CN107149945A - A kind of catalyst of VPO/SBA 15 and preparation method and purposes - Google Patents
A kind of catalyst of VPO/SBA 15 and preparation method and purposes Download PDFInfo
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- CN107149945A CN107149945A CN201710273203.1A CN201710273203A CN107149945A CN 107149945 A CN107149945 A CN 107149945A CN 201710273203 A CN201710273203 A CN 201710273203A CN 107149945 A CN107149945 A CN 107149945A
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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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
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 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
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention provides a kind of catalyst of VPO/SBA 15 and preparation method and purposes, preparation process is as follows：Vanadic anhydride is weighed first, is added in three-necked flask, isobutanol and phenmethylol is added, constant temperature is stirred at reflux, until vanadic anhydride is completely dissolved；A certain amount of phosphoric acid is weighed, continues constant temperature back flow reaction after being slowly added into flask, until solution is in sapphirine, that is, obtains vanadium phosphorus oxide, be designated as VPO；SBA 15, quick stirring reaction are added into above-mentioned three-necked flask；After completion of the reaction, take out sample and carry out suction filtration, after being washed with isobutanol and acetone, dry, grind, roasting, by sample tabletting, the catalyst of VPO/SBA 15 is made in screening.The catalyst of VPO/SBA 15 that the notable feature of the present invention is used, during the course of the reaction with good catalytic activity and stability.
Description
Technical field
Prepared the present invention relates to a kind of VPO/SBA-15 catalyst and preparation method thereof and catalysis acetic acid, metaformaldehyde condensation
The purposes of acrylic acid, belongs to organic catalysis field.
Background technology
Acrylic acid is that have special double bond structure and acidic functionality in a kind of important industrial chemicals, its molecule.By
The polymer produced in acrylic acid and its derivative has water white transparency, has stickiness and elasticity, to light stabilization, the not spy such as easy-weathering
Point, is widely used in coating, weaving, binder, pulp processing, glazing agent, leather, fiber, detergent and superabsorbent materials
Deng field.Extensive use based on it in terms of chemical industry, in recent years, the demand of acrylic acid are continuously increased, while with
The abundant and development of downstream product, its market will also further expand.All acrylic acid large production equipments in the whole world use third
Alkene two-step penetration method is produced, and patented technology and process units are generally external grasp.
With the successful exploitation of methyl alcohol carbonyl synthetic method production technology, domestic acetic acid industry has also begun to the industry of a new round
Upgrading, production capacity increases sharply.Again because country lacks effective control measures to building acetic acid project, acetic acid production capacity much surpasses
Domestic demand growth is crossed, by the end of the year 2015, the aggregated capacity of domestic carbonylation method synthesis acetic acid reaches 9,000,000 tons.In face of this
The transformation of essence, expert proposes research and development acetic acid downstream product energetically, gradually forms the change of the raw material based on acetic acid
The plan of the reply of chemical product chain.Thus, find new downstream product also one of emphasis as follow-up developments.There is potential exploitation
In the acetic acid downstream product of value, large batch of acetic acid resource will be fundamentally solved by Material synthesis acrylic acid of acetic acid, is
One non-petroleum with potential value synthesizes the route of large chemical products.And the technology path meet China's coal it is many, oil less,
The Chemical Industry policy that the poor resource structures of gas and country advocate.But with the increasingly reduction of petroleum resources, propylene feedstocks are come
Source can be greatly affected, and using acetic acid and formaldehyde to prepare acrylic acid for raw material has low in raw material price and abundance
Advantage.
The content of the invention
It is contemplated that the catalyst of a kind of high activity and high selectivity is developed, for acetic acid, formaldehyde condensation one-step method system
Standby acrylic acid.Acetic acid, stiasny method described in the present invention prepare acrylic acid, react in continuous fixed bed reactors
In, carried out under conditions of ordinary-pressure gas-phase.
CH3COOH+CH2O→CH2CHCOOH+H2O
The present invention is carrier, a kind of mesoporous silicon based molecular sieve, the hexagon straight hole knot with high-sequential from SBA-15
Structure, its aperture can change in the range of 5~50nm, and hole wall is thicker, hence in so that material has higher hot and hydro-thermal steady
It is qualitative, it is a kind of material for having application prospect.
SBA-15 is as VPO carrier in a kind of VPO/SBA-15 catalyst, the catalyst, and VPO is vanadium phosphorus oxide；
P and V total mass fraction is 10%~30% in the catalyst, and the amount ratio of P, V material is 1.2~2.8：1.
A kind of preparation method of VPO/SBA-15 catalyst, comprises the following steps：
The preparation of step 1, vanadium phosphorus oxide：Vanadic anhydride is weighed first, is added in three-necked flask, adds isobutyl
Alcohol and phenmethylol, constant temperature are stirred at reflux, until vanadic anhydride is completely dissolved；A certain amount of phosphoric acid is weighed, burning is slowly added into
Continue constant temperature back flow reaction after in bottle, until solution is in sapphirine, that is, obtains vanadium phosphorus oxide, be designated as VPO；
The preparation of step 2, VPO/SBA-15 catalyst：SBA-15 is added in three-necked flask into step 1, quick stirring
Reaction；After completion of the reaction, take out sample and carry out suction filtration, after being washed with isobutanol and acetone, dry, grind, roasting, by sample
Product tabletting, screening, is made VPO/SBA-15 catalyst.
In step 1, the amount ratio of used vanadic anhydride, isobutanol and phenmethylol is 1.5270g：30mL：30mL；
The temperature that described constant temperature is stirred at reflux is 140 DEG C, and the time is 6h；The V's in P and vanadic anhydride in used phosphoric acid
The ratio between amount of material is 1.2~2.8：1；The temperature for continuing constant temperature back flow reaction is 140 DEG C, and the time is 6h.
In step 2, described SBA-15 consumption accounted for according to P, V quality P, V, SBA-15 gross mass 10%~
30% adds,；The time of described quick stirring reaction is 2~4h, and described drying temperature is 120 DEG C, and drying time is
24h, described sintering temperature is 400~600 DEG C, and roasting time is 4.5h, and described screening is that sample is sieved into 20~40
Mesh.
The VPO/SBA-15 catalysts acetic acid, metaformaldehyde condensation prepare the purposes of acrylic acid, and step is as follows：
Using acetic acid, metaformaldehyde as raw material, enter after raw material is vaporized through 240 DEG C and be mounted with VPO/SBA-15 catalyst
Fixed bed reactors carry out gas phase reaction, at a given temperature continuous sampling l h, and product is collected in condensation.
In described raw material, the ratio between acetic acid, amount of material of formaldehyde are 3：1, described feed vaporization temperature for 240~
280 DEG C, the long 20cm of fixed bed reactors, internal diameter 0.5cm, the VPO/SBA-15 loaded catalysts are 3g, the original
Sample introduction the flow velocity 8mL/h, carrier gas N of material2Flow velocity is 20mL/min, reaction carry out at ambient pressure, give reaction temperature be 320~
400 DEG C, at a given temperature continuous sampling l h.
Beneficial effect：
The VPO/SBA-15 catalyst that the notable feature of the present invention is used, lives with good catalysis during the course of the reaction
Property and stability；For example, being 1.6h in liquid phase air speed using the catalyst of the present invention-1Left and right, normal pressure, 360 DEG C of reaction conditions
Under, the conversion per pass of formaldehyde is up to 53.10%, and the selectivity of acrylic acid reaches 93.53%.
Embodiment
It is described further with reference to the present invention more than specific embodiment：
Embodiment 1
The preparation of catalyst:
VPO/SBA-15 catalyst is prepared by organic phase method:1.5270g vanadic anhydride is weighed first, is added
30ml isobutanols and 30ml phenmethylols (V are added into three-necked flask:V=1:1) 6h, is stirred at reflux at 140 DEG C, until five
V 2 O is completely dissolved.According to the middle P/V=1.2 of catalyst than composition requirement, 3.3216g phosphoric acid is weighed, is slowly added to
Backflow 6h after into flask；Heater switch is closed, the requirement that load capacity is 20% is accounted for according to load P and V content, adds 8g's
SBA-15, stirring；Quick stirring 3 hours, VPO components are sufficiently mixed with carrier, sample suction filtration, are washed, put with isobutanol, acetone
Enter and dried 24 hours at 120 DEG C, is fully ground, 500 DEG C of roasting 4.5h, by sample in 10Mpa pressure lower sheetings, are sieved into
The catalyst Precursors of 20~40 mesh.
Acetic acid formaldehyde condensation prepares acrylic acid：
Using fixed bed reactors, loaded catalyst 3g catalyst, raw material enters stainless steel tube shape after gasification and reacted
Device (long 20cm, internal diameter 0.5cm) reacts；Raw material is transported to the vapour of above-mentioned fixed bed reactors under normal pressure with 8ml/h speed
Change in room, enter reactor reaction after being vaporized at 240 DEG C, keep carrier gas (N2) flow velocity is 20ml/min, investigates reaction temperature point
Wei not be 320 DEG C, 340 DEG C, 360 DEG C, 380 DEG C, 400 DEG C, continuous sampling l h, condense and collect product and tail at a given temperature
Qi leel is not analyzed with the gas chromatograph with FID and TCD detectors, and exhaust flow is demarcated with soap-foam flowmeter,
The result of test is listed in table 1 by calculating.
Table 1.VPO/SBA-15 (P/V=1.2/1) catalysis acetic acid formaldehyde prepares acrylic acid result table
Embodiment 2
Be the same as Example 1, but change the ratio of P/V in catalyst, it is 2.0/1 to make P/V mol ratios, and acquired results are shown in Table 2.
Table 2.VPO/SBA-15 (P/V=2.0/1) catalysis acetic acid formaldehyde prepares acrylic acid result table
Embodiment 3
Be the same as Example 1, but change the ratio of P/V in catalyst, it is 2.8/1 to make P/V mol ratios, and acquired results are shown in Table 3.
Table 3.VPO/SBA-15 (P/V=2.8/1) catalysis acetic acid formaldehyde prepares acrylic acid result table
Embodiment 4
Be the same as Example 2, but change the sintering temperature of catalyst, respectively at 400 DEG C, 500 DEG C, 600 DEG C of roastings, reaction temperature
For 360 DEG C, 4 must be the results are shown in Table.
Table 4.VPO/SBA-15 (P/V=2.0/1) catalysis acetic acid formaldehyde prepares acrylic acid result table
Embodiment 5
Be the same as Example 3, but change the gross mass of P and V in catalyst, account for respectively catalyst Precursors mass fraction for 10%,
20%th, 30%, reaction temperature is 360 DEG C, must the results are shown in Table 5.
Table 5.VPO/SBA-15 (P/V=2.0/1) catalysis acetic acid formaldehyde prepares acrylic acid result table
Claims (6)
1. a kind of VPO/SBA-15 catalyst, it is characterised in that SBA-15 is as VPO carrier in the catalyst, and VPO is vanadium
Phosphorous oxides；P and V total mass fraction is 10%~30% in the catalyst, and the amount ratio of P, V material is 1.2~2.8：
1。
2. the preparation method of a kind of VPO/SBA-15 catalyst according to claim 1, it is characterised in that including following step
Suddenly：
The preparation of step 1, vanadium phosphorus oxide：Weigh vanadic anhydride first, be added in three-necked flask, add isobutanol and
Phenmethylol, constant temperature is stirred at reflux, until vanadic anhydride is completely dissolved；A certain amount of phosphoric acid is weighed, is slowly added into flask
Continue constant temperature back flow reaction afterwards, until solution is in sapphirine, that is, obtains vanadium phosphorus oxide, be designated as VPO；
The preparation of step 2, VPO/SBA-15 catalyst：SBA-15 is added in three-necked flask into step 1, quick stirring is anti-
Should；After completion of the reaction, take out sample and carry out suction filtration, after being washed with isobutanol and acetone, dry, grind, roasting, by sample
Tabletting, screening, is made VPO/SBA-15 catalyst.
3. the preparation method of a kind of VPO/SBA-15 catalyst according to claim 2, it is characterised in that in step 1, institute
The amount ratio of the vanadic anhydride, isobutanol and the phenmethylol that use is 1.5270g：30mL：30mL；Described constant temperature is stirred at reflux
Temperature be 140 DEG C, the time is 6h；The ratio between V amount of material in P and vanadic anhydride in used phosphoric acid is 1.2
~2.8：1；The temperature for continuing constant temperature back flow reaction is 140 DEG C, and the time is 6h.
4. the preparation method of a kind of VPO/SBA-15 catalyst according to claim 2, it is characterised in that in step 2, institute
The SBA-15 stated consumption accounts for 10%~30% addition of P, V, SBA-15 gross mass according to P, V quality,；Described is quick
The time of stirring reaction is 2~4h, and described drying temperature is 120 DEG C, and drying time is 24h, and described sintering temperature is 400
~600 DEG C, roasting time is 4.5h, and described screening is that sample is sieved into 20~40 mesh.
5. the VPO/SBA-15 catalysts acetic acid described in claim 1, metaformaldehyde condensation prepare the purposes of acrylic acid, its
It is characterised by, step is as follows：
Using acetic acid, metaformaldehyde as raw material, by raw material after vaporization enter be mounted with VPO/SBA-15 catalyst fixed bed it is anti-
Device is answered to carry out gas phase reaction, product is collected in continuous sampling at a given temperature, condensation.
6. VPO/SBA-15 catalysts acetic acid according to claim 5, metaformaldehyde condensation prepare the use of acrylic acid
On the way, it is characterised in that in described raw material, the ratio between acetic acid, amount of material of formaldehyde are 3：1, described feed vaporization temperature is
240~280 DEG C, the long 20cm of fixed bed reactors, internal diameter 0.5cm, the VPO/SBA-15 loaded catalysts are 3g, institute
State sample introduction the flow velocity 8mL/h, carrier gas N of raw material2Flow velocity is 20mL/min, and reaction is carried out at ambient pressure, and it is 320 to give reaction temperature
~400 DEG C, at a given temperature continuous sampling lh.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107649155A (en) * | 2017-09-29 | 2018-02-02 | 吉林大学 | A kind of doping Nb vpo catalyst, preparation method and its application in acrylic acid is produced |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151583A (en) * | 2011-02-21 | 2011-08-17 | 化学工业第二设计院宁波工程有限公司 | Method for preparing vanadium phosphate catalyst used in reaction of acrylic acid synthesized by acetic acid and formaldehyde |
-
2017
- 2017-04-25 CN CN201710273203.1A patent/CN107149945A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102151583A (en) * | 2011-02-21 | 2011-08-17 | 化学工业第二设计院宁波工程有限公司 | Method for preparing vanadium phosphate catalyst used in reaction of acrylic acid synthesized by acetic acid and formaldehyde |
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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107649155A (en) * | 2017-09-29 | 2018-02-02 | 吉林大学 | A kind of doping Nb vpo catalyst, preparation method and its application in acrylic acid is produced |
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