CN102114427B - Method for preparing catalyst in preparation of acrylic acid by oxidizing acrolein - Google Patents
Method for preparing catalyst in preparation of acrylic acid by oxidizing acrolein Download PDFInfo
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Abstract
The invention relates to a method for preparing a catalyst in preparation of acrylic acid by oxidizing acrolein. The general formula of the catalyst is Mo12VaCubWcXdYeOf/Z; and the catalyst is molded by baking for 1 to 24h at the temperature of between 350 and 410 DEG C, and is treated for 3 to 60 hours in mixed gas of air and vapor in any proportion at the temperature of between 260 and 390 DEG C before reaction. The method has the characteristics that: after the catalyst is treated before the reaction, the activity is greatly improved and the catalyst can achieve a steady state at an initial stage of the reaction, so that the danger that the interlocking is caused or the catalyst is damaged caused by hot spot jump or temperature runaway due to overhigh temperature in the running process is avoided; and the catalyst is favorable for being used on industrial devices and is applicable to exhaust gas cycling and non-exhaust gas cycling processes.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof of prepared by acrolein oxidation acrylic acid catalyst.
Background technology
Mo-V system composite oxides are the acrylic acid effective catalysts of prepared by acrolein oxidation.In industrial production, in order to improve output, employing contains the methacrylaldehyde raw material of higher concentration or improves the method for air speed, and the intrinsic strong exothermal nature of reaction, make the amount of heat that produces in the course of reaction in beds, form high-temperature part, cause over oxidation easily and catalyst selectivity and yield are reduced, also can cause simultaneously acceleration inactivation even the damage of catalyst.And the larger problem that it brings is, or runaway reaction that temperature runaway cause too high because of bed temperature makes startup procedure unusually difficult, even can face chain problem.
In order to address this problem, can take to reduce the method for reaction tube diameter, thereby alleviate the accumulation of heat of hotspot location, but cause and reduced production capacity, be disadvantageous economically.For this reason, the variations of adopting along bed position, reactor feedstocks porch to exit more, change successively the method for Catalyst packing structure, come the dilute catalyst bed also to reduce successively the method for thinner ratio such as the JP30688 description with inert substance, describe the size that changes catalyst and the method that reduces successively granular size such as JP241209 and CN1070840C, describe the method that changes catalyst activity and add successively high activated catalyst such as JP10802, CN1266106C and CN1672790A.These methods are suppressing to have played certain effect aspect the temperature of focus position, but the catalyst activity molar ratio exit catalyst activity amount of substance of the unstripped gas porch of general reactor is few, cause the catalyst of porch faster than the catalysqt deactivation in exit, affect the stability that catalyst moves for a long time under high yield condition.The adding toxic component reduces the activity of catalyst, although can reach the inhibition to the hot spot temperature, but so that the conversion ratio of stage methacrylaldehyde is not high in early days, cause the reduction of productive rate, and toxic component can affect the stability of catalyst after the oxidation reaction of long period after the absorption of catalyst activity position.
The present invention has prepared the Mo-V Containing Oxide Catalyst and has been used in the method for dividing one-step baking in the different atmosphere, make the performance of catalyst reach a kind of comparatively desirable state, the activity of catalyst is largely increased and stable state can be reaches in the reaction starting stage, avoid in startup procedure, causing that because of excess Temperature focus is climbed sharply or temperature runaway, thereby cause danger chain even that catalyst is destroyed, be very beneficial for using at commercial plant, be applicable to circulation of tail gas and non-exhaust gas circulation process.
Summary of the invention
The purpose of this invention is to provide preparation method and the application thereof of the acrylic acid catalyst of a kind of prepared by acrolein oxidation.
A kind of preparation method of prepared by acrolein oxidation acrylic acid catalyst, be characterized in: catalyst is by Mo
12V
aCu
bW
cX
dY
eO
f/ Z forms, X is Nb, Sb, Te, Ce, at least a among La, Nd, Sm, Cs, the Ge, Y is at least a among Mg, Ca, Sr, the Ba, the scope of a is 1～10, the scope of b is 0～6, the scope of c is that the scope of 0～7, d is that the scope of 0～4, e is 0～5, f is by the determined numerical value of the oxidation state of component, and Z is the simple substance silica flour; Preformed catalyst in the gaseous mixture of oxygen or oxygen and inert gas, roasting 1～24h under 350～410 ℃ condition; Before the roasting rear catalyst reaction again with in the gaseous mixture of arbitrary ratio air and steam in 260-390 ℃ of lower processing 3-60h.
During catalyst of the present invention forms, molybdic acid, ammonium paramolybdate or molybdenum oxide are adopted in the Mo source, ammonium metavanadate, vanadium oxide or oxalic acid vanadyl are adopted in the V source, wolframic acid, ammonium paratungstate or ammonium metatungstate are adopted in the W source, copper nitrate, Schweinfurt green or cupric oxalate are adopted in the Cu source, and X and Y source adopt corresponding oxide maybe can be decomposed into salt or the hydroxide of oxide.
The preparation method of preformed catalyst is among the present invention, a. with Mo, V and the W source A solution that gets soluble in water under 70～100 ℃ of conditions, with Cu, X and the Y source B solution that gets soluble in water under 60～80 ℃ of conditions, under 40～80 ℃ of conditions, B solution poured in the A solution to get into C solution, direct adding Z component mixes and obtains D solution in the solution, and D solution drying is obtained catalyst powder; Perhaps first C solution drying is obtained powder, again this powder and Z component are mixed to get catalyst powder; B. add in the catalyst powder and be selected from one or more shaping assistants among water, Ludox, glycerine, the cellulose and be selected from a kind of strength improving agent among ceramic fibre, the inorganic crystal whisker, be shaped to spherical, solid or the hollow cylindrical particle, the shaping assistant addition is 0.01 % by weight-25 % by weight of catalyst powder weight, and strength improving agent addition is 0.01 % by weight-15 % by weight of catalyst powder weight.
D solution drying or C solution drying are to carry out the static state drying under 90～200 ℃ of conditions or carry out spray-drying under 280～350 ℃ of inlet temperatures, 130～160 ℃ of conditions of outlet temperature among the present invention.
Among the present invention acrolein oxidation prepare acrylic acid be in the presence of oxygen the reaction, the volume integral percentage of unstripped gas consists of methacrylaldehyde 2～14%, oxygen 0.5～25%, steam 1～30%, unreacted propylene and other organic compound 1.3%～1.5%, all the other are nitrogen, reaction temperature is 200～300 ℃, reaction pressure is normal pressure～0.02Mpa, and air speed is 900～8000h
-1
The present invention has following features: the activity of catalyst can reach stable state in the reaction starting stage, avoid in startup procedure, causing that because of excess Temperature focus is climbed sharply or temperature runaway, thereby cause danger chain even that catalyst is destroyed, be very beneficial for using at commercial plant, be applicable to circulation of tail gas and non-exhaust gas circulation process.
The specific embodiment
The present invention is further described by the following embodiment, but protection domain is not subjected to the restriction of embodiment.
Embodiment 1
Add 163g ammonium molybdate, 31.3g ammonium metatungstate and 47.5g ammonium metavanadate in 80 ℃ 750g water, stirring and dissolving gets A solution; Add 2.1g lanthanum nitrate and 47.4g copper nitrate in 60 ℃ 100g water, stirring and dissolving gets B solution, B solution is poured in the A solution to get into C solution under 60 ℃, and C solution gets dry powder at 150 ℃ of lower dry 10h.Add 19.5g Ludox (20wt%) in 100g dry powder and the 88g silica flour and mix, extruded moulding is diameter 1mm, long 2mm cylindrical pellet, obtains preformed catalyst at 380 ℃ of lower roasting 5h.
Oxidation reaction is that the little evaluation response device of 20mm (in have external diameter 3mm sleeve pipe) carries out at internal diameter, preformed catalyst loadings 15ml, the percent by volume of unstripped gas consists of: methacrylaldehyde 7%, oxygen 9%, steam 15%, unreacted propylene and other organic compound 1.4%, all the other are nitrogen, air speed 1200h
-1The reaction procatalyst is at 385 ℃ of lower air and steam treatment 5h of using, and then cooling is reacted, 250 ℃ of lower acrolein conversion rate 99.5%, and acrylic acid yield 97.3%.
Embodiment 2
Add 163g ammonium molybdate, 28.7g ammonium metatungstate and 39.5g ammonium metavanadate in 80 ℃ 750g water, stirring and dissolving gets A solution; Add 47.4g copper nitrate and 2.8g strontium nitrate in 60 ℃ 100g water, stirring and dissolving gets B solution, B solution is poured in the A solution to get into C solution under 60 ℃, and C solution gets dry powder at 150 ℃ of lower dry 10h.Adding 12g propane diols and 19.5g Ludox (20wt%) mix in 100g dry powder and the 88g silica flour, and extruded moulding is diameter 1mm, long 2mm cylindrical pellet, obtains preformed catalyst in 380 ℃ of lower roasting 5h in nitrogen.
Oxidation reaction is that the little evaluation response device of 20mm (in have external diameter 3mm sleeve pipe) carries out at internal diameter, preformed catalyst loadings 15ml, the percent by volume of unstripped gas consists of: methacrylaldehyde 7%, oxygen 10%, steam 16%, unreacted propylene and other organic compound 1.5%, all the other are nitrogen, air speed 1400h
-1Then the reaction procatalyst cools the temperature to 254 ℃ of reactions, acrolein conversion rate 99.2%, acrylic acid yield 97.5% at 340 ℃ of lower air and steam treatment 30h of using.
Embodiment 3
Add 22g ethylene glycol, 130.2g ammonium molybdate, 28.4g ammonium metatungstate and 38.1g ammonium metavanadate in 90 ℃ 600g water, stirring and dissolving gets A solution; Add 2.6g lanthanum nitrate, 4.2g ammonium niobium oxalate and 38.1g copper nitrate in 60 ℃ 80g water, stirring and dissolving gets B solution, B solution is poured in the A solution to get into C solution under 60 ℃, and C solution gets dry powder at 120 ℃ of lower dry 20h.Adding 3.8g graphite and 19g Ludox (30%) mix in 100g dry powder and the 90g silica flour, and kneading, extruded moulding are diameter 1mm, long 2mm cylindrical pellet.This particle obtains preformed catalyst in 380 ℃ of lower roasting 5h in air.
Oxidation reaction is that the little evaluation response device of 20mm (in have external diameter 3mm sleeve pipe) carries out at internal diameter, preformed catalyst loadings 15ml, the percent by volume of unstripped gas consists of: methacrylaldehyde 7.5%, oxygen 11%, steam 10%, unreacted propylene and other organic compound 1.5%, all the other are nitrogen, air speed 1500h
-1Then the reaction procatalyst cools the temperature to 256 ℃ of reactions, acrolein conversion rate 99.2%, acrylic acid yield 96.6% at 280 ℃ of lower air and steam treatment 50h of using.
Embodiment 4
In 90 ℃ 6000g water, add 300g oxalic acid, 1302g ammonium molybdate, 280g ammonium metatungstate and 364g ammonium metavanadate, stirring and dissolving gets A solution; Add 26g lanthanum nitrate, 42g ammonium niobium oxalate and 381g copper nitrate in 60 ℃ 800g water, stirring and dissolving gets B solution, B solution is poured in the A solution to get into C solution under 60 ℃, and C solution gets dry powder at 120 ℃ of lower dry 20h.1000g dry powder and 900g silica flour, 38g graphite and 190g Ludox (30wt%) mix, and granulation, beat the cylindrical hollow particle that sheet is shaped to external diameter 5mm, internal diameter 2mm, long 3mm.This preformed catalyst is used for the acrolein oxidation reaction behind 380 ℃ of lower roasting 5h.
Oxidation reaction is carried out at the single hose system of internal diameter 27mm (in have external diameter 8mm sleeve pipe), long 3400mm, and the filling of reactor inlet place is with the catalyst of 40wt% inertia bead dilution, and loading height is 1000mm; The preformed catalyst that the lower end filling is diluted with 10% inertia bead, loading height is 2000mm; The percent by volume of unstripped gas consists of: methacrylaldehyde 7%, and oxygen 9%, steam 15%, unreacted propylene and other organic compound 1.3%, all the other are nitrogen, air speed 1500h
-1Be used in 300 ℃ before the reaction with the mixture process 48h of air and steam, then be down to 258 ℃ and react, acrolein conversion rate is about 99.5%, acrylic acid yield about 97.5%.
Comparative Examples 1
Method for preparing catalyst is with embodiment 1, and reaction condition is with embodiment 1, and just catalyst directly reacts without any processing before reaction, at 273 ℃ of lower acrolein conversion rate 91.2%, acrylic acid yield 86.8%.
Comparative Examples 2
Method for preparing catalyst is with implementing 2, and reaction condition is with implementing 2, and just catalyst directly reacts without any processing before reaction, at 277 ℃ of lower acrolein conversion rate 98.1%, acrylic acid yield 94.8%.
Comparative Examples 3
Method for preparing catalyst is with embodiment 3, and reaction condition is with implementing 3, and just catalyst directly reacts without any processing before reaction, at 264 ℃ of lower acrolein conversion rate 99.1%, acrylic acid yield 94.4%.
Claims (4)
1. the preparation method of a prepared by acrolein oxidation acrylic acid catalyst, it is characterized in that: catalyst is by Mo
12V
aCu
bW
cX
dY
eO
f/ Z forms, X is Nb, Sb, Te, Ce, at least a among La, Nd, Sm, Cs, the Ge, Y is at least a among Mg, Ca, Sr, the Ba, the scope of a is 1～10, the scope of b is 0～6, the scope of c is that the scope of 0～7, d is that the scope of 0～4, e is 0～5, f is by the determined numerical value of the oxidation state of component, and Z is the simple substance silica flour; Preformed catalyst in the gaseous mixture of oxygen or oxygen and inert gas, roasting 1～24h under 350～410 ℃ condition; Before the roasting rear catalyst reaction again with in the gaseous mixture of arbitrary ratio air and steam in 260-390 ℃ of lower processing 3-60h; The preparation method of preformed catalyst is, (a) with Mo, V and the W source A solution that gets soluble in water under 70～100 ℃ of conditions, with Cu, X and the Y source B solution that gets soluble in water under 60～80 ℃ of conditions, under 40～80 ℃ of conditions, B solution poured in the A solution to get into C solution, direct adding Z component mixes and obtains D solution in the solution, and D solution drying is obtained catalyst powder; Perhaps first C solution drying is obtained powder, again this powder and Z component are mixed to get catalyst powder; (b) add in the catalyst powder and be selected from one or more shaping assistants among water, Ludox, glycerine, the cellulose and be selected from a kind of strength improving agent among ceramic fibre, the inorganic crystal whisker, be shaped to spherical, solid or the hollow cylindrical particle, the shaping assistant addition is 0.01 % by weight-25 % by weight of catalyst powder weight, and strength improving agent addition is 0.01 % by weight-15 % by weight of catalyst powder weight.
2. method according to claim 1, it is characterized in that the employing of Mo source molybdic acid, ammonium paramolybdate or molybdenum oxide, ammonium metavanadate, vanadium oxide or oxalic acid vanadyl are adopted in the V source, wolframic acid, ammonium paratungstate or ammonium metatungstate are adopted in the W source, copper nitrate, Schweinfurt green or cupric oxalate are adopted in the Cu source, and X and Y source adopt corresponding oxide maybe can be decomposed into salt or the hydroxide of oxide.
3. method according to claim 1 is characterized in that D solution drying or C solution drying are to carry out the static state drying under 90～200 ℃ of conditions or carry out spray-drying under 280～350 ℃ of inlet temperatures, 130～160 ℃ of conditions of outlet temperature.
4. the application of the catalyst for preparing of method according to claim 1, it is characterized in that it is reaction in the presence of oxygen that acrolein oxidation prepares acrylic acid, the percent by volume of unstripped gas consists of methacrylaldehyde 2～14%, oxygen 0.5～25%, steam 1～30%, unreacted propylene and other organic compound 1.3%～1.5%, all the other are nitrogen, reaction temperature is 200～300 ℃, and reaction pressure is normal pressure～0.02Mpa, and air speed is 900～8000h
-1
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| CN102658120B (en) * | 2012-05-02 | 2014-04-09 | 国电科学技术研究院 | Preparation method of SCR (Selective Catalytic Reduction) catalyst |
| CN103721756B (en) * | 2012-10-12 | 2015-10-28 | 上海华谊丙烯酸有限公司 | Catalyst carrier and preparation method thereof, composite oxide catalysts |
| CN103041830A (en) * | 2012-12-26 | 2013-04-17 | 新兴能源科技有限公司 | Method for preparing acrylic acid catalyst from propylene by one-step oxidation method |
| CN104646014B (en) * | 2013-11-18 | 2017-02-22 | 上海华谊新材料有限公司 | Modified composite oxide catalyst and modification method |
| CN106881128B (en) * | 2015-12-15 | 2019-12-31 | 上海华谊新材料有限公司 | Heteropolyacid salt catalyst, preparation method and application thereof |
| CN106881101B (en) * | 2015-12-15 | 2020-06-23 | 上海华谊新材料有限公司 | Composite oxide catalyst, preparation method and application thereof |
| CN112439442B (en) * | 2019-09-05 | 2023-08-11 | 中石油吉林化工工程有限公司 | Preparation method of catalyst for preparing acrolein by propylene oxidation |
| CN111138266B (en) * | 2019-11-18 | 2023-07-14 | 中国寰球工程有限公司 | Method and device for preparing acrylic acid or methacrylic acid |
| CN111659408A (en) * | 2020-04-23 | 2020-09-15 | 宜兴市申生催化剂有限公司 | Preparation method of catalyst for preparing acrylic acid by acrolein oxidation |
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| JP3972718B2 (en) * | 2002-04-16 | 2007-09-05 | 住友化学株式会社 | Method for regenerating catalyst for methacrylic acid production |
| CN100417446C (en) * | 2006-03-29 | 2008-09-10 | 上海华谊丙烯酸有限公司 | Forming method of methacrylic acid catalyst synthesized by selective oxidation of methylacrolein |
| CN101507927B (en) * | 2009-02-10 | 2011-12-21 | 上海华谊丙烯酸有限公司 | Preparation method of composite oxides catalyst and use thereof in acrylic acid synthesizing process |
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