CN108636440A - A kind of catalyst and preparation method thereof of glycerine water solution Hydrogenation 1,3- propylene glycol - Google Patents
A kind of catalyst and preparation method thereof of glycerine water solution Hydrogenation 1,3- propylene glycol Download PDFInfo
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- CN108636440A CN108636440A CN201810336749.1A CN201810336749A CN108636440A CN 108636440 A CN108636440 A CN 108636440A CN 201810336749 A CN201810336749 A CN 201810336749A CN 108636440 A CN108636440 A CN 108636440A
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- propylene glycol
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The present invention relates to a kind of glycerine water solution Hydrogenations for the catalyst and 1 of 1,3 propylene glycol, the preparation method of 3 propylene glycol, and catalyst includes molecular sieve, Pt, X and W for being supported on the molecular sieve, wherein X is Mo and/or Co.The preparation method of 1,3-PD be 10%~60% by mass percent concentration glycerine water solution be 130~200 DEG C in reaction temperature in the presence of above-mentioned catalyst, being passed through hydrogen makes pressure control in 1~6MPa, and air speed is 0.1~5h‐1, reaction generation 1,3-PD.The stability of catalyst of the present invention is high, is suitable for glycerine water solution Hydrogenation for 1,3 propylene glycol, method using the present invention prepares 1,3 propylene glycol, raw material are easy to get, and reaction condition is mild, reaction temperature, only need water as solvent, the generating rate of 1,3 propylene glycol is high, meet green chemical industry requirement, there is great market value and prospects for commercial application.
Description
Technical field
The present invention relates to a kind of glycerine water solution Hydrogenations for the catalyst of 1,3- propylene glycol and the preparation method of catalyst.
Background technology
The Rapid Expansion of production of biodiesel ability all over the world, causes the excess capacity of by-product glycerol.It is sweet to make
Oil becomes the raw material of great cost attractive.
1,3-PD is a kind of important industrial chemicals, using it as the polyester fiber terephthalic acid (TPA) the third two of monomer synthesis
Ester (PTT) has both the high-performance and polybutylene terephthalate (PBT) easy processing of polyethylene terephthalate ester (PET)
Property, it has broad application prospects in the fields such as production plasticizer, detergent, preservative, emulsifier.
Currently, the preparation method of 1,3-PD mainly has：Epoxyethane method, acrolein hydration method, microbe fermentation method
With glycerine hydrogenation catforming.Epoxyethane method and acrolein hydration method all need two-step reaction to prepare 1,3-PD, reaction
Technique is cumbersome, and equipment requirement is high, and operating condition is harsh；And microbe fermentation method production concentration is low, separating step is cumbersome, biological enzyme
It is short life, stringent to technological requirement；Therefore, the simplest using glycerine as the technique of the direct hydrogenation catalyzed conversion of raw material.
Chinese patent CN96198050.8 discloses a kind of method that oxirane carbonyl is hydrogenated to 1,3 propylene glycol,
3-HPA is generated with reacting ethylene oxide in the presence of a catalyst with synthesis gas, 3-HPA is with hydrogen in catalyst
Under effect, reaction generates 1,3-PD.Chinese patent CN93114516.3 discloses a kind of acrylic acid hydration hydrogenation method generation
The technology of 1,3-PD, first glycerine are dehydrated under the action of catalyst generates methacrylaldehyde, and methacrylaldehyde generates 3- through hydration reaction
Hydroxy propanal, for 3-HPA with hydrogen under catalytic action, reaction generates 1,3-PD.Both methods technique it is cumbersome and
Severe reaction conditions, there are larger problem of environmental pollutions.
Document (Appl.Microbiol.Biothechnol.1995,16,79-80) reports a kind of glycerine can be by Chinese holly
The method that rafter acidfast bacilli category, Klebsiella and clostruidium bacterial strain are converted into 1,3- propylene glycol.But this method produces
It is less efficient.
Solvent in Chinese patent 200810224899.X and 201010262066.X is all made of double solvents 1,3- diformazans
Base -2- imidazolones-water or alcohols-aqueous mixtures, solvent recovery are complex.
Chinese patent 200910237839.6 includes ZrO using Pt, W, refractory oxide or its predecessor, carrier2
Or TiO2.But the yield of its 1,3- propylene glycol is less than 6%.
Invention content
The object of the present invention is to provide a kind of glycerine water solution Hydrogenations for the catalyst of 1,3-PD, utilizes the catalysis
When agent prepares 1,3-PD, reaction condition is mild, stable reaction, and solvent is only water.
It is a further object to provide the preparation methods of above-mentioned catalyst.
Third object of the present invention is to provide the method using above-mentioned catalyst preparation 1,3-PD, prepared by this method
The generating rate of 1,3- propylene glycol is high.
In order to solve the above technical problems, the present invention adopts the following technical scheme that：
It is an object of the present invention to provide a kind of glycerine water solution Hydrogenations for the catalyst of 1,3-PD, described
Catalyst includes molecular sieve, and the catalyst further includes Pt, X and the W being supported on the molecular sieve, wherein X Mo
And/or Co.
Preferably, the quality of the X is the 0.1~5% of the catalyst gross mass.
It is further preferred that the quality of the X is the 0.1~3% of the catalyst gross mass.
Preferably, the quality of the Pt is the 0.1~5% of the catalyst gross mass.
It is further preferred that the quality of the Pt is the 1~3% of the catalyst gross mass.
Preferably, the quality of the W is the 5~20% of the catalyst gross mass.
It is further preferred that the quality of the W is the 10~15% of the catalyst gross mass.
Preferably, when the X is Mo and Co, the mass ratio of the Mo and the Co are 3~5:1.
Preferably, the mass percent of described Pt, X and W are 2:0.5~2.5:9~11, further preferably 2:1~
2.5:9~11.
It is a further object to provide a kind of glycerine water solution Hydrogenations for the catalysis of 1,3- propylene glycol
The preparation method of agent, includes the following steps：
(1), ammonium metatungstate aqueous solution is impregnated into molecular sieve, is kept for 15~25 hours at 90~100 DEG C, is then existed
It dries at 105~115 DEG C, then is roasted 2~4 hours at 650~750 DEG C；
(2), intermediate products made from step (1) are impregnated in the mixed solution or chloroplatinic acid of chloroplatinic acid and nitric acid molybdenum
In the mixed solution of the mixed solution or chloroplatinic acid of cobalt nitrate, nitric acid molybdenum and cobalt nitrate, aging 8~10 hours, drying,
Then it is roasted 2~4 hours at 400~500 DEG C, the catalyst is made.
Preferably, the calcination temperature of step (2) is 450~500 DEG C.
Third object of the present invention is to provide a kind of preparation methods of 1,3-PD, are by mass percent concentration
10%~60% glycerine water solution is in the presence of a catalyst 130~200 DEG C in reaction temperature, being passed through hydrogen makes pressure
Control generates the 1,3-PD in 1~6MPa, reaction, wherein the catalyst is above-mentioned catalyst.
Preferably, the air speed of the glycerine water solution is 0.1~0.5h-1。
Preferably, the reactor is fluid bed or fixed bed.
Due to the implementation of above technical scheme, the present invention has following advantage compared with prior art：
The stability of the catalyst of the present invention is high, is suitable for glycerine water solution Hydrogenation for 1,3-PD, using this hair
Bright method prepares 1,3-PD, and raw material is easy to get, and reaction condition is mild, reaction temperature, it is only necessary to and water is as solvent, and 1,3- third
The generating rate of glycol is high, meets green chemical industry requirement, has great market value and prospects for commercial application.
Specific implementation mode
The present invention is described in further details below in conjunction with specific embodiment.It should be understood that these embodiments are for saying
The bright basic principles, principal features and advantages of the present invention, and the present invention is not limited by the following examples.It is used in embodiment
Implementation condition can do further adjustment according to specific requirement, and the implementation condition being not specified is usually the condition in routine experiment.
Embodiment 1
Catalyst used is Pt/Mo/W- molecular sieves, and metal quality percentage is Pt：Mo：W=2：1：10.Catalyst system
Include for step:1) it is impregnated into molecular sieve with the ammonium metatungstate aqueous solution of requirement, 90 DEG C are kept for 20 hours, 110 DEG C of bakings
Dry, 700 DEG C roast 3 hours, obtain tungsten-molecular sieve composite oxide carrier；2) use requirement chloroplatinic acid and nitric acid molybdenum with
Carrier mixes, and impregnates 9 hours, 110 DEG C of drying, 400 DEG C roast 3 hours, obtain catalyst A.
Embodiment 2
Catalyst used is Pt/Mo/W- molecular sieves, and metal quality percentage is Pt：Mo：W=2：1：10.Preparation process
Same as Example 1, the calcination temperature of only second step is changed to 500 DEG C, obtains catalyst B.
Embodiment 3
Catalyst used is Pt/Mo/W- molecular sieves, and metal quality percentage is Pt：Mo：W=2：2：10.Preparation process
It is same as Example 1, obtain catalyst C.
Embodiment 4
Catalyst used is Pt/Mo/W- molecular sieves, and metal quality percentage is Pt：Mo：W=2：5：10.Preparation process
It is same as Example 1, obtain catalyst D.
Embodiment 5
Catalyst used is Pt/Co/W- molecular sieves, and metal quality percentage is Pt：Co：W=2：0.5：10.Prepare step
It is rapid same as Example 1, obtain catalyst E.
Embodiment 6
Catalyst used is Pt/Co/W- molecular sieves, and metal quality percentage is Pt：Co：W=2：1：10.Preparation process
It is same as Example 1, obtain catalyst F.
Embodiment 7
Catalyst used is Pt/Co/W- molecular sieves, and metal quality percentage is Pt：Co：W=2：2：10.Preparation process
It is same as Example 1, obtain catalyst G.
Embodiment 8
Catalyst used is Pt/Mo/Co/W- molecular sieves, and metal quality percentage is Pt：Mo：Co：W=2：2：0.5：
10.Preparation process is same as Example 1, obtains catalyst H.
Comparative example 1
Catalyst used is Pt/W- molecular sieves, and metal quality percentage is Pt：Mo：W=2：0：10.Preparation process with
Embodiment 1 is identical, obtains catalyst L.
The evaluation of catalyst：
It is carried out on fixed bed reactors, the glycerine water solution that mass concentration is 30%, 10g catalyst, reaction temperature is added
Degree is 160 DEG C, Hydrogen Vapor Pressure 4MPa, and the air speed of glycerine water solution is 0.3h-1。
Experimental result is listed in table 1, and there is shown glycerol conversion yields and primary product selective data (by gas chromatography
Detection calculates gained).According to comparing, it is known that the conversion ratio and 1,3-PD yield of glycerine, Mo can be improved in addition Mo and Co
Effect be better than Co.The effect of Mo and Co is added simultaneously better than individually addition.
Table 1
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention, all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of glycerine water solution Hydrogenation, for the catalyst of 1,3-PD, the catalyst includes molecular sieve, feature
It is：The catalyst further includes Pt, X and the W being supported on the molecular sieve, wherein X is Mo and/or Co.
2. glycerine water solution Hydrogenation according to claim 1 is for the catalyst of 1,3-PD, it is characterised in that：It is described
X quality be the catalyst gross mass 0.1~5%.
3. glycerine water solution Hydrogenation according to claim 2 is for the catalyst of 1,3-PD, it is characterised in that：It is described
X quality be the catalyst gross mass 0.1~3%.
4. glycerine water solution Hydrogenation according to claim 1 is for the catalyst of 1,3-PD, it is characterised in that：It is described
Pt quality be the catalyst gross mass 0.1~5%.
5. glycerine water solution Hydrogenation according to claim 4 is for the catalyst of 1,3-PD, it is characterised in that：It is described
Pt quality be the catalyst gross mass 1~3%.
6. glycerine water solution Hydrogenation according to claim 1 is for the catalyst of 1,3-PD, it is characterised in that：It is described
W quality be the catalyst gross mass 5~20%.
7. glycerine water solution Hydrogenation according to claim 6 is for the catalyst of 1,3-PD, it is characterised in that：It is described
W quality be the catalyst gross mass 10~15%.
8. glycerine water solution Hydrogenation according to claim 1 is for the catalyst of 1,3-PD, it is characterised in that：Work as institute
When the X stated is Mo and Co, the mass ratio of the Mo and the Co are 3~5:1.
9. a kind of catalyst such as glycerine water solution Hydrogenation described in any item of the claim 1 to 8 for 1,3- propylene glycol
Preparation method, it is characterised in that：Include the following steps：
(1), ammonium metatungstate aqueous solution is impregnated into molecular sieve, is kept for 15~25 hours at 90~100 DEG C, then 105
It dries at~115 DEG C, then is roasted 2~4 hours at 650~750 DEG C；
(2), intermediate products made from step (1) are impregnated in the mixed solution or chloroplatinic acid and nitre of chloroplatinic acid and nitric acid molybdenum
In the mixed solution of the mixed solution or chloroplatinic acid of sour cobalt, nitric acid molybdenum and cobalt nitrate, aging 8~10 hours, drying, then
It is roasted 2~4 hours at 400~500 DEG C, the catalyst is made.
10. a kind of preparation method of 1,3-PD, it is characterised in that：The glycerine for being 10%~60% by mass percent concentration
Aqueous solution is in the presence of a catalyst 130~200 DEG C in reaction temperature, and being passed through hydrogen makes pressure control in 1~6MPa, instead
The 1,3-PD should be generated, wherein the catalyst is such as catalyst described in any item of the claim 1 to 8.
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| CN201810336749.1A CN108636440B (en) | 2018-04-16 | 2018-04-16 | Catalyst for preparing 1, 3-propylene glycol by hydrogenation of glycerol aqueous solution and preparation method thereof |
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| CN201810336749.1A CN108636440B (en) | 2018-04-16 | 2018-04-16 | Catalyst for preparing 1, 3-propylene glycol by hydrogenation of glycerol aqueous solution and preparation method thereof |
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Cited By (1)
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|---|---|---|---|---|
| CN113429260A (en) * | 2021-05-24 | 2021-09-24 | 中科合成油技术有限公司 | Method for preparing propylene glycol by catalytic hydrogenolysis of glycerol |
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