CN102652922B - Supported phosphorus-vanadium-cesium-lanthanum catalyst and application thereof - Google Patents
Supported phosphorus-vanadium-cesium-lanthanum catalyst and application thereof Download PDFInfo
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Abstract
The invention relates to a supported phosphorus-vanadium-cesium-lanthanum catalyst and application thereof, particularly a catalyst for synthesizing methyl acrylate from formaldehyde and methyl acetate and application thereof.. The invention aims to provide a catalyst for preparing methyl acrylate from methyl acetate and formaldehyde, which has the advantages of high catalytic performance and long service life, and application thereof. According to the technical scheme, the active components of the catalyst are vanadium, phosphorus, cesium and lanthanum, the charge capacity of vanadium is 0.2-2 mmol/g, and the V:P:Cs:La mol ratio is 1:(0.5-1.5):(0.1-1.1):(0.01-0.05). The invention can be used for preparing methyl acrylate from methyl acetate and formaldehyde, and has the advantages of high catalytic performance and long service life.
Description
Technical field
The present invention relates to a kind of support type phosphorus vanadium caesium lanthanum catalyst and application thereof, especially relating to a kind of is raw material with formaldehyde and methyl acetate, synthesizing methyl acrylate catalyst and application thereof.
Background technology
Methyl acrylate is important Organic Chemicals, can be used for producing super absorbent resin, helps washing agent and water treatment agent etc., is widely used in every field such as coating, chemical fibre, weaving, leather, plastics, bonding agent, oil exploitation.Industrial, methyl acrylate is mainly by acrylic acid and methanol esterification and get.Oxidation of propylene is the method for production of acrylic acid that generally adopts in the world at present.The acrylic acid production device of China all adopts the method.In addition, in the middle of the propane selective oxidation processes is also being developed.But because the deep oxidation problem of propane is difficult to solution, the conversion ratio of propane and acrylic acid selectively not high, industrial prospect is uncertain.
The production of propylene mainly depends on steam heat cracking technology and catalytic cracking process, and needing naphtha, diesel oil or oil products such as weight/residual oil, wax oil is raw material.Because oil is consumed as the energy greatly, causes producing the petroleum shortage of propylene, thereby restricts acrylic acid production.Therefore, the research of reinforcement alternative materials production acrylic acid (ester) is imperative.
According to the national conditions of China, from national energy security and socio-economic development need, development is the Coal Chemical Industry industry of raw material with the coal, can alleviate oil supply and demand contradiction, to ensureing China's economic society steady development the important strategic meaning is arranged.Be raw material with methyl acetate and formaldehyde, also can make methyl acrylate by aldol reaction.Formaldehyde, acetic acid (methyl esters) all are the downstream derivatives of methyl alcohol, and coal acetic acid processed (methyl esters) and coal formaldehyde processed have had ripe production technology, have realized large-scale industrial production.Be that the technical process that raw material is produced methyl acrylate has good development prospect by coal-based chemical products.
The history that many decades has abroad been arranged about the research of aldol reaction catalyst and aldol condensation acrylic acid synthesizing (methyl esters).Be that the key that raw material is produced methyl acrylate is the synthetic of high performance catalyst with methyl acetate and formaldehyde.The document of comprehensive existing research acrylic acid (methyl esters) preparation as can be seen, the aldol condensation catalyst that uses in the document mainly comprises loading type alkali metal, alkaline-earth metal catalyst (Sun Wuyang, lift a sail, Xu Qingliang. the research of solid base catalyst synthesizing methyl acrylate activity. oil refining and chemical industry, 2009,02): 17-19,67.) and phosphorus vanadium catalyst (Ai M. Vapor-phase aldol condensation of formaldehyde with acetic acid on V
2O
5-P
2O
5Catalysts. Journal of Catalysis, 1987,107 (1): 201-208.) two big classes.
No matter loading type alkali metal, alkaline-earth metal catalyst, or phosphorus vanadium catalyst, service life is all shorter.More than two types catalyst in application, all exist catalysqt deactivation problem rapidly.For loading type alkali metal, alkaline-earth metal catalyst, its deactivation cause mainly is because self reuniting and running off of metal oxide causes.And for the phosphorus vanadium catalyst, though its catalytic performance is good, very big DEVELOPMENT PROSPECT is arranged, because v element can be combined (VO, V with multiple valence state with oxygen element
2O
3, VO
2, V
2O
5), catalyst in use plays the v element (V of catalytic activity effect
4+) be easy to oxidized or reduction and change valence state, the inactivation of this catalyst is more rapid.The inactivation of catalyst will cause the industrial production expense to improve, and operation easier strengthens.Thereby, be necessary further to improve the performance of catalyst, improve life of catalyst, obtain the methyl acrylate preparation method that production cost is low, product yield is high.
Summary of the invention
The present invention is in order to overcome the deficiencies in the prior art, provides a kind of catalytic performance height, life-span long, can be catalyst and the application thereof of feedstock production methyl acrylate with methyl acetate and formaldehyde.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is: a kind of support type phosphorus vanadium caesium lanthanum catalyst, this catalyst activity component is vanadium, phosphorus, caesium and lanthanum, the load capacity of described vanadium is 0.2-2mmol/g, the mol ratio of described vanadium and phosphorus, caesium and lanthanum is V:P:Cs:La=1:0.5-1.5:0.1-1.1:0.01-0.05, and adopts following method preparation:
A, with NH
4VO
3Adding concentration of volume percent is the lactic acid aqueous solution dissolving of 5-20%, adds 20～40 purpose silica-gel carriers, stirs 1-3h, then with H
3PO
4The aqueous solution adds wherein, stirs 1-3h, is 105-120 ℃ of dry 3-12h in temperature, and 400～600 ℃ of roasting 4-10h in nitrogen atmosphere obtain phosphorus vanadium catalyst intermediate;
The mol ratio of described vanadium and phosphorus is 1:0.5-1.5, described NH
4VO
3, lactic acid and silica gel weight part ratio be 0.07-0.7:0.6-2.4:3;
B, with cesium salt and the lanthanum salt mixed solution of making soluble in water, flood described phosphorus vanadium catalyst intermediate, be 105-120 ℃ of dry 3-12h in temperature, 400～600 ℃ of roasting 4-10h in nitrogen atmosphere make support type phosphorus vanadium caesium lanthanum catalyst then;
The mol ratio of described vanadium and caesium and lanthanum is V:Cs:La=1:0.1-1.1:0.01-0.05.
Described cesium salt is CsNO
3Or CH
3The mixture of one or both among the COOCs; Described lanthanum salt is La (CH
3COO)
3Or La (NO
3)
3In one or both mixture.
A kind of application of support type phosphorus vanadium caesium lanthanum catalyst; with the described support type phosphorus vanadium caesium lanthanum catalyst fixed bed reactors of packing into; under nitrogen protection, catalytic bed is warming up to 250～400 ℃; be carrier gas with nitrogen; methyl acetate and formaldehyde mixed solution are fed in the reactor, and react by catalytic bed preheating gasification back, and control methyl acetate and formaldehyde mole ratio are 1-3:1; methyl acetate and carrier gas mol ratio are 0.2-1:1, and the feed volume air speed is 1～6h
-1, make methyl acrylate.
The beneficial effect that the present invention compared with prior art has is: it is the feedstock production methyl acrylate that the present invention can adopt methyl acetate and formaldehyde, and the catalytic performance height, and the life-span is long.The present invention adopts in the process of preparation support type phosphorus vanadium caesium lanthanum catalyst, first load phosphorus vanadium on silica-gel carrier, the step of load caesium lanthanum again, the adding of this kind mode of loading and lanthanum element can be played stabilization to vanadium and the cesium element of load, avoid reunion, the loss of the change of v element valence state and cesium element, improve life of catalyst, reduce catalyst activation and renewal cost, reduce the production cost of methyl acrylate.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1
With 1.17g NH
4VO
3Add the 100ml concentration of volume percent and be heating for dissolving in 5% the lactic acid aqueous solution, add 30.0g20～30 purpose silica-gel carriers, stir 2h, add the 85%H of 0.69g
3PO
4The aqueous solution stirs 2h, 110 ℃ of dry 6h, and 450 ℃ of roastings are 6 hours in nitrogen atmosphere.CsNO with 0.20g
3La (NO with 0.04g
3)
36H
2O is dissolved in 100ml water, the solid of gained behind the impregnation-calcination, and 110 ℃ of dry 6h, 450 ℃ of roastings made support type phosphorus vanadium caesium lanthanum catalyst in 6 hours in nitrogen atmosphere.
Get above-mentioned catalyst that 10ml the makes fixed bed reactors (constant temperature zone of φ 10 * 500mm) of packing into; under nitrogen protection catalytic bed being warming up to 300 ℃, is carrier gas with nitrogen, is 1:1 according to methyl acetate/formaldehyde mole ratio; methyl acetate/carrier gas mol ratio is 1:2, feed volume air speed 1.7h
-1, the formalin of methyl acetate and 37% is fed in the reactor, react by catalytic bed preheating gasification back, makes methyl acrylate.React after 1 hour, the formaldehyde conversion ratio is 21.7%, methyl acrylate selectively be 65.5%, the yield of methyl acrylate is 14.2%.React after 20 hours, the yield of methyl acrylate is 10.6%.
Embodiment 2
With 5.40g NH
4VO
3Add the 100ml concentration of volume percent and be heating for dissolving in 20% the lactic acid aqueous solution, add 30.0g30～40 purpose silica-gel carriers, stir 1h, add the 85%H of 6.39g
3PO
4The aqueous solution stirs 1h, 115 ℃ of dry 4h, and 500 ℃ of roastings are 4 hours in nitrogen atmosphere.CsNO with 2.61g
3La (NO with 1.00g
3)
36H
2O is dissolved in 100ml water, the solid of gained behind the impregnation-calcination, and 115 ℃ of dry 4h, 500 ℃ of roastings made support type phosphorus vanadium caesium lanthanum catalyst in 10 hours in nitrogen atmosphere.
Get above-mentioned catalyst that 10ml the makes fixed bed reactors (constant temperature zone of φ 10 * 500mm) of packing into; under nitrogen protection catalytic bed being warming up to 360 ℃, is carrier gas with nitrogen, is 3:1 according to methyl acetate/formaldehyde mole ratio; methyl acetate/carrier gas mol ratio is 1:5, feed volume air speed 5.2h
-1, the formalin of methyl acetate and 37% is fed in the reactor, react by catalytic bed preheating gasification back, makes methyl acrylate.React after 1 hour, the formaldehyde conversion ratio is 51.4%, methyl acrylate selectively be 87.1%, the yield of methyl acrylate is 44.8%.React after 20 hours, the yield of methyl acrylate is 28.5%.
Embodiment 3
With 6.74g NH
4VO
3Add the 100ml concentration of volume percent and be heating for dissolving in 20% the lactic acid aqueous solution, add 30.0g20～30 purpose silica-gel carriers, stir 3h, add the 85%H of 7.31g
3PO
4The aqueous solution stirs 3h, 105 ℃ of dry 12h, and 550 ℃ of roastings are 8 hours in nitrogen atmosphere.CsNO with 12.35g
3La (NO with 0.49g
3)
36H
2O is dissolved in 100ml water, the solid of gained behind the impregnation-calcination, and 105 ℃ of dry 12h, 550 ℃ of roastings made support type phosphorus vanadium caesium lanthanum catalyst in 8 hours in nitrogen atmosphere.
Get above-mentioned catalyst that 10ml the makes fixed bed reactors (constant temperature zone of φ 10 * 500mm) of packing into; under nitrogen protection catalytic bed being warming up to 400 ℃, is carrier gas with nitrogen, is 3:1 according to methyl acetate/formaldehyde mole ratio; methyl acetate/carrier gas mol ratio is 1:3, feed volume air speed 2.6h
-1, the formalin of methyl acetate and 37% is fed in the reactor, react by catalytic bed preheating gasification back, makes methyl acrylate.React after 1 hour, the formaldehyde conversion ratio is 57.7%, methyl acrylate selectively be 75.5%, the yield of methyl acrylate is 43.6%.React after 20 hours, the yield of methyl acrylate is 20.6%.
Embodiment 4
With 2.77g NH
4VO
3Add the 100ml concentration of volume percent and be heating for dissolving in 10% the lactic acid aqueous solution, add 30.0g20～30 purpose silica-gel carriers, stir 2h, add the 85%H of 2.98g
3PO
4The aqueous solution stirs 2h, 120 ℃ of dry 6h, and 450 ℃ of roastings are 10 hours in nitrogen atmosphere.CH with 0.61g
3La (the NO of COOCs and 0.27g
3)
36H
2O is dissolved in 100ml water, the solid of gained behind the impregnation-calcination, and 120 ℃ of dry 6h, 450 ℃ of roastings made support type phosphorus vanadium caesium lanthanum catalyst in 4 hours in nitrogen atmosphere.
Get above-mentioned catalyst that 10ml the makes fixed bed reactors (constant temperature zone of φ 10 * 500mm) of packing into; under nitrogen protection catalytic bed being warming up to 380 ℃, is carrier gas with nitrogen, is 2:1 according to methyl acetate/formaldehyde mole ratio; methyl acetate/carrier gas mol ratio is 1:2, feed volume air speed 5.5h
-1, the formalin of methyl acetate and 37% is fed in the reactor, react by catalytic bed preheating gasification back, makes methyl acrylate.React after 1 hour, the formaldehyde conversion ratio is 54.4%, methyl acrylate selectively be 82.0%, the yield of methyl acrylate is 44.6%.React after 20 hours, the yield of methyl acrylate is 28.4%.
Embodiment 5
With 3.82g NH
4VO
3Add the 100ml concentration of volume percent and be heating for dissolving in 10% the lactic acid aqueous solution, add 30.0g20～30 purpose silica-gel carriers, stir 2h, add the 85%H of 3.71g
3PO
4The aqueous solution stirs 2h, 110 ℃ of dry 3h, and 450 ℃ of roastings are 6 hours in nitrogen atmosphere.CsNO with 1.66g
3La (NO with 0.28g
3)
36H
2O is dissolved in 100ml water, the solid of gained behind the impregnation-calcination, and 110 ℃ of dry 3h, 450 ℃ of roastings made support type phosphorus vanadium caesium lanthanum catalyst in 6 hours in nitrogen atmosphere.
Get above-mentioned catalyst that 10ml the makes fixed bed reactors (constant temperature zone of φ 10 * 500mm) of packing into; under nitrogen protection catalytic bed being warming up to 360 ℃, is carrier gas with nitrogen, is 3:1 according to methyl acetate/formaldehyde mole ratio; methyl acetate/carrier gas mol ratio is 1:3, feed volume air speed 2.6h
-1, the formalin of methyl acetate and 37% is fed in the reactor, react by catalytic bed preheating gasification back, makes methyl acrylate.React after 1 hour, the formaldehyde conversion ratio is 49.2%, methyl acrylate selectively be 74.7%, the yield of methyl acrylate is 36.8%.React after 20 hours, the yield of methyl acrylate is 15.5%.
Embodiment 6
With 2.14g NH
4VO
3Add the 100ml concentration of volume percent and be heating for dissolving in 10% the lactic acid aqueous solution, add 30.0g20～30 purpose silica-gel carriers, stir 2h, add the 85%H of 2.22g
3PO
4The aqueous solution stirs 2h, 110 ℃ of dry 10h, and 500 ℃ of roastings are 6 hours in nitrogen atmosphere.CsNO with 3.14g
3La (NO with 0.16g
3)
36H
2O is dissolved in 100ml water, the solid of gained behind the impregnation-calcination, and 110 ℃ of dry 10h, 500 ℃ of roastings made support type phosphorus vanadium caesium lanthanum catalyst in 6 hours in nitrogen atmosphere.
Get above-mentioned catalyst that 10ml the makes fixed bed reactors (constant temperature zone of φ 10 * 500mm) of packing into; under nitrogen protection catalytic bed being warming up to 380 ℃, is carrier gas with nitrogen, is 3:1 according to methyl acetate/formaldehyde mole ratio; methyl acetate/carrier gas mol ratio is 1:2, feed volume air speed 4.7h
-1, the formalin of methyl acetate and 37% is fed in the reactor, react by catalytic bed preheating gasification back, makes methyl acrylate.React after 1 hour, the formaldehyde conversion ratio is 40.9%, methyl acrylate selectively be 80.3%, the yield of methyl acrylate is 32.8%.React after 20 hours, the yield of methyl acrylate is 10.3%.
Embodiment 7
With 2.77g NH
4VO
3Add the 100ml concentration of volume percent and be heating for dissolving in 10% the lactic acid aqueous solution, add 30.0g20～30 purpose silica-gel carriers, stir 2h, add the 85%H of 2.98g
3PO
4The aqueous solution stirs 2h, 110 ℃ of dry 5h, and 450 ℃ of roastings are 6 hours in nitrogen atmosphere.CH with 0.61g
3La (the CH of COOCs and 0.19g
3COO)
3Be dissolved in 100ml water, the solid of gained behind the impregnation-calcination, 110 ℃ of dry 5h, 450 ℃ of roastings made support type phosphorus vanadium caesium lanthanum catalyst in 6 hours in nitrogen atmosphere.
Get above-mentioned catalyst that 10ml the makes fixed bed reactors (constant temperature zone of φ 10 * 500mm) of packing into; under nitrogen protection catalytic bed being warming up to 380 ℃, is carrier gas with nitrogen, is 2:1 according to methyl acetate/formaldehyde mole ratio; methyl acetate/carrier gas mol ratio is 1:2, feed volume air speed 5.5h
-1, the formalin of methyl acetate and 37% is fed in the reactor, react by catalytic bed preheating gasification back, makes methyl acrylate.React after 1 hour, the formaldehyde conversion ratio is 50.7%, methyl acrylate selectively be 68.1%, the yield of methyl acrylate is 34.5%.React after 20 hours, the yield of methyl acrylate is 25.9%.
Embodiment 8
With 3.43g NH
4VO
3Add the 100ml concentration of volume percent and be heating for dissolving in 15% the lactic acid aqueous solution, add 30.0g20～30 purpose silica-gel carriers, stir 2h, add the 85%H of 3.72g
3PO
4The aqueous solution stirs 2h, 110 ℃ of dry 12h, and 550 ℃ of roastings are 6 hours in nitrogen atmosphere.CH with 1.69g
3La (the CH of COOCs and 0.09g
3COO)
3Be dissolved in 100ml water, the solid of gained behind the impregnation-calcination, 110 ℃ of dry 12h, 550 ℃ of roastings made support type phosphorus vanadium caesium lanthanum catalyst in 6 hours in nitrogen atmosphere.
Get above-mentioned catalyst that 10ml the makes fixed bed reactors (constant temperature zone of φ 10 * 500mm) of packing into; under nitrogen protection catalytic bed being warming up to 400 ℃, is carrier gas with nitrogen, is 3:1 according to methyl acetate/formaldehyde mole ratio; methyl acetate/carrier gas mol ratio is 1:3, feed volume air speed 3.6h
-1, the formalin of methyl acetate and 37% is fed in the reactor, react by catalytic bed preheating gasification back, makes methyl acrylate.React after 1 hour, the formaldehyde conversion ratio is 36.6%, methyl acrylate selectively be 42.9%, the yield of methyl acrylate is 15.7%.React after 20 hours, the yield of methyl acrylate is 13.2%.
The invention is not restricted to above-described embodiment, in the ken that those of ordinary skills possess, can also not break away under the prerequisite of aim of the present invention and make a variety of changes.
Claims (3)
1. support type phosphorus vanadium caesium lanthanum catalyst, it is characterized in that this catalyst activity component is vanadium, phosphorus, caesium and lanthanum, the load capacity of described vanadium is 0.2-2mmol/g, the mol ratio of described vanadium and phosphorus, caesium and lanthanum is V:P:Cs:La=1:0.5-1.5:0.1-1.1:0.01-0.05, and adopts following method preparation:
A, with NH
4VO
3Adding concentration of volume percent is the lactic acid aqueous solution dissolving of 5-20%, adds 20～40 purpose silica-gel carriers, stirs 1-3h, then with H
3PO
4The aqueous solution adds wherein, stirs 1-3h, is 105-120 ℃ of dry 3-12h in temperature, and 400～600 ℃ of roasting 4-10h in nitrogen atmosphere obtain phosphorus vanadium catalyst intermediate;
The mol ratio of described vanadium and phosphorus is 1:0.5-1.5, described NH
4VO
3, lactic acid and silica gel weight part ratio be 0.07-0.7:0.6-2.4:3;
B, with cesium salt and the lanthanum salt mixed solution of making soluble in water, flood described phosphorus vanadium catalyst intermediate, be 105-120 ℃ of dry 3-12h in temperature, 400～600 ℃ of roasting 4-10h in nitrogen atmosphere make support type phosphorus vanadium caesium lanthanum catalyst then;
The mol ratio of described vanadium and caesium and lanthanum is V:Cs:La=1:0.1-1.1:0.01-0.05.
2. a kind of support type phosphorus vanadium caesium lanthanum catalyst according to claim 1 is characterized in that described cesium salt is CsNO
3Or CH
3The mixture of one or both among the COOCs; Described lanthanum salt is La (CH
3COO)
3Or La (NO
3)
3In one or both mixture.
3. the application of the described support type phosphorus of claim 1 a vanadium caesium lanthanum catalyst; it is characterized in that: with the described support type phosphorus vanadium caesium lanthanum catalyst fixed bed reactors of packing into; under nitrogen protection, catalytic bed is warming up to 250～400 ℃; be carrier gas with nitrogen; methyl acetate and formaldehyde mixed solution are fed in the reactor; react by catalytic bed preheating gasification back; control methyl acetate and formaldehyde mole ratio are 1-3:1; methyl acetate and carrier gas mol ratio are 0.2-1:1, and the feed volume air speed is 1～6h
-1, make methyl acrylate.
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| CN103524345B (en) * | 2013-10-23 | 2015-02-11 | 上海浦景化工技术股份有限公司 | Product separation process for preparing methyl acrylate from methyl acetate |
| 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 |
| CN104275172A (en) * | 2014-09-10 | 2015-01-14 | 江苏金聚合金材料有限公司 | High-stability catalyst for synthesizing methyl acrylate and preparation method of high-stability catalyst for synthesizing methyl acrylate |
| CN106278865B (en) * | 2016-08-03 | 2018-08-21 | 江苏大学 | A kind of acetic acid formaldehyde condensation prepares acrylic acid |
| CN106631771B (en) * | 2016-12-29 | 2019-12-17 | 沈阳化工大学 | Acrylic acid synthesis method |
| CN107159299B (en) * | 2017-04-25 | 2019-12-31 | 江苏大学 | Ce-VPO/SBA-15 catalyst and preparation method and application thereof |
| CN107126970B (en) * | 2017-04-25 | 2019-10-01 | 江苏大学 | A kind of Nd-VPO/SiO2Catalyst and its preparation method and application |
| CN110639492A (en) * | 2018-06-27 | 2020-01-03 | 中国石油化工股份有限公司 | Catalyst for preparing methyl acrylate from methyl acetate and formaldehyde and application thereof |
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