CN106345516A - Load type vanadium phosphorus oxide catalyst, preparation method and application thereof - Google Patents
Load type vanadium phosphorus oxide catalyst, preparation method and application thereof Download PDFInfo
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- CN106345516A CN106345516A CN201610627959.7A CN201610627959A CN106345516A CN 106345516 A CN106345516 A CN 106345516A CN 201610627959 A CN201610627959 A CN 201610627959A CN 106345516 A CN106345516 A CN 106345516A
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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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst, and in particular to a load type vanadium phosphorus oxide catalyst, a preparation method and an application of the catalyst. The catalyst is VPO (vapor pressure osmoetry)/HZSM-5 catalyst; the molecular sieve silica-alumina ratio of the selected HZSM-5 is 360: 1, thus the surface acidity of the catalyst is not too strong; the mass ratio scale of (V+P) atoms and a carrier HZSM-5 in the catalyst is 10%-30%; the atom ratio scale of V/P is 1:1.5-1:2.5. the catalyst is simple in preparation process and low in cost; compared with a non-load vanadium phosphorus oxide catalyst, the catalyst is large in specific surface area, big in surface acid content, and others in reaction process; VPO/HZSM-5 shows good catalytic activity and stability in reaction of preparing acrylic acid by acetic formaldehyde condensation; the catalytic reaction is carried out in a fixed bed reactor, and is a continuous reaction process; the catalyst is big in production capacity and good in industrial prospect.
Description
Technical field
The present invention relates to a kind of catalyst, refer in particular to a kind of load-type vanadium phosphor oxide catalyst and its production and use, use
Prepare acrylic acid in acetic acid formaldehyde condensation, belong to organic catalysis field.
Background technology
Acrylic acid is one of the particularly important basic material of modern chemical industry and intermediate, because its active strong polarity,
Unsaturated double-bond and carboxylic acid structure, make acrylic acid have excellent polymerization and esterification function, can derive a variety of acrylic acid
Ester type compound.Polymer due to acrylic acid and its derivant production has good elasticity and viscosity, to light stably simultaneously
Not the features such as easy-weathering, it is widely used in coating, adhesive, pulp processing, glazing agent, leather, chemical fibre, detergent, oil
The field such as exploitation and superabsorbent materials.Acrylicacidandesters, since the thirties in 20th century realizes industrialized production, have had been subjected to
Cyanoethanol method, reppe (Lei Pu) method, ketenes method, acrylonitrile hydrolysis method and oxidation of propylene.Above 4 kinds of techniques are because of technology
Economic cause is eliminated substantially.Oxidation of propylene is the method that the sixties in 20th century grows up, and is originally divided into one-step method
And two-step method.After the eighties in 20th century, the newly-built acroleic acid device with enlarging is all using propylene two-step oxidizing process.
Oxidation of propylene commonly used at present is petroleum path, and this route technological process length and product separate difficult.Vinegar
Sour formaldehyde acrylic acid synthesizing is a kind of new potential method, belongs to Coal Chemical Industry Route, and the development of the method route meets
The energy resource structure of China, has a very big significance for overcoming the dependence to oil.Domestic acetic acid, formaldehyde market production capacity mistake at present
Surplus and inexpensive, using acetic acid, formaldehyde produces acrylic acid becomes study hotspot.The key of this technology is new and effective catalysis
The exploitation of agent.Previous studies find, acidity becomes acrylic acid reaction all to have with base catalyst for tumer al symphysis
Active, acidic catalyst mainly has vanadium phosphorus oxide, niobium oxide, zirconium aluminum oxide, and base catalyst is typically alkali metal
Or alkaline-earth metal is supported on silicon dioxide or zeolite, this reaction problem maximum at present is acrylic acid once through yield relatively
Low.
Content of the invention
The invention provides a kind of new load-type vanadium phosphor oxide catalyst is used for being catalyzed acetic acid formaldehyde condensation and prepares acrylic acid
Reaction.
Hzsm-5 molecular screen material has well-regulated pore passage structure and large specific surface area, and molecular sieve surface is in certain
Acidity, be very suitable for as catalyst carrier, provide more chain carriers for catalytic reaction.
Used catalyst of the present invention is vpo/hzsm-5 catalyst, and the hzsm-5 molecular sieve silica alumina ratio of selection is 360:1, makes
Catalyst surface acidity will not be too strong；In catalyst, the quality of (v+p) atom and carrier hzsm-5 is 10%～30% than scope,
V/p atomic ratio scope is 1:1.5～1:2.5.
The preparation process of catalyst adopts equi-volume impregnating, and acrylic acid preparation complete procedure comprises the following steps:
(1) adopt ammonium metavanadate (nh4vo3) as vanadium source, phosphoric acid (h3po4) as phosphorus source, with oxalic acid (h2c2o4·2h2o)
As dissolving medium, nh4vo3And h2c2o4·2h2The mol ratio of o is 1:2.Weigh the nh of respective quality4vo3And h2c2o4·2h2o
In beaker, then under conditions of 50 DEG C of heating in water bath and magnetic agitation to beaker in add deionized water dissolved, directly
It is changed into sky blue to solution, then to Deca h in solution3po4, drip h3po4Continue stirring reaction 0.5h afterwards, make catalyst
Impregnation liquid required for preparation.
(2) and then weigh hzsm-5 molecular sieve, 6h, sample after dipping are impregnated under normal temperature condition with the impregnation liquid made
Product are dried overnight at 120 DEG C, 500 DEG C of roasting 4h, and sample tabletting is sieved into the granule of 20-40 mesh, makes catalyst.
(3) formaldehyde acetic acid condensation reaction is carried out in fixed bed reactors (long 20cm, internal diameter 0.5cm), and reaction raw materials are
Formalin (formalin of mass fraction 38%) and acetic acid mixed solution, the formaldehyde in formalin and acetic acid mole
Ratio 1:3, reaction raw materials is entered after overflash be mounted with and enters circulation of qi promoting in the fixed bed reactors of catalyst described in step (2)
Phase catalytic dehydrogenating reaction, wherein loaded catalyst are 6ml, sample introduction flow velocity 6ml/h, carrier gas n2Flow velocity is 20ml/min, reaction
Carry out at ambient pressure, reaction temperature 340-400 DEG C, at a given temperature continuous sampling lh, product is collected in ice-water bath condensation.Collect
Product gas chromatograph be analyzed.
The vpo/hzsm-5 catalyst preparation process that the marked feature of the present invention is adopted is simple, with low cost, catalyst
Have compared to non-loaded vanadium-phosphor oxide catalyst and there is the advantages of specific surface area is big, and Surface acidity is big during the course of the reaction,
Vpo/hzsm-5 acetic acid formaldehyde condensation prepare acrylic acid reaction in show good catalysis activity and stability；This is urged
Change reaction to carry out in fixed bed reactors, be tandem reaction sequence, production capacity is big, has good industrial prospect.Example
As using the catalyst of the present invention, in sample introduction flow velocity 6ml/h, carrier gas n2Flow velocity is 20ml/min, normal pressure, 400 DEG C of reaction conditions
Under, the conversion per pass of formaldehyde is up to 70.29%, has reached 68.15% based on the acrylic acid selectivity of formaldehyde.
Compared with existing acrylic acid synthetic technology, the present invention, with cheap acetic acid and formaldehyde as raw material, is prepared with infusion process
Novel supported vanadium-phosphor oxide catalyst, and be used for being catalyzed formaldehyde acetic acid condensation and prepare acrylic acid, can be more by introducing carrier
The surface acidic-basic property of good regulation and control catalyst, makes catalytic reaction process have conversion ratio and selectivity.Catalyst has preferably
Catalysis activity and stability, the acrylic acid production process invented has good industrial prospect.
Specific embodiment
With reference to being embodied as example, the present invention will be further described
Embodiment 1
The preparation of catalyst:
(1) weigh 2.4gnh4vo3And 5.1692gh2c2o4·2h2O in beaker, then in 50 DEG C of heating in water bath and magnetic force
Deionized water is added to be dissolved, until solution is changed into sky blue, then to Deca in solution under conditions of stirring in beaker
3.0153g h3po4(v/p mol ratio is 1:1.5), drips h3po4Continue stirring reaction 0.5h afterwards, make catalyst preparation
Required 80ml impregnation liquid.
(2) and then weigh the hzsm-5 molecular sieve of 10g, impregnate 6h under normal temperature condition with the impregnation liquid made, leaching
After stain, sample is dried overnight at 120 DEG C, 500 DEG C of roasting 4h, and sample tabletting is sieved into the granule of 20-40 mesh, makes catalysis
Agent.
Catalyst formaldehyde acetic acid condensation reaction with having prepared:
Formaldehyde acetic acid condensation reaction is carried out in fixed bed reactors (long 20cm, internal diameter 0.5cm), reaction raw materials formal
Formaldehyde in woods and mol ratio 1:3 of acetic acid, reaction raw materials are entered after overflash and are mounted with catalyst described in step (2)
Fixed bed reactors in carry out vapor catalytic dehydrogenation reaction, wherein loaded catalyst is 6ml, sample introduction flow velocity 6ml/h, carrier gas
n2Flow velocity is 20ml/min, and reaction is carried out at ambient pressure, reaction temperature 340-400 DEG C, continuous sampling lh at a given temperature, ice
Product is collected in water-bath condensation.The product gas chromatograph collected is analyzed.
The result of test is listed in table 1 through calculating.
Table 1.vpo/hzsm-5 (vanadium phosphorus load capacity 20%, p/v=1.5:1) is catalyzed formaldehyde acetic acid condensation reaction test result
Embodiment 2
With embodiment 1, only p/v in catalyst is adjusted to 2:1, the survey of catalysis formaldehyde acetic acid condensation reaction than by 1.5:1
Test result is as shown in table 2.
Table 2.vpo/hzsm-5 (vanadium phosphorus load capacity 20%, p/v=2:1) is catalyzed formaldehyde acetic acid condensation reaction test result
Embodiment 3
With embodiment 1, only p/v in catalyst is adjusted to 2.5:1 than by 1.5:1, catalysis formaldehyde acetic acid condensation reaction
Test result is as shown in table 3.
Table 3.vpo/hzsm-5 (vanadium phosphorus load capacity 20%, p/v=2.5:1) is catalyzed formaldehyde acetic acid condensation reaction test result
Embodiment 4
With embodiment 1, only p/v in catalyst is adjusted to 2:1 than by 1.5:1, vanadium phosphorus load capacity is adjusted to 10%, catalysis
The test result of formaldehyde acetic acid condensation reaction is as shown in table 4.
Table 4.vpo/hzsm-5 (vanadium phosphorus load capacity 10%, p/v=2:1) is catalyzed formaldehyde acetic acid condensation reaction test result
Embodiment 5
With embodiment 1, only p/v in catalyst is adjusted to 2:1 than by 1.5:1, vanadium phosphorus load capacity is adjusted to 30%, catalysis
The test result of formaldehyde acetic acid condensation reaction is as shown in table 5.
Table 5.vpo/hzsm-5 (vanadium phosphorus load capacity 30%, p/v=2:1) is catalyzed formaldehyde acetic acid condensation reaction test result
Claims (7)
1. a kind of load-type vanadium phosphor oxide catalyst it is characterised in that: the hzsm-5 molecular sieve of selection is as catalyst carrier；Catalysis
In agent, the quality of (v+p) atom and carrier hzsm-5 is 10%～30% than scope, and v/p atomic ratio scope is 1:1.5～1:
2.5.
2. as claimed in claim 1 a kind of load-type vanadium phosphor oxide catalyst it is characterised in that: the hzsm-5 molecular sieve silicon of selection
Aluminum ratio is 360:1, makes catalyst surface acidity too strong；V/p atomic ratio is 1:2；(v+p) matter of atom and carrier hzsm-5
Amount is 20%～30% than scope.
3. a kind of preparation method of load-type vanadium phosphor oxide catalyst as claimed in claim 1, using equi-volume impregnating preparation,
It is characterized in that carrying out in accordance with the following steps:
(1) adopt ammonium metavanadate (nh4vo3) as vanadium source, phosphoric acid (h3po4) as phosphorus source, with oxalic acid (h2c2o4·2h2O) conduct
Dissolving medium, nh4vo3And h2c2o4·2h2The mol ratio of o is 1:2；Weigh the nh of respective quality4vo3And h2c2o4·2h2O is in burning
In cup, then under conditions of 50 DEG C of heating in water bath and magnetic agitation to beaker in add deionized water to be dissolved, until molten
Liquid is changed into sky blue, then to Deca h in solution3po4, drip h3po4Continue stirring reaction 0.5h afterwards, make catalyst preparation
Required impregnation liquid；
(2) and then weigh hzsm-5 molecular sieve, impregnate 6h with the impregnation liquid made under normal temperature condition, after dipping, sample exists
It is dried overnight at 120 DEG C, 500 DEG C of roasting 4h, sample tabletting is sieved into the granule of 20-40 mesh, makes catalyst.
4. a kind of load-type vanadium phosphor oxide catalyst prepares acrylic acid use for acetic acid formaldehyde condensation as claimed in claim 1
On the way.
5. purposes as claimed in claim 4 it is characterised in that: formaldehyde acetic acid condensation reaction is carried out in fixed bed reactors,
Reaction raw materials are formalin and acetic acid mixed solution, the formaldehyde in formalin and mol ratio 1:3 of acetic acid, by reaction raw materials
Enter in the fixed bed reactors be mounted with described catalyst after overflash and carry out vapor catalytic dehydrogenation reaction, wherein catalyst
Loadings are 6ml, sample introduction flow velocity 6ml/h, carrier gas n2Flow velocity is 20ml/min, and reaction is carried out at ambient pressure, reaction temperature 340-
400 DEG C, continuous sampling lh at a given temperature, product is collected in ice-water bath condensation.The product collected is carried out with gas chromatograph point
Analysis.
6. purposes as claimed in claim 5 it is characterised in that: the long 20cm of fixed bed reactors, internal diameter 0.5cm.
7. purposes as claimed in claim 5 it is characterised in that: formalin be mass fraction 38% formalin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610627959.7A CN106345516A (en) | 2016-08-03 | 2016-08-03 | Load type vanadium phosphorus oxide catalyst, preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610627959.7A CN106345516A (en) | 2016-08-03 | 2016-08-03 | Load type vanadium phosphorus oxide catalyst, preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109174164A (en) * | 2018-08-14 | 2019-01-11 | 江苏大学 | A kind of vanadium phosphorus oxide/MCM-41 catalyst and its preparation method and application |
| CN113877612A (en) * | 2021-11-10 | 2022-01-04 | 中国科学院山西煤炭化学研究所 | Multifunctional catalyst compounded by FeMo component and VPO component, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161005A (en) * | 2011-02-21 | 2011-08-24 | 化学工业第二设计院宁波工程有限公司 | Preparation method of phosphorus vanadium catalyst for using acetic acid and formaldehyde to synthesize crylic acid |
| CN103638956A (en) * | 2013-11-14 | 2014-03-19 | 中国科学院过程工程研究所 | Catalyst for synthesizing methyl acrylate by trioxymethylene or paraformaldehyde and acetic acid and acetic acid aqueous solution, its preparation and its application method |
-
2016
- 2016-08-03 CN CN201610627959.7A patent/CN106345516A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102161005A (en) * | 2011-02-21 | 2011-08-24 | 化学工业第二设计院宁波工程有限公司 | Preparation method of phosphorus vanadium catalyst for using acetic acid and formaldehyde to synthesize crylic acid |
| CN103638956A (en) * | 2013-11-14 | 2014-03-19 | 中国科学院过程工程研究所 | Catalyst for synthesizing methyl acrylate by trioxymethylene or paraformaldehyde and acetic acid and acetic acid aqueous solution, its preparation and its application method |
Non-Patent Citations (1)
| Title |
|---|
| JING HU，ET.AL.: "Aldol condensation of acetic acid with formaldehyde to acrylic acid over SiO2-, SBA-15-, and HZSM-5-supported V-P-O catalysts", 《JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109174164A (en) * | 2018-08-14 | 2019-01-11 | 江苏大学 | A kind of vanadium phosphorus oxide/MCM-41 catalyst and its preparation method and application |
| CN109174164B (en) * | 2018-08-14 | 2022-02-15 | 江苏大学 | Vanadium phosphorus oxide/MCM-41 catalyst and preparation method and application thereof |
| CN113877612A (en) * | 2021-11-10 | 2022-01-04 | 中国科学院山西煤炭化学研究所 | Multifunctional catalyst compounded by FeMo component and VPO component, and preparation method and application thereof |
| CN113877612B (en) * | 2021-11-10 | 2024-04-19 | 中国科学院山西煤炭化学研究所 | Multifunctional catalyst compounded by FeMo component and VPO component, and preparation method and application thereof |
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