CN109772389A - A kind of glycerine hydrogenation prepares molybdenum sulfide-phosphoric acid Zr catalyst of propenyl and its preparation method and application - Google Patents
A kind of glycerine hydrogenation prepares molybdenum sulfide-phosphoric acid Zr catalyst of propenyl and its preparation method and application Download PDFInfo
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- CN109772389A CN109772389A CN201910156859.4A CN201910156859A CN109772389A CN 109772389 A CN109772389 A CN 109772389A CN 201910156859 A CN201910156859 A CN 201910156859A CN 109772389 A CN109772389 A CN 109772389A
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Abstract
The invention discloses molybdenum sulfide-phosphoric acid Zr catalysts and its preparation method and application that a kind of glycerine hydrogenation prepares propenyl, basic zirconium phosphate and molybdenum sulfide are mixed to prepare by the molybdenum sulfide-phosphoric acid Zr catalyst using ball-milling method, and the mass ratio of the basic zirconium phosphate and molybdenum sulfide is 0.5~2:1.Gas phase hydrogenation of the molybdenum sulfide-phosphoric acid Zr catalyst for glycerol is prepared in the reaction of propenyl, control 185~225 DEG C of reaction temperature, Hydrogen Vapor Pressure is 1~3MPa, glycerol conversion yield after reaction is up to 49.5%~82.8%, for the selectivity of propenyl up to 40.5%, the space-time yield of propenyl reaches as high as 0.25g- propenyl/g- catalyst/hour.
Description
Technical field
The present invention relates to catalysis technical fields, and in particular to a kind of glycerine hydrogenation prepares molybdenum sulfide-basic zirconium phosphate of propenyl
Catalyst and its preparation method and application.
Background technique
Currently, the production line of industrial propenyl mainly has allyl chloride hydrolysis, propylene oxide isomerization, methacrylaldehyde reduction
And four kinds of methods of acetate propylene ester hydrolysis.Allyl chloride hydrolysis method can generate a large amount of waste residues in hydrolytic process；Propylene oxide is different
Though structure method has the characteristics that simple process, yield are higher, corrosion-free to equipment, due to by propylene oxide source and price
Limitation, yield is lower；The advantages of methacrylaldehyde reduction method is to be not required to chlorine, but since yield is lower, the toxicity of methacrylaldehyde is big,
Easily polymerization the problems such as and be difficult to promote；Allyl acetate Hydrolyze method is the technique that Japanese Showa electrician developed in 1985,
The method reaction condition is mild, and production can stablize progress, and propenyl purity is high.But the raw material of above-mentioned production line are petroleum
Pyrolysis product-propylene, with the increasingly scarcity of petroleum resources, the price of propylene is gradually risen, and there is lack of raw materials.Therefore, it adopts
It is raw material with reproducible glycerol, one-step method highly-selective preparation of propylene alcohol has important innovative significance, and this technique has
Very high technology and economic value.
The reaction process that existing one-step glycerol prepares propenyl can be divided into two class of homogeneous reaction and gas-solid phase reaction.
Gas-solid phase reaction mainly has hydrogen migration method and hydrogenolysis method.Wherein, hydrogen migration method be using Organic Alcohol or glycerol as
Hydrogen source, catalyst are deviate from firstly the need of by the part hydrogen in these hydrogen sources, then in situ again to be transferred in glycerol molecule, these works
Skill is mainly using ferriferous oxide and molybdenum oxide as catalyst.Yong Liu et al. reports the oxidation that metal salt is mixed and burned method preparation
Iron catalyst can catalyzing glycerol and a variety of fatty alcohols propenyl generated by hydrogen transfer reaction, but the selectivity of propenyl only has 20
~23% (Chem.Commun., 46 (2010), 1238-1240).It is catalyst, glycerol that other, which also have document report ferriferous oxide,
Both it had done raw material or had done the technique of hydrogen donor, but at 300~340 DEG C, propenyl yield is still lower than 30% in above-mentioned technique
(Appl.Catal.B-Environ., 146 (2014) 267-273 prepare K/Al using coprecipitation2O3-ZrO2-FeOxCatalysis
Agent, Appl.Catal.B-Environ., 152-153 (2014) 117-128 are using anhydrous infusion process preparation alkali metals modified
Fe2O3/Al2O3Catalyst, Appl.Catal.A-Gen., 509 (2016) 130-142 prepare Fe using ion-exchange2O3/
ZSM-5 catalyst).The patent specification of Publication No. CN 104926604A is disclosed to contain MoO3-TiO2Combined oxidation
Object is catalyst, the technique that glycerine hydrogenation is prepared to propenyl in fixed bed, is 160~240 DEG C in reaction temperature, pressure is
Under conditions of 0.1~3.0MPa, propenyl selectivity is up to 80% or more, but its raw material used is glycerol methanol solution.
Gas-solid phase hydrogenolysis method just had report in 2016, and Santos et al. is under 250 DEG C, hydrogen atmosphere, with CuMoAlO
Glycerol directly conversion is prepared propenyl by catalyst, but the selectivity of product lower than 15% (Catal.Sci.&Technol.,
6(2016)4986-5002)。
Summary of the invention
In the technique for directly synthesizing propenyl for glycerol, formic acid, Organic Alcohol are high as the at high cost of hydrogen donor, catalyst
Expensive, toxic, easy in inactivation, and the problems such as product is complicated, propenyl yield is low and separating technology is cumbersome, the present invention provides one kind
Glycerine hydrogenation prepares molybdenum sulfide-phosphoric acid Zr catalyst of propenyl, is mixed basic zirconium phosphate with molybdenum sulfide using easy ball-milling method
It is made.The acidic site and redox site that the molybdenum sulfide-phosphoric acid Zr catalyst has make it in gas phase glycerine hydrogenation
It prepares in propenyl reaction and shows good activity, realize the more highly selective of propenyl.
A kind of glycerine hydrogenation prepares molybdenum sulfide-phosphoric acid Zr catalyst of propenyl, by basic zirconium phosphate and is vulcanized using ball-milling method
Molybdenum is mixed to prepare, and the mass ratio of the basic zirconium phosphate and molybdenum sulfide is 0.5~2:1.
The present invention also provides the molybdenum sulfide described in one kind-phosphoric acid Zr catalyst preparation methods, first pass through hydro-thermal legal system
Basic zirconium phosphate is obtained, then basic zirconium phosphate and molybdenum sulfide ball milling are made by molybdenum sulfide-phosphoric acid Zr catalyst by easy ball-milling method.
A kind of molybdenum sulfide-phosphoric acid Zr catalyst preparation method, comprising: obtain basic zirconium phosphate and molybdenum sulfide ball milling
The mass ratio of molybdenum sulfide-phosphoric acid Zr catalyst, the basic zirconium phosphate and molybdenum sulfide is 0.5~2:1.Propenyl is prepared according to glycerol
Reaction mechanism (need to be dehydrated, dehydration plus hydrogen), and the reactivity of product propylene alcohol is high, it is easy to further plus hydrogen
Or polymerization, suitable basic zirconium phosphate can guarantee the dehydration activity of glycerol, and the molybdenum sulfide with weak Hydrogenation can be reduced
Propenyl adds hydrogen or polymerization, and the two has significant synergistic effect.
The specific steps of the ball milling include: by basic zirconium phosphate and molybdenum sulfide ground and mixed it is uniform after, with 250~350rpm
Rate 1~3h of ball milling, the quality of agate ball used in mechanical milling process be the quality sum of basic zirconium phosphate and molybdenum sulfide 40~
60 times, obtain molybdenum sulfide-phosphoric acid Zr catalyst.It, can be by two by grinding since basic zirconium phosphate and molybdenum sulfide are all stratified materials
Person is sufficiently compound, to form alternate basic zirconium phosphate-molybdenum sulfide-basic zirconium phosphate-molybdenum sulfide composite laminates, so as to realize that it is de-
Water-plus hydrogen-dehydrating function synergistic effect, and then guarantee going on smoothly for reaction.
The molybdenum sulfide-phosphoric acid Zr catalyst is black powder.
Preferably, the preparation method of the basic zirconium phosphate includes:
(1) phosphoric acid solution is added drop-wise in eight water zirconium oxychloride aqueous solutions, 0.5~2h of stirring obtains gelatinous precipitate, institute
The molar ratio of the P in phosphoric acid solution and the Zr in eight water zirconium oxychloride aqueous solutions that state are 2~4:1；
(2) gelatinous precipitate that step (1) obtains is transferred in reaction kettle, at 160~200 DEG C hydrothermal crystallizing 36~
60h；
(3) by the product obtained after step (2) hydrothermal crystallizing centrifugation, washing to neutrality, drying and grinding obtains white powder；
(4) white powder for obtaining step (3) roasts 1~3h under conditions of air atmosphere, 400~500 DEG C, obtains
Basic zirconium phosphate.
The effect of step (1) and step (2) mainly increases the crystallinity of basic zirconium phosphate, prevents unformed material from generating.
In step (4), the effect of the roasting mainly sufficiently removes the crystallization water in basic zirconium phosphate while maintaining its layer
Hardened structure is constant.
Preferably, the heating rate of the roasting is 1~3 DEG C/min, prevents from bursting due to laminate is too fast because heating up.
The present invention also provides the molybdenum sulfide described in one kind-phosphoric acid Zr catalysts to prepare answering in propenyl in glycerine hydrogenation
With.
The molybdenum sulfide-phosphoric acid Zr catalyst is used for glycerol gas phase hydrogenation reaction, the molybdenum sulfide-basic zirconium phosphate catalysis
Agent carries out glycerol gas phase hydrogenation reaction after first activating 0.5~2h under conditions of hydrogen atmosphere, 220~280 DEG C again.
The reaction temperature of the glycerol gas phase hydrogenation reaction is 185~225 DEG C, and Hydrogen Vapor Pressure is 1~3MPa, and glycerol is molten
The solvent of liquid is selected from isopropanol, methanol, ethyl alcohol or water, is to consider that solvent is miscible with glycerol and product energy first, secondly also wants
Consider price and safety.
Compared with prior art, the present invention major advantage includes:
(1) it is at high cost that the present invention overcomes hydrogen donors, expensive catalyst (rhenium, silver etc.), toxic (chromium etc.), easy in inactivation, instead
It answers condition harshness and propenyl yield low (gas-solid phase reaction) and preparative separation technique is cumbersome, discontinuous (liquid phase reactor) etc. is asked
Topic, the molybdenum sulfide-phosphoric acid Zr catalyst synthesis is simple and efficient, selectivity is high, stability is high, cheap, and reaction condition is mild
And propenyl selectivity is high.
(2) molybdenum sulfide prepared by the present invention-phosphoric acid Zr catalyst, the gas phase hydrogenation for glycerol prepare the reaction of propenyl
In, 185~225 DEG C of reaction temperature of control, Hydrogen Vapor Pressure are 1~3MPa.Glycerol conversion yield after reaction up to 49.5%~
82.8%, for the selectivity of propenyl up to 40.5%, the space-time yield of propenyl reaches as high as 0.25g- propenyl/g- catalysis
Agent/hour.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip
Part, or according to the normal condition proposed by manufacturer.
Embodiment 1
It weighs 10.3 gram of eight water oxygen zirconium chloride to be dissolved in 5 ml deionized waters, stirring makes it dissolve uniformly, slowly for 10 minutes
The molar ratio of the phosphoric acid solution of 11.1 gram 85% of dropwise addition, phosphorus and zirconium is 3:1, obtains gelatinous precipitate after being mixed 1 hour；It will
Gelatinous precipitate is transferred in the stainless steel cauldron containing polytetrafluoroethyllining lining, and hydrothermal crystallizing 48 hours, obtain at 180 DEG C
The product arrived is after cooling, washing centrifugation to pH are 7 or so, drying and grinding up to white powder；Above-mentioned white powder is shifted
It into Muffle furnace, is calcined 2 hours at 450 DEG C in static air atmosphere, controls 2 DEG C/min of heating rate, obtain white
Basic zirconium phosphate solid.0.4~0.8 gram of basic zirconium phosphate and 0.4~0.8 gram of molybdenum sulfide are weighed again, that is, molybdenum sulfide and phosphoric acid are controlled when preparing
The mass ratio of zirconium is that 1:2,1:1 and 2:1 are uniformly mixed, prior to grinding 15 minutes in mortar then with 300 revs/min of speed
Rate ball milling 2 hours, the quality of agate ball was 50 times of powder sample in ball grinder, and obtained black powder is molybdenum sulfide-phosphoric acid
Zr catalyst.By above-mentioned catalyst tabletting, the particle of 40~60 mesh is screened.
It is 6 millimeters that the molybdenum sulfide-phosphoric acid Zr catalyst for weighing 0.2 gram of 40-60 mesh, which is loaded on internal diameter, and a length of 540 millimeters are not
Rust steel reaction tube middle-end, both ends are sealed with quartz sand；Before reaction starts, catalyst is first 100 ml/mins in 250 DEG C, flow velocity
Hydrogen atmosphere under activate 1 hour；It is cooled to 205 DEG C of reaction temperature and Hydrogen Vapor Pressure is adjusted to 3MPa, with high-pressure pump by matter
It measures the glycerine water solution that score is 40% to inject in reaction tube with the flow velocity of 0.01 ml/min, reaction starts and to stablize 1.5 small
When；The cold-trap of -5 DEG C of reaction product warp is cooling, gained product liquid capillary gas chromatography, quantified by external standard method analysis.
Different molybdenum sulfides and the conversion ratio of glycerol under basic zirconium phosphate mass ratio and the selectivity of propenyl are as shown in table 1.
The conversion ratio of glycerol and the selectivity of propenyl under the different molybdenum sulfides of table 1 and basic zirconium phosphate mass ratio
| Molybdenum sulfide and basic zirconium phosphate mass ratio | 1:2 | 1:1 | 2:1 |
| Glycerol conversion yield (%) | 53.6 | 63.7 | 58.3 |
| Propenyl selectivity (%) | 8.7 | 9.8 | 8.0 |
Embodiment 2
The catalyst of molybdenum sulfide Yu basic zirconium phosphate mass ratio 1:1 is prepared using catalyst preparation process same in embodiment 1,
And same method filling and activated catalyst, reaction temperature are 205 DEG C, Hydrogen Vapor Pressure 3MPa, it will be different with high-pressure pump
The glycerite that the mass fraction of solvent is 40% is injected in reaction tube with the flow velocity of 0.01 ml/min, and reaction beginning is simultaneously steady
It is 1.5 hours fixed；The cold-trap of -5 DEG C of reaction product warp is cooling, gained product liquid capillary gas chromatography, and external standard is legal
Amount analysis.The conversion ratio of glycerol and the selectivity of propenyl are as shown in table 2 in different solvents.
The conversion ratio of glycerol and the selectivity of propenyl in 2 different solvents of table
| Solvent | Isopropanol | Methanol | Ethyl alcohol | Water |
| Glycerol conversion yield (%) | 64.4 | 57.6 | 81.9 | 63.7 |
| Propenyl selectivity (%) | 40.5 | 38.9 | 11.7 | 9.8 |
Embodiment 3
Using same catalyst in embodiment 2 and the filling of same method and activated catalyst, reaction temperature 185
~225 DEG C, Hydrogen Vapor Pressure 3MPa, with high-pressure pump by mass fraction be 40% glycerol isopropyl alcoholic solution with 0.01 ml/min
In the flow velocity injection reaction tube of clock, reaction starts and stablizes 1.5 hours；- 5 DEG C of cold-traps of reaction product warp are cooling, and gained liquid produces
Object capillary gas chromatography, quantified by external standard method analysis.The selectivity of the conversion ratio of glycerol and propenyl under different temperatures
As shown in table 3.
The conversion ratio of glycerol and the selectivity of propenyl under 3 different temperatures of table
| Temperature (DEG C) | 185 | 205 | 225 |
| Glycerol conversion yield (%) | 49.5 | 64.4 | 82.8 |
| Propenyl selectivity (%) | 33.4 | 40.5 | 30.5 |
Embodiment 4
Using same catalyst in embodiment 2 and the filling of same method and activated catalyst, reaction temperature 205
DEG C, Hydrogen Vapor Pressure be 1~3MPa, with high-pressure pump by mass fraction be 40% glycerol isopropyl alcoholic solution with 0.01 ml/min
Flow velocity injection reaction tube in, reaction start simultaneously stablize 1.5 hours；- 5 DEG C of cold-traps of reaction product warp are cooling, gained product liquid
With capillary gas chromatography, quantified by external standard method analysis.The selection of the conversion ratio and propenyl of glycerol under different hydrogen pressure
Property is as shown in table 4.
The conversion ratio of glycerol and the selectivity of propenyl under 4 different hydrogen pressure of table
| Hydrogen Vapor Pressure (MPa) | 1 | 2 | 3 |
| Glycerol conversion yield (%) | 36.9 | 44.0 | 64.4 |
| Propenyl selectivity (%) | 63.4 | 58.5 | 40.5 |
In addition, it should also be understood that, those skilled in the art can be to this hair after having read foregoing description content of the invention
Bright to make various changes or modifications, these equivalent forms also fall within the scope of the appended claims of the present application.
Claims (7)
1. molybdenum sulfide-phosphoric acid Zr catalyst that a kind of glycerine hydrogenation prepares propenyl, which is characterized in that use ball-milling method by phosphoric acid
Zirconium is mixed to prepare with molybdenum sulfide, and the mass ratio of the basic zirconium phosphate and molybdenum sulfide is 0.5~2:1.
2. molybdenum sulfide-phosphoric acid Zr catalyst that glycerine hydrogenation according to claim 1 prepares propenyl, which is characterized in that
The specific steps of the ball-milling method include: by basic zirconium phosphate and molybdenum sulfide ground and mixed it is uniform after, with the rate of 250~350rpm
1~3h of ball milling, the quality of agate ball used in mechanical milling process are 40~60 times of the quality sum of basic zirconium phosphate and molybdenum sulfide, are obtained
To molybdenum sulfide-phosphoric acid Zr catalyst.
3. glycerine hydrogenation according to claim 1 or 2 prepares molybdenum sulfide-phosphoric acid Zr catalyst of propenyl, feature exists
In the preparation method of the basic zirconium phosphate includes:
(1) phosphoric acid solution is added drop-wise in eight water zirconium oxychloride aqueous solutions, 0.5~2h of stirring obtains gelatinous precipitate, described
The molar ratio of P in the phosphoric acid solution and Zr in eight water zirconium oxychloride aqueous solutions is 2~4:1；
(2) gelatinous precipitate that step (1) obtains is transferred in reaction kettle, 36~60h of hydrothermal crystallizing at 160~200 DEG C；
(3) by the product obtained after step (2) hydrothermal crystallizing centrifugation, washing to neutrality, drying and grinding obtains white powder；
(4) white powder for obtaining step (3) roasts 1~3h under conditions of air atmosphere, 400~500 DEG C, obtains phosphoric acid
Zirconium.
4. molybdenum sulfide-phosphoric acid Zr catalyst that glycerine hydrogenation according to claim 3 prepares propenyl, which is characterized in that
In step (4), the heating rate of the roasting is 1~3 DEG C/min.
5. molybdenum sulfide-basic zirconium phosphate that glycerine hydrogenation described in a kind of any claim according to claim 1~4 prepares propenyl
Catalyst prepares the application in propenyl in glycerol gas phase hydrogenation, which is characterized in that the molybdenum sulfide-phosphoric acid Zr catalyst is first
Glycerol gas phase hydrogenation is carried out again after 0.5~2h of activation under conditions of hydrogen atmosphere, 220~280 DEG C prepares propenyl.
6. molybdenum sulfide-phosphoric acid Zr catalyst that glycerine hydrogenation according to claim 5 prepares propenyl adds in glycerol gas phase
Hydrogen prepares the application in propenyl, which is characterized in that and the reaction temperature that glycerol gas phase hydrogenation prepares propenyl is 185~225 DEG C,
Hydrogen Vapor Pressure is 1~3MPa.
7. glycerine hydrogenation according to claim 5 or 6 prepares molybdenum sulfide-phosphoric acid Zr catalyst of propenyl in glycerol gas phase
Hydrogen is added to prepare the application in propenyl, which is characterized in that using glycerite as raw material, the solvent of the glycerite is selected from isopropyl
Alcohol, methanol, ethyl alcohol or water.
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| CN201910156859.4A CN109772389B (en) | 2019-03-01 | 2019-03-01 | Molybdenum sulfide-zirconium phosphate catalyst for preparing allyl alcohol by glycerol hydrogenation, and preparation method and application thereof |
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| CN201910156859.4A CN109772389B (en) | 2019-03-01 | 2019-03-01 | Molybdenum sulfide-zirconium phosphate catalyst for preparing allyl alcohol by glycerol hydrogenation, and preparation method and application thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190401A (en) * | 2014-07-25 | 2014-12-10 | 上海华谊丙烯酸有限公司 | Molybdenum-based composite metal oxide catalyst for synthesizing propenyl alcohol by glycerol and preparation method of molybdenum-based composite metal oxide catalyst |
| CN107115879A (en) * | 2017-04-14 | 2017-09-01 | 复旦大学 | Phosphorus composite oxide catalysts of chromium of propenyl and preparation method thereof are synthesized for glycerine |
| CN107384527A (en) * | 2017-07-14 | 2017-11-24 | 太原理工大学 | A kind of compound extreme pressure grease of bedded zirconium phosphate and molybdenum disulfide and preparation method thereof |
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2019
- 2019-03-01 CN CN201910156859.4A patent/CN109772389B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104190401A (en) * | 2014-07-25 | 2014-12-10 | 上海华谊丙烯酸有限公司 | Molybdenum-based composite metal oxide catalyst for synthesizing propenyl alcohol by glycerol and preparation method of molybdenum-based composite metal oxide catalyst |
| CN107115879A (en) * | 2017-04-14 | 2017-09-01 | 复旦大学 | Phosphorus composite oxide catalysts of chromium of propenyl and preparation method thereof are synthesized for glycerine |
| CN107384527A (en) * | 2017-07-14 | 2017-11-24 | 太原理工大学 | A kind of compound extreme pressure grease of bedded zirconium phosphate and molybdenum disulfide and preparation method thereof |
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| 兰海 等: "无额外供氢体下负载型MoFeOx催化剂催化甘油制丙烯醇", 《物料化学学报》 * |
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