CN102962052B - Catalyst for process of synthesizing acrylic acid by using acetic acid and paraformaldehyde, preparation and application of catalyst - Google Patents
Catalyst for process of synthesizing acrylic acid by using acetic acid and paraformaldehyde, preparation and application of catalyst Download PDFInfo
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Abstract
The invention relates to a catalyst for a process of synthesizing acrylic acid by using acetic acid and paraformaldehyde. The catalyst comprises an active component, an active additive and a carrier, wherein niobium of the active component is from niobium oxide, boron of the active component is from one of boric acid and boric oxide, cesium in the active additive is from cesium acetate, vanadium in the active additive is from ammonium metavanadate, lead in the active additive is from lead acetate, phosphorus in the active additive is from phosphoric acid, and the carrier is one or more of silicon dioxide, aluminum oxide, kaoline and titanium dioxide. The invention also discloses preparation and application of the catalyst. The catalyst has better activity and selectivity and good stability, is simple in preparation process, is suitable for large-scale industrial application, and is environmental-friendly.
Description
Technical field
The present invention relates to the catalyst of acrylic acid synthesizing, particularly the catalyst of a kind of acetic acid and paraformaldehyde acrylic acid synthesizing.
Background technology
Acrylic acid is basic material and intermediate very important in modern chemical industry, can prepare the polymer such as plasticity is crosslinked through emulsion polymerisation, polymerisation in solution etc., can be widely used in the numerous areas such as super absorbent resin, adhesive, coating, textile auxiliary and oil field chemical.
Method for production of acrylic acid has much both at home and abroad, main method has chlorethanol method, cyanoethanol method, high pressure Reppe method, ethene Carbonyl group oxidation method, direct oxidation of propylene method, propane oxidation, propylene two-step oxidizing process etc., and propylene two-step oxidizing process is the process of the main flow of current production acrylic acid.First step propylene oxidation generates methacrylaldehyde, second step, and acrolein oxidation becomes acrylic acid.
At present, the nearly all large-scale acrylic acid production device of industrialization all adopts propylene two-step oxidizing process in the world.What oxidation of propylene adopted is petroleum path, and acetic acid and paraformaldehyde acrylic acid synthesizing are to belong to Coal Chemical Industry Route, and the method route has great importance for the dependence overcoming oil.
No matter acetic acid and formaldehyde do raw material acrylic acid synthesizing or propylene oxidation acrylic acid processed, core technology is all catalyst, propylene two-step oxidation preparing propone acid catalyst great majority are O composite metallic oxide catalysts, little about the catalyst report of acetic acid and formaldehyde acrylic acid synthesizing.Chinese patent CN102151583A discloses a kind of phosphorus vanadium catalyst, this catalyst be with phosphorus vanadium as active component, its making step is: vanadic anhydride, isobutanol and phenmethylol are mixed, add hot reflux certain hour, stir simultaneously.Solid orthophosphoric acid and isobutanol Hybrid Heating are stirred, after orthophosphoric acid dissolves, two parts of solution are mixed, add thermal agitation 4-10h, cooling, vacuum filtration, simultaneously dry, then calcining and activating.This catalyst manufacturing process is very long, complicated, and catalyst activity is not high, makes in the remaining filtrate of catalyst and contains a large amount of isobutanols and phenmethylol, has toxicity, easily to environment.
Summary of the invention
The object of the invention is in order to overcome prior art above shortcomings, the catalyst that a kind of acetic acid and paraformaldehyde acrylic acid synthesizing are provided, has good activity and selectivity, good stability, manufacture craft is simply applicable to heavy industrialization application, environmental friendliness.In addition, the present invention also provides preparation method and the application of described catalyst.
To achieve these goals, the present invention adopts following technical proposals:
A catalyst for acetic acid and paraformaldehyde acrylic acid synthesizing, the component of catalyst comprises active component, coagent and carrier, wherein:
In active component, niobium carrys out automatic oxidation niobium, and boron is from the one in boric acid, boron oxide;
In coagent, caesium is from cesium acetate, and vanadium is from ammonium metavanadate, and plumbous from lead acetate, phosphorus is from phosphoric acid;
Carrier is selected one or several the mixture in silica, aluminium oxide, kaolin, titanium dioxide.
Each component taking the content of the quality percentage composition of carrier as:
The content of niobium oxide is 5%-9%, and boron is in boron oxide, and content is 10%-15%;
Cesium acetate is in cesium oxide, and content is 8%-12%, and ammonium metavanadate is in vanadic anhydride, and content is 2.2%-3.5%, and lead acetate is in lead oxide, and content is 0.5-1.8%, and phosphoric acid is in phosphorus pentoxide, and content is 4%-8%.
Catalyst also has binding agent and lubricant.Described binding agent is selected sesbania powder, and described lubricant is selected graphite powder.Sesbania powder does binding agent and lubricant, is beneficial to extruded moulding, and sintering after heat is burnt and lost.
Described catalyst adopts kneading method preparation.
A preparation method for described acetic acid and the catalyst of paraformaldehyde acrylic acid synthesizing, carries out in accordance with the following steps:
(1) compound that contains active component and coagent that can be dissolved in water is mixed with solution;
(2) carrier, water-fast active component, water-fast coagent, pore former are proportionally mixed, add the solution of preparation in step (1), add again appropriate amount of deionized water, extrusion after kneading 3h, air-dry, dry 2 ~ 4h at 80 ~ 120 DEG C, roasting 2 ~ 5h at 400 ~ 600 DEG C, cooling, to obtain final product.
The application of the catalyst of a kind of described acetic acid and paraformaldehyde acrylic acid synthesizing, its process using two stage process process, raw material is through superheat section and conversion zone acrylic acid synthesizing, feed molar proportioning acetic acid: paraformaldehyde=12:1, charging rate 0.3mL/min, nitrogen flow rate 6L/h, catalyst 35mL; 360 ~ 400 DEG C of superheat section temperature, 340 ~ 400 DEG C of conversion zone temperature.
What take that 35mL prepares resolves into short grained Catalyst packing in reactor centre position, two sections of filling quartz sands.Mol ratio acetic acid preparing: the raw material of paraformaldehyde=12:1, under the drive of nitrogen, enter superheat section by constant-flux pump, superheat section Temperature Setting is 360 ~ 400 DEG C, nitrogen flow is 6L/h.Raw material enters after superheat section, gasification, and paraformaldehyde decomposes.Gas after decomposition enters conversion zone, generates acrylic acid, and conversion zone Temperature Setting is 340 ~ 400 DEG C.Finally, calculate paraformaldehyde conversion ratio, acrylic acid selectively and product yield with paraformaldehyde.
Described method for preparing catalyst is simple, is applicable to heavy industrialization application.
Compared with prior art, the invention has the beneficial effects as follows:
Catalyst of the present invention has good activity and selectivity, good stability, and manufacture craft is simply applicable to heavy industrialization application, environmental friendliness.
Detailed description of the invention
Below in conjunction with detailed description of the invention, foregoing invention content of the present invention is described in further detail.But this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, make various replacements and change, all should comprise within the scope of the invention.
embodiment 1
Take titanium dioxide 400.0g, boric acid 106.5g(remembers with boron oxide, account for carrier 15%), ammonium metavanadate 11.32g is (in vanadic anhydride, account for carrier 2.2%), graphite 8.0g, sesbania powder 12.0g be in blender, after fully mixing, add deionized water 116.0g, kneading 3h, take out the dry wet uniform catalyst of suitable distribution after kneading, on banded extruder with the big or small extrusion of diameter ￠ 3.Then leave standstill air dried overnight.Catalyst after air-dry is put into baking oven, 110 DEG C of dry 2h, then roasting 2h at 450 DEG C in Muffle furnace, takes out and puts into drier, stand-by.
What take that 35mL prepares resolves into short grained Catalyst packing in reactor centre position, two sections of filling quartz sands.Mol ratio acetic acid preparing: the raw material of paraformaldehyde=12:1, under the drive of nitrogen, enter superheat section by constant-flux pump, superheat section Temperature Setting is 400 DEG C, nitrogen flow is 6L/h.Raw material enters after superheat section, gasification, and paraformaldehyde decomposes.Gas after decomposition enters conversion zone, generates acrylic acid, and conversion zone Temperature Setting is 400 DEG C.Calculate with paraformaldehyde, paraformaldehyde conversion ratio is 91.2%, and acrylic acid is selective 81.1%, product yield 73.96%.
embodiment 2
Take titanium dioxide 400.0g, boric acid 106.5g(remembers with boron oxide, account for carrier 15%), ammonium metavanadate 14.00g is (in vanadic anhydride, account for carrier 3.5%), graphite 8.0g, sesbania powder 12.0g be in blender, after fully mixing, add deionized water 116.0g, kneading 3h, take out the dry wet uniform catalyst of suitable distribution after kneading, on banded extruder with the big or small extrusion of diameter ￠ 3.Then leave standstill air dried overnight.Catalyst after air-dry is put into baking oven, 110 DEG C of dry 2h, then roasting 2h at 450 DEG C in Muffle furnace, takes out and puts into drier, stand-by.
Synthesis process is same as Example 1, and superheat section Temperature Setting is 380 DEG C, and conversion zone Temperature Setting is 400 DEG C, and test result is calculated with paraformaldehyde, and formaldehyde conversion ratio is 89.30%, and acrylic acid is selective 80.47%, product yield 71.86%.
embodiment 3
Take superfine silicon dioxide powder 150.0g, kaolin 30.0g, sesbania powder 7.5g, graphite powder 4.5g, niobium oxide 12.0g(account for carrier 6.7%), cesium acetate 18.39g(is in cesium oxide, account for carrier 9.0%) mix, be placed in mixed kneading machine, add 105mL alkaline silica sol and appropriate amount of deionized water, fully kneading 4h, on banded extruder with the big or small extrusion of diameter ￠ 3.Air dried overnight.Catalyst after air-dry is placed in to 80 DEG C of baking ovens, and dry 2h, is then warming up to 120 DEG C and continues dry 2h, and put into Muffle furnace Program and be warming up to 600 DEG C, calcining 4h, cooling, for subsequent use.
Synthesis process is same as Example 1, and superheat section Temperature Setting is 360 DEG C, and conversion zone Temperature Setting is 360 DEG C, and test result is calculated with paraformaldehyde, and formaldehyde conversion ratio is 67.27%, and acrylic acid is selective 86.58%, product yield 58.24%.
embodiment 4
Take superfine silicon dioxide powder 150.0g, kaolin 30.0g, sesbania powder 7.5g, graphite powder 4.5g, cesium acetate 24.52g(in cesium oxide, account for carrier 12.0%), lead acetate 1.29g(is in lead oxide, account for carrier 0.5%), mix, be placed in mixed kneading machine, add 105mL alkaline silica sol and appropriate amount of deionized water, fully kneading 4h, on banded extruder with the big or small extrusion of diameter ￠ 3.Air dried overnight.Catalyst after air-dry is placed in to 80 DEG C of baking ovens, and dry 2h, is then warming up to 120 DEG C and continues dry 2h, and put into Muffle furnace Program and be warming up to 600 DEG C, calcining 4h, cooling, for subsequent use.
Synthesis process is same as Example 1, and superheat section Temperature Setting is 360 DEG C, and conversion zone Temperature Setting is 340 DEG C, and test result is calculated with paraformaldehyde, and formaldehyde conversion ratio is 62.37%, and acrylic acid is selective 80.76%, product yield 50.37%.
embodiment 5
Take superfine silicon dioxide 100.0g, kaolin 20.0g, sesbania powder 5.0g, graphite powder 3.0g, boric acid 31.96g(in boron oxide, account for carrier 10%), mix, be placed in mixed kneading machine, add appropriate amount of deionized water, fully kneading 3h, on banded extruder with the big or small extrusion of diameter ￠ 3.Air dried overnight.Catalyst after air-dry is placed in to 120 DEG C of baking ovens, and dry 2h, puts into Muffle furnace Program and is warming up to 500 DEG C, and calcining 5h is cooling, for subsequent use.
Synthesis process is same as Example 1, and superheat section Temperature Setting is 360 DEG C, and conversion zone Temperature Setting is 360 DEG C, and test result is calculated with paraformaldehyde, formaldehyde conversion ratio 80.29%, and acrylic acid is selective 74.89%, product yield 60.13%.
embodiment 6
Take superfine silicon dioxide 100.0g, boehmite (monohydrate alumina) 100.0g, the ratio formulation vehicle of 1:1.Take phosphoric acid (in phosphorus pentoxide, account for carrier 4%) 11.05g, niobium oxide 16.0g(account for carrier 8%), sesbania powder 6.0g, graphite powder 4.0g, and carrier mixes.Phosphoric acid adds in mixture after dissolving by appropriate amount of deionized water, kneading 3h, and the big or small extrusion of ￠ 3, air dried overnight, at 100 DEG C, dry 3h, puts into Muffle furnace Program and is warming up to 600 DEG C, and calcining 2h is cooling, for subsequent use.
Synthesis process is same as Example 1, and superheat section Temperature Setting is 380 DEG C, and conversion zone Temperature Setting is 380 DEG C, and test result is calculated with paraformaldehyde, formaldehyde conversion ratio 85.32%, and acrylic acid is selective 70.73%, product yield 60.34%.
embodiment 7
Take superfine titanic oxide 300.0g, as carrier.Take phosphoric acid 34.5g(in phosphorus pentoxide, account for carrier 8%), boric acid 66.56g(is in boron oxide, account for carrier 12.5%), sesbania powder 6.0g, graphite powder 4.0g, and carrier mixes.Phosphoric acid adds in mixture after dissolving by appropriate amount of deionized water, kneading 3h, and the big or small extrusion of ￠ 3, air dried overnight, at 100 DEG C, dry 3h, puts into Muffle furnace Program and is warming up to 400 DEG C, and calcining 2h is cooling, for subsequent use.
Synthesis process is same as Example 1, and superheat section Temperature Setting is 400 DEG C, and conversion zone Temperature Setting is 400 DEG C, and test result is calculated with paraformaldehyde, formaldehyde conversion ratio 86.18%, and acrylic acid is selective 50.36%, product yield 43.40%.
embodiment 8
Take titanium dioxide 250.0g, boehmite (monohydrate alumina) 50.0g, according to the ratio formulation vehicle of 5:1.Take boric acid 66.56g(in boron oxide, account for carrier 12.5%), lead acetate 6.6g(is in lead oxide, account for carrier 1.5%), graphite powder 6.0g, sesbania powder 9.0g, and carrier mixes.Add appropriate amount of deionized water, kneading 3h, the big or small extrusion of ￠ 3, air dried overnight, at 90 DEG C, dry 4h, puts into Muffle furnace Program and is warming up to 400 DEG C, and calcining 5h is cooling, for subsequent use.
Synthesis process is same as Example 1, and superheat section Temperature Setting is 380 DEG C, and conversion zone Temperature Setting is 400 DEG C, and test result is calculated with paraformaldehyde, paraformaldehyde conversion ratio 70.5%, and acrylic acid is selective 56.6%, product yield 39.9%.
embodiment 9
Take superfine silicon dioxide powder 140.0g, kaolin 40.0g, sesbania powder 6.5g, graphite powder 5.5g, niobium oxide 17.3g(account for carrier 9%), cesium acetate 16.34g(is in cesium oxide, account for carrier 8%) mix, be placed in mixed kneading machine, add 100mL alkaline silica sol and appropriate amount of deionized water, fully kneading 4h, on banded extruder with the big or small extrusion of diameter ￠ 3.Air dried overnight.Catalyst after air-dry is placed in to 100 DEG C of baking ovens, and dry 2h, is then warming up to 120 DEG C and continues dry 2h, and put into Muffle furnace Program and be warming up to 500 DEG C, calcining 4h, cooling, for subsequent use.
Synthesis process is same as Example 1, and superheat section Temperature Setting is 380 DEG C, and conversion zone Temperature Setting is 400 DEG C, and test result is calculated with paraformaldehyde, and paraformaldehyde conversion ratio is 86.2%, and acrylic acid is selective 80.3%, product yield 59.88%.
embodiment 10
Take titanium dioxide 200.0g, boehmite (monohydrate alumina) 100.0g, according to the ratio formulation vehicle of 2:1.Take niobium oxide 14.9g(account for carrier 5%), lead acetate 7.92g(is in lead oxide, account for carrier 1.8%), graphite powder 5.0g, sesbania powder 7.0g, and carrier mixes.Add appropriate amount of deionized water, kneading 3h, the big or small extrusion of ￠ 3, air dried overnight, at 90 DEG C, dry 4h, puts into Muffle furnace Program and is warming up to 600 DEG C, and calcining 2h is cooling, for subsequent use.
Synthesis process is same as Example 1, and superheat section Temperature Setting is 400 DEG C, and conversion zone Temperature Setting is 400 DEG C, and test result is calculated with paraformaldehyde, paraformaldehyde conversion ratio 70.5%, and acrylic acid is selective 56.6%, product yield 39.9%.
In sum, show that catalyst of the present invention has good activity and selectivity, good stability, manufacture craft is simply applicable to heavy industrialization application, environmental friendliness.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, be equal to and replace and improvement etc., within all should being included in protection scope of the present invention.
Claims (2)
1. a preparation method for the catalyst of acetic acid and paraformaldehyde acrylic acid synthesizing, is characterized in that carrying out in accordance with the following steps:
(1) compound that contains active component and coagent that can be dissolved in water is mixed with solution;
(2) carrier, water-fast active component, water-fast coagent, pore former are proportionally mixed, add the solution of preparation in step (1), add again appropriate amount of deionized water, extrusion after kneading 3h, air-dry, dry 2-4h at 80-120 DEG C, roasting 2-5h at 400-600 DEG C, cooling, to obtain final product;
Active component comprises one or both in niobium, boron, and niobium carrys out automatic oxidation niobium, and boron is from the one in boric acid, boron oxide;
Coagent comprises one or more in caesium, vanadium, lead, and caesium is from cesium acetate, and vanadium is from ammonium metavanadate, plumbous from lead acetate;
Carrier is selected one or several the mixture in silica, aluminium oxide, kaolin, titanium dioxide;
Each component taking the content of the quality percentage composition of carrier as:
The content of niobium oxide is 5%-9%, and boron is in boron oxide, and content is 10%-15%;
Cesium acetate is in cesium oxide, and content is 8%-12%, and ammonium metavanadate is in vanadic anhydride, and content is 2.2%-3.5%, and lead acetate is in lead oxide, and content is 0.5-1.8%.
2. the application of the catalyst of an acetic acid as claimed in claim 1 and paraformaldehyde acrylic acid synthesizing, it is characterized in that: its process using two stage process process, raw material is through superheat section and conversion zone acrylic acid synthesizing, feed molar proportioning acetic acid: paraformaldehyde=12:1, charging rate 0.3mL/min, nitrogen flow rate 6L/h, catalyst 35mL; Superheat section temperature 360-400 DEG C, conversion zone temperature 340-400 DEG C.
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| CN103230789A (en) * | 2013-04-27 | 2013-08-07 | 江门谦信化工发展有限公司 | Preparation method of nanometer solid super base catalyst applied to synthesis of acrylic acid by utilizing acetic acid and formaldehyde |
| CN103611522B (en) * | 2013-07-09 | 2016-03-02 | 中国科学院过程工程研究所 | One formaldehyde and acetic acid are catalyst and its preparation method of Material synthesis acrylic acid (ester) |
| CN103586067B (en) * | 2013-07-09 | 2017-02-08 | 中国科学院过程工程研究所 | Method for synthesizing acrylic acid by aqueous formaldehyde solution and acetic 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 |
| DE102014008081A1 (en) * | 2014-05-30 | 2015-11-19 | Basf Se | A process for the production of acrylic acid using an alkali and alkaline earth free zeolitic material |
| CN107866259B (en) * | 2016-09-23 | 2019-12-10 | 中国石油化工股份有限公司 | catalyst for durene gas-phase oxidation reaction |
| CN106748720A (en) * | 2016-12-21 | 2017-05-31 | 沈阳化工大学 | One kind prepares acrylic acid |
| CN108380201A (en) * | 2018-03-05 | 2018-08-10 | 江苏索普（集团）有限公司 | Solid acid catalyst for aldol condensation acrylic acid and preparation method thereof and application method |
| CN112371100B (en) * | 2020-11-07 | 2023-02-17 | 江苏大学 | Metal Cs modified B 2 O 3 Catalyst, preparation method and application thereof |
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| DE3561456D1 (en) * | 1984-05-21 | 1988-02-25 | Toa Gosei Chem Ind | Process for the production of acrylic acid or methacrylic acid |
| US5808148A (en) * | 1997-01-03 | 1998-09-15 | Eastman Chemical Company | Preparation of α,β-unsaturated carboxylic acids and esters |
| GB9807498D0 (en) * | 1998-04-08 | 1998-06-10 | Ici Plc | Production of unsaturated acids therfore and catalysts therfor |
| JP2003267924A (en) * | 2002-03-18 | 2003-09-25 | Mitsubishi Rayon Co Ltd | Method of producing methacrylic acid and method of producing methacrylic acid ester |
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