0.3%, be transferred in autoclave, adding the good Ru particle of above-mentioned washing to its mass fraction in this mixed solution is 5%, 150 DEG C, 5MPa hydrogen pressure, react 3h under 1000r/min speed of agitator molecular modification carried out to Ru particle surface;
5. post processing: by the Ru particle centrifugation through molecular modification, washing is to neutral, and freeze drying, obtains final catalyst.
Transmission electron microscope (TEM) photo and x-ray photoelectron power spectrum O1s, the characterization result of the meticulous spectrum of S2p, Ru3d5/2 and full spectrum is with embodiment 1.
Embodiment 5
A kind of using method of dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate catalyst:
With 50mL methyl alcohol for solvent, dimethyl terephthalate (DMT) 2g, embodiment 1 catalyst 0.03g, 150 DEG C, 4MPa hydrogen pressure, under 1000r/min speed of agitator, reaction 1.0h, adopts gas chromatographic detection product composition, Isosorbide-5-Nitrae-dimethyl hexahydrophthalate selective 98.56%.
Embodiment 6
A kind of using method of dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate catalyst:
With 50mL methyl alcohol for solvent, dimethyl terephthalate (DMT) 2g, embodiment 2 catalyst 0.03g, 150 DEG C, 6MPa hydrogen pressure, under 1200r/min speed of agitator, reaction 1.0h, adopts gas chromatographic detection product composition, Isosorbide-5-Nitrae-dimethyl hexahydrophthalate selective 98.99%.
Embodiment 7
A kind of using method of dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate catalyst:
With 50mL methyl alcohol for solvent, dimethyl terephthalate (DMT) 2g, embodiment 3 catalyst 0.03g, 210 DEG C, 4MPa hydrogen pressure, under 1000r/min speed of agitator, reaction 1.0h, adopts gas chromatographic detection product composition, Isosorbide-5-Nitrae-dimethyl hexahydrophthalate selective 99.42%.
Embodiment 8
A kind of using method of dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate catalyst:
With 50mL methyl alcohol for solvent, dimethyl terephthalate (DMT) 2g, embodiment 4 catalyst 0.03g, 210 DEG C, 6MPa hydrogen pressure, under 1200r/min speed of agitator, reaction 1.0h, adopts gas chromatographic detection product composition, Isosorbide-5-Nitrae-dimethyl hexahydrophthalate selective 99.50%.
Embodiment 5 ~ 8 the results are shown in table 1:
Above preferred embodiment of the present invention has been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalization changes done according to the present patent application scope with improve, within the protection domain that still all should belong to patent of the present invention.

Claims (4)

1. dimethyl terephthalate (DMT) selective hydrogenation Isosorbide-5-Nitrae-dimethyl hexahydrophthalate catalyst, is characterized in that: this catalyst is Ru particle, and Ru particle surface is modified with Ru-S and Ru-O coordinate bond.
2. prepare a method for catalyst as claimed in claim 1, it is characterized in that: the method is with RuCl 3xH 2o is active component precursors, and polyethylene glycol is stabilizing agent, and thiophene dicarboxylic acid is dressing agent, and sodium borohydride or hydrogen are reducing agent, and preparation process is:
1. solution preparation: preparation RuCl 3xH 2o mass fraction is 5 ~ 10%, polyethylene glycol mass fraction is the mixed solution of 2 ~ 6%;
2. reduction reaction: mixed solution is transferred in autoclave, 80 ~ 150 DEG C, 3 ~ 5MPa hydrogen pressure, reduction reaction 2 ~ 8h under 800 ~ 1200r/min speed of agitator; Or 20 ~ 40 DEG C, normal pressure, under 300-800r/min speed of agitator, adopt the aqueous solution of the sodium borohydride of mass fraction 0.4 ~ 1% to make reducing agent, it is colourless for dropping to solution;
3. washing of precipitate: after reduction reaction terminates, shifts out supernatant, and precipitum is Ru particle, and Ru particles rinsed with water is to neutrality, without chlorion;
4. molecular modification: preparation thiophene dicarboxylic acid mass fraction is 0.05 ~ 0.5%, NaOH mass fraction is the mixed solution of 0.01 ~ 0.3%, be transferred in autoclave, adding the Ru particle that washed to its mass fraction in this mixed solution is 1 ~ 5%, 130 ~ 150 DEG C, 4 ~ 5MPa hydrogen pressure, reaction 1 ~ 4h carries out molecular modification to Ru particle surface under 800 ~ 1000r/min speed of agitator;
5. post processing: isolate the Ru particle after molecular modification, washing is to neutral, dry, obtains final catalyst.
3. preparation method as claimed in claim 2, is characterized in that: the molecular weight of polyethylene glycol is 2000 ~ 10000.
4. the using method of a catalyst as claimed in claim 1, it is characterized in that: take methyl alcohol as solvent, dimethyl terephthalate (DMT) and catalyst 150 ~ 250 DEG C, 4.0 ~ 6.0MPa hydrogen pressure, reaction 1 ~ 4h under 1000 ~ 1200r/min speed of agitator, obtained Isosorbide-5-Nitrae-dimethyl hexahydrophthalate; Mass ratio 1:(20 ~ 100 of catalyst and dimethyl terephthalate (DMT)), the mass ratio of terephthalic acid (TPA) and methyl alcohol is 1:(10 ~ 30).
CN201510513293.8A 2015-08-20 2015-08-20 Catalyst for selectively hydrogenating dimethyl terephthalate to prepare 1,4-cyclohexane dimethyl isophthalate and preparation method and use method of catalyst Active CN105056996B (en)

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CN105056997A (en) * 2015-08-20 2015-11-18 郑州大学 Catalyst for preparing 1,4-cyclohexanedicarboxylic acid in selective hydrogenation mode through terephthalic acid, preparing method thereof and utilization method thereof
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
CN109896958A (en) * 2017-12-07 2019-06-18 中国科学院大连化学物理研究所 A kind of synthetic method of 1,2,4,5- cyclohexanetetracarboxylic acid tetra-ethyl ester
CN111672508A (en) * 2020-06-23 2020-09-18 中国天辰工程有限公司 Preparation and application of catalyst for preparing 1, 4-cyclohexane dimethyl phthalate by hydrogenating dimethyl terephthalate

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CN105056997A (en) * 2015-08-20 2015-11-18 郑州大学 Catalyst for preparing 1,4-cyclohexanedicarboxylic acid in selective hydrogenation mode through terephthalic acid, preparing method thereof and utilization method thereof

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