CN103877987A - Catalyst for acrylic acid and preparation method thereof - Google Patents

Catalyst for acrylic acid and preparation method thereof Download PDF

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CN103877987A
CN103877987A CN201210553150.6A CN201210553150A CN103877987A CN 103877987 A CN103877987 A CN 103877987A CN 201210553150 A CN201210553150 A CN 201210553150A CN 103877987 A CN103877987 A CN 103877987A
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CN103877987B (en
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徐文杰
杨斌
缪晓春
奚美珍
汪国军
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The invention relates to a catalyst for acrylic acid and a preparation method thereof, and mainly solves the problems that a catalyst is relatively low in activity and selectivity in the prior art. The catalyst comprises the active component represented by Mo12VaCubWcXdYeZfOg, wherein X represents at least one element of Cr, Mn and Sb, Y is at least one element selected from Fe, Bi, Co, Ni, Ge, Ga, Nb, Ce, La, Zr and Sr, and Z is at least one element selected from alkali metals or alkaline earth metals. The active component is obtained by adding an aqueous dispersion containing compounds of Mo, Cu, W, X, Y and Z into a pre-prepared active phase VMo3O11 powder, stirring for 1-24 h and performing drying and pre-roasting. The technical scheme relatively well solves the problems and is applicable to industrial production of acrylic acid.

Description

Acrylic acid Catalysts and its preparation method
Technical field
The present invention relates to acrylic acid Catalysts and its preparation method.
Background technology
Acrylic acid (CH 2=CH-COOH) be the simplest unsaturated carboxylic acid, it is important organic synthesis raw material and synthetic resin monomer.Great majority are in order to manufacture the esters of acrylic acids such as methyl acrylate, ethyl ester, butyl ester, hydroxyl ethyl ester, and its polymer is for the synthesis of industrial departments such as resin, synthetic fibers, super absorbent resin, building materials, coating.
Acrylic acid and series of products thereof, be mainly its ester class, in recent years developed rapidly, and 2010, acrylicacidandesters class whole world total output exceeded 5,000,000 tons, and process units mainly concentrates on the U.S., Europe, Japan and Chinese.Industrial production acrylic acid large-scale plant in the whole world all adopts propylene oxidation technology, and this technology has had the history of decades, and a large amount of technological development is gradually improved its production technology.
Up to now, many patent authorizings for produce the relevant invention of catalyst of acrylic acid method from methacrylaldehyde, wherein great majority are the catalyst that contain molybdenum-vanadium (Mo-V), as Chinese patent CN 1070468C, CN 1031488A, CN 1146438A, CN 100378058C, CN 1031050C, CN 1169619C, CN 1583261A and CN 1146439A etc., the described catalyst of these patents, its preparation method mostly is many metallic compounds and makes solution under solvent or water existence, add again insoluble oxide in heating and under stirring, evaporate dry, then calcining, the preparation method of pulverizing and moulding.And element composition differs greatly, catalyst principal component as disclosed in Chinese patent CN 1169619C is molybdenum, vanadium and copper, add again necessary tellurium, think that tellurium can make active phase oxidation molybdenum and the molybdic acid copper of this catalyst more stable, can delay catalyst and cause inactivation because Mo runs off; The disclosed catalyst of Chinese patent CN 1583261A be by
Figure 2012105531506100002DEST_PATH_IMAGE001
molybdenum, vanadium, copper are main active component,
Figure 190182DEST_PATH_IMAGE002
requisite at least by the stable component of titanium and antimony and
Figure 2012105531506100002DEST_PATH_IMAGE003
the complex chemical compound of nickel, iron, silicon, aluminium, alkali metal alkaline earth metal composition; Its basic composition of the disclosed catalyst of Chinese patent CN 1050779C comprises molybdenum, vanadium, tungsten, the copper and mickel element of oxide form; The disclosed catalyst of Chinese patent CN 1146439A contains molybdenum, vanadium, copper and contains one or more elements in elemental tungsten, niobium, tantalum, chromium and cerium, and contains copper, molybdenum and at least one and be selected from the oxo metal oxide of the HT molybdic acid steel structure type of element in elemental tungsten, vanadium, niobium and tantalum.
And point out VMo in document Applied Catalysis A:General 157 (1997) 363 3o 11most important active phase in the reaction of prepared by acrolein oxidation acrylic acid, V in this reaction 4+be conducive to stablize intermediate product acrylates, be conducive to add fast response rate determining step rapid, VMo 3o 11in V 4+content is 98%, far above other Mo-V oxides.Its acrolein conversion rate is up to 97%, and acrylic acid is selectively up to 92%, and under suitable reaction condition, has good stability, therefore acquisition VMo as much as possible in catalyst how 3o 11both be conducive to improve the performance of catalyst, be also conducive to the lifting of its stability, and under the effect of other auxiliary agents, the conversion ratio of catalyst and the selective space that also has further raising.
Summary of the invention
One of technical problem to be solved by this invention is to produce at acrolein oxidation the bad technical problem of catalyst stability existing in acrylic acid reaction in present technology, and a kind of catalyst is provided.This catalyst is produced acrylic acid reaction for acrolein oxidation, has acrylic acid yield high, the feature of good stability.
Two of technical problem to be solved by this invention is to provide the preparation method of the described catalyst of one of above-mentioned technical problem.
Three of technical problem to be solved by this invention is to provide a kind of method for producing propenoic acid that adopts the described catalyst of one of above-mentioned technical problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of catalyst, its active component formation is represented by following formula (I):
Mo 12V aCu bW cX dY eZ fO g (I)
Wherein Mo, V, Cu, W and O represent molybdenum, vanadium, copper, tungsten and oxygen; X represents at least one element in Cr, Mn, Sb; Y be selected from Fe, Bi, Co, Ni,, at least one element in Ge, Ga, Nb, Ce, La, Zr, Sr; Z is at least one element being selected from alkali metal or alkaline-earth metal; A, b, c, d, e, f and g represent their atomic ratios of element separately, atomic ratio based on Mo element is 12, the span of a is 0.5～4.0, the span of b is that the span that the span of 0.1～5.0, c is 0～5.0, d is 0～5.0, the span of e is 0～5.0, the span of f is that 0～1.0, g is the number that meets the total valent required oxygen atom of other element, and described active component is by previously prepared good active phase VMo 3o 11in powder, add the aqueous dispersion of the compound that contains Mo, Cu, W, X, Y and Z, stir 1～24 hour, obtain through super-dry and roasting, wherein 150～400 DEG C of pre-calcination temperatures, the time of roasting is 0.5～24 hour, active phase VMo 3o 11the average grain diameter of powder is 50～400 microns.
In technique scheme, described active phase VMo 3o 11the average grain diameter of powder is preferably 100～200 microns; Most preferably Sb of X in technique scheme.
In technique scheme, described catalyst can not adopt carrier, but described catalyst preferably includes and is selected from SiO 2, Al 2o 3and TiO 2in at least one carrier, more preferably the mass fraction scope of carrier is 5%～65%; The shape of described catalyst is preferably Raschig ring, and more preferably the external diameter of Raschig ring is 4-7mm, and internal diameter is 1.5-3mm.
For solve the problems of the technologies described above two, technical scheme of the present invention is as follows: the preparation method of the described catalyst of one of above-mentioned technical problem, comprises the following steps: (a) active phase VMo 3o 11in powder, add the aqueous dispersion of the compound that contains aequum Mo, Cu, W, X, Y and Z, stir 1～24 hour, obtain active component (I) through super-dry and preroast, wherein 150～400 DEG C of pre-calcination temperatures, the time of roasting is 0.5～24 hour; (b) by described active component (I), described carrier, be selected from least one organic polymer binding agent of Span80, sesbania powder or polyethylene glycol and be selected from hydroxypropyl cellulose or methylcellulose at least one cellulose derivative pore creating material together mediate and moulding, within 0.5～24 hour, obtain described catalyst through super-dry with 350～600 DEG C of roastings.
In technique scheme, described organic binder bond addition preferably accounts for the 0-15% of added catalyst weight; Described cellulose derivative weight average molecular weight range preferably 10,000 to 300,000, preferably addition accounts for the 0-15% of added active component (I) weight.
For solve the problems of the technologies described above three, technical scheme of the present invention is as follows: method for producing propenoic acid, under the described catalyst of one of above-mentioned technical problem exists, 240～350 DEG C of reaction temperatures, consist of methacrylaldehyde in volume ratio reaction raw materials: air: water vapour=1:2.5 ~ 5:1 ~ 3, reaction raw materials volume space velocity is 1000～1600 hours -1.
The preparation method of catalyst of the present invention is with commonsense method difference: in catalyst, most important activity is by previously prepared good VMo mutually 3o 11powder joins in the aqueous dispersion of the aqueous solution that contains other active components or compound, stirs after a period of time, and drying and preroast obtain active phase VMo 3o 11finely disseminated mixture, in order to obtain the active phase constituent of maximum level.
The VMo preparing according to following condition according to document Applied Catalysis A:General 157 (1997) 363 3o 11powder all can be used for the present invention, its preparation method is: the ammonium molybdate and the ammonium metavanadate that are 3:1 by Mo:V mol ratio are dissolved in the water, add again taking ethylenediamine: the mol ratio of V, as the ethylenediamine of 2:1 ~ 6:1 metering, stirs 1～24 hour, obtains active phase VMo through super-dry, roasting with after pulverizing and sieving 3o 11powder, wherein 200～400 DEG C of sintering temperatures, roasting time is 0.5～24 hour, average grain diameter is 50～400 microns.
In the present invention, the drying means of slurry is not particularly limited, and conventional drying means is all suitable for, and preferably rotary evaporation is dried and sprays dry.
Using catalyst of the present invention to prepare acrylic acid for methacrylaldehyde selective oxidation, is that 260 DEG C, reaction velocity are 1400 hours in reaction temperature -1condition under, after 2000 hours, its acrolein conversion rate can reach 99.3%, acrylic acid selectively can reach 94.3%, product acrylic acid yield can reach 93.6%, has obtained good technique effect.
In the embodiment providing below, to the investigation appreciation condition of catalyst be:
Reactor: fixed bed reactors, 25.4 millimeters of internal diameters, 750 millimeters of reactor length
Catalyst filling amount: 150 grams
Reaction temperature: 240 ~ 350 DEG C
Reaction time: 2000 hours
Volume feed: methacrylaldehyde: air: water vapour=1:2.5 ~ 5:1 ~ 3
Raw material volume space velocity: 1000 ~ 1600 hours -1
Product absorbs with 0 DEG C of diluted acid, uses gas chromatographic analysis product.And calculate Carbon balance, when Carbon balance is valid data 95～105% time.
Acrolein conversion rate, product yield and be optionally defined as:
Figure 169639DEST_PATH_IMAGE004
Figure 2012105531506100002DEST_PATH_IMAGE005
Figure 74010DEST_PATH_IMAGE006
Below by embodiment, the present invention is further elaborated:
Detailed description of the invention
comparative example 1
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 1000ml, by 200 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o), 34.2 grams of copper nitrate (Cu (NO 3) 23H 2o), 32.9 grams of ammonium metavanadate (NH 4vO 3) and 30.6 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring.In mixer B, in 200ml deionized water, add the manganese nitrate aqueous solution that 10 grams of concentration are 50wt% (Mn (NO 3) 2), 19.3 grams of ferric nitrate (Fe (NO 3) 39H 2o) and 0.64 gram of potassium hydroxide, and add batching to fill with in A obtained aqueous dispersion, and at 80 DEG C, stir 2 hours, form catalyst pulp, after rotary evaporation, obtain powder.
Again the powder of acquisition is obtained to active component through 250 DEG C of preroasts after 1 hour, from the active component (I) obtaining, take out 200 grams for moulding, wherein add 10 grams of methylcellulose (weight average molecular weight 20000), 44.4 grams of Ludox (SiO 2content 50wt%), 10 grams of deionized waters and 30 grams of Span80, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, then roasting obtains catalyst finished product for 2 hours, sintering temperature is 400 DEG C, and the composition of catalyst and main preparation condition are listed in to table 1, and reaction appraisal result is listed in to table 2.
comparative example 2
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 1000ml, by 200 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o), 34.2 grams of copper nitrate (Cu (NO 3) 23H 2o), 32.9 grams of ammonium metavanadate (NH 4vO 3) and 30.6 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring, continue to add the manganese nitrate aqueous solution that 10 grams of concentration are 50wt% (Mn (NO 3) 2), 19.3 grams of ferric nitrate (Fe (NO 3) 39H 2o) and 0.64 gram of potassium hydroxide, and at 80 DEG C, stir 2 hours, form catalyst pulp, after spraying is dry, obtain powder, spraying drying condition is: 250 DEG C of inlet temperatures, 120 DEG C of outlet temperatures, atomizing disk rotating speed 20000rpm/min.
Again the powder of acquisition is obtained to active component through 250 DEG C of preroasts after 1 hour, from the active component obtaining, take out 200 grams for moulding, wherein add 10 grams of methylcellulose (weight average molecular weight 20000), 44.4 grams of Ludox (SiO 2content 50wt%), 10 grams of deionized waters and 30 grams of Span80, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, then roasting obtains catalyst finished product for 2 hours, sintering temperature is 400 DEG C, and the composition of catalyst and main preparation condition are listed in to table 1, and reaction appraisal result is listed in to table 2.
comparative example 3
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 1000ml, by 200 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o), 34.2 grams of copper nitrate (Cu (NO 3) 23H 2o), 32.9 grams of ammonium metavanadate (NH 4vO 3) and 30.6 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring.In mixer B, in 200ml deionized water, add 4.2 grams of antimony oxides, 19.3 grams of ferric nitrate (Fe (NO 3) 39H 2o) and 0.64 gram of potassium hydroxide, and add batching to fill with in A obtained aqueous dispersion, and at 80 DEG C, stir 2 hours, form catalyst pulp, after rotary evaporation, obtain powder.
Again the powder of acquisition is obtained to active component through 250 DEG C of preroasts after 1 hour, from the active component obtaining, take out 200 grams for moulding, wherein add 10 grams of methylcellulose (weight average molecular weight 20000), 44.4 grams of Ludox (SiO 2content 50wt%), 10 grams of deionized waters and 30 grams of Span80, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, then roasting obtains catalyst finished product for 2 hours, sintering temperature is 400 DEG C, and the composition of catalyst and main preparation condition are listed in to table 1, and reaction appraisal result is listed in to table 2.
comparative example 4
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 1000ml, by 200 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o), 34.2 grams of copper nitrate (Cu (NO 3) 23H 2o), 32.9 grams of ammonium metavanadate (NH 4vO 3) and 30.6 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring, continuation will add 4.2 grams of antimony oxides, 19.3 grams of ferric nitrate (Fe (NO 3) 39H 2o) and 0.64 gram of potassium hydroxide, and at 80 DEG C, stir 2 hours, form catalyst pulp, after spraying is dry, obtain powder.
Again the powder of acquisition is obtained to active component through 250 DEG C of preroasts after 1 hour, from the active component obtaining, take out 200 grams for moulding, wherein add 10 grams of methylcellulose (weight average molecular weight 20000), 44.4 grams of Ludox (SiO 2content 50wt%), 10 grams of deionized waters and 30 grams of Span80, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm,, then roasting obtains catalyst finished product for 2 hours, and sintering temperature is 400 DEG C, the composition of catalyst and main preparation condition are listed in to table 1, reaction appraisal result is listed in to table 2.
embodiment 1
Active phase VMo is described according to document Applied Catalysis A:General 157 (1997) 363 3o 11the preparation method of powder is: by 300 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o) and 69.5 grams of ammonium metavanadate (NH 4vO 3) be dissolved in the water, then add 50.5 grams of ethylenediamines, and stir lower 2 hours, after super-dry, roasting 2 hours at 300 DEG C, cooling rear pulverizing, gets powder between 100 mesh sieves and 120 mesh sieves, obtains active phase VMo 3o 11powder, its average grain diameter is 130 microns.
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 800ml, by 49.4 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o), 34.2 grams of copper nitrate (Cu (NO 3) 23H 2o), 10 grams of manganese nitrate aqueous solution (Mn (NO that concentration is 50wt% 3) 2), 19.3 grams of ferric nitrate (Fe (NO 3) 39H 2o), 0.64 gram of potassium hydroxide and 30.6 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring, and at 80 DEG C, stir 2 hours, then add 144.4 grams of above-mentioned VMo 3o 11powder, continues to stir 1h, forms catalyst pulp, obtains powder after rotary evaporation, and powder after 1 hour, is obtained to active component (I) through 250 DEG C of preroasts.
From the active component (I) obtaining, take out 200 grams for moulding, wherein add 10 grams of methylcellulose (weight average molecular weight 20000), 44.4 grams of Ludox (SiO 2content 50wt%), 10 grams of deionized waters and 30 grams of Span80, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, then roasting obtains catalyst finished product for 2 hours, sintering temperature is 400 DEG C, and the composition of catalyst and main preparation condition are listed in to table 1, and reaction appraisal result is listed in to table 2.
embodiment 2
Active phase VMo is described according to document Applied Catalysis A:General 157 (1997) 363 3o 11the preparation method of powder is: by 300 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o) and 69.5 grams of ammonium metavanadate (NH 4vO 3) be dissolved in the water, then add 50.5 grams of ethylenediamines, and stir lower 2 hours, after super-dry, roasting 2 hours at 300 DEG C, cooling rear pulverizing, gets powder between 160 mesh sieves and 200 mesh sieves, obtains active phase VMo 3o 11powder, its average grain diameter is 85 microns.
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 800ml, by 49.4 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o), 34.2 grams of copper nitrate (Cu (NO 3) 23H 2o), 10 grams of manganese nitrate aqueous solution (Mn (NO that concentration is 50wt% 3) 2), 19.3 grams of ferric nitrate (Fe (NO 3) 39H 2o), 0.64 gram of potassium hydroxide and 30.6 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring, and at 80 DEG C, stir 2 hours, then add 144.4 grams of above-mentioned VMo 3o 11powder, continues to stir 1h, forms catalyst pulp, obtains powder after rotary evaporation, and powder after 1 hour, is obtained to active component (I) through 250 DEG C of preroasts.
From the active component (I) obtaining, take out 200 grams for moulding, wherein add 10 grams of methylcellulose (weight average molecular weight 20000), 44.4 grams of Ludox (SiO 2content 50wt%), 10 grams of deionized waters and 30 grams of Span80, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, then roasting obtains catalyst finished product for 2 hours, sintering temperature is 400 DEG C, and the composition of catalyst and main preparation condition are listed in to table 1, and reaction appraisal result is listed in to table 2.
embodiment 3
Active phase VMo is described according to document Applied Catalysis A:General 157 (1997) 363 3o 11the preparation method of powder is: by 300 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o) and 69.5 grams of ammonium metavanadate (NH 4vO 3) be dissolved in the water, then add 50.5 grams of ethylenediamines, and stir lower 2 hours, after super-dry, roasting 2 hours at 300 DEG C, cooling rear pulverizing, gets powder between 60 mesh sieves and 80 mesh sieves, obtains active phase VMo 3o 11powder, its average grain diameter is 200 microns.
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 800ml, by 49.4 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o), 34.2 grams of copper nitrate (Cu (NO 3) 23H 2o), 10 grams of manganese nitrate aqueous solution (Mn (NO that concentration is 50wt% 3) 2), 19.3 grams of ferric nitrate (Fe (NO 3) 39H 2o), 0.64 gram of potassium hydroxide and 30.6 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring, and at 80 DEG C, stir 2 hours, then add 144.4 grams of above-mentioned VMo 3o 11powder, continues to stir 1h, forms catalyst pulp, obtains powder after rotary evaporation, and powder after 1 hour, is obtained to active component (I) through 250 DEG C of preroasts.
From the active component (I) obtaining, take out 200 grams for moulding, wherein add 10 grams of methylcellulose (weight average molecular weight 20000), 44.4 grams of Ludox (SiO 2content 50wt%), 10 grams of deionized waters and 30 grams of Span80, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, then roasting obtains catalyst finished product for 2 hours, sintering temperature is 400 DEG C, and the composition of catalyst and main preparation condition are listed in to table 1, and reaction appraisal result is listed in to table 2.
embodiment 4
Active phase VMo is described according to document Applied Catalysis A:General 157 (1997) 363 3o 11the preparation method of powder is: by 300 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o) and 69.5 grams of ammonium metavanadate (NH 4vO 3) be dissolved in the water, then add 50.5 grams of ethylenediamines, and stir lower 2 hours, after super-dry, roasting 2 hours at 300 DEG C, cooling rear pulverizing, gets powder between 40 mesh sieves and 50 mesh sieves, obtains active phase VMo 3o 11powder, its average grain diameter is 325 microns.
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 800ml, by 49.4 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o), 34.2 grams of copper nitrate (Cu (NO 3) 23H 2o), 10 grams of manganese nitrate aqueous solution (Mn (NO that concentration is 50wt% 3) 2), 19.3 grams of ferric nitrate (Fe (NO 3) 39H 2o), 0.64 gram of potassium hydroxide and 30.6 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring, and at 80 DEG C, stir 2 hours, then add 144.4 grams of above-mentioned VMo 3o 11powder, continues to stir 1h, forms catalyst pulp, obtains powder after rotary evaporation, and powder after 1 hour, is obtained to active component (I) through 250 DEG C of preroasts.
From the active component (I) obtaining, take out 200 grams for moulding, wherein add 10 grams of methylcellulose (weight average molecular weight 20000), 44.4 grams of Ludox (SiO 2content 50wt%), 10 grams of deionized waters and 30 grams of Span80, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, then roasting obtains catalyst finished product for 2 hours, sintering temperature is 400 DEG C, and the composition of catalyst and main preparation condition are listed in to table 1, and reaction appraisal result is listed in to table 2.
embodiment 5
Active phase VMo is described according to document Applied Catalysis A:General 157 (1997) 363 3o 11the preparation method of powder is: by 300 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o) and 69.5 grams of ammonium metavanadate (NH 4vO 3) be dissolved in the water, then add 50.5 grams of ethylenediamines, and stir lower 2 hours, after super-dry, roasting 2 hours at 300 DEG C, cooling rear pulverizing, gets powder between 30 mesh sieves and 40 mesh sieves, obtains active phase VMo 3o 11powder, its average grain diameter is 400 microns.
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 800ml, by 49.4 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o), 34.2 grams of copper nitrate (Cu (NO 3) 23H 2o), 10 grams of manganese nitrate aqueous solution (Mn (NO that concentration is 50wt% 3) 2), 19.3 grams of ferric nitrate (Fe (NO 3) 39H 2o), 0.64 gram of potassium hydroxide and 30.6 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring, and at 80 DEG C, stir 2 hours, then add 144.4 grams of above-mentioned VMo 3o 11powder, continues to stir 1h, forms catalyst pulp, obtains powder after rotary evaporation, and powder after 1 hour, is obtained to active component (I) through 250 DEG C of preroasts.
From the active component (I) obtaining, take out 200 grams for moulding, wherein add 10 grams of methylcellulose (weight average molecular weight 20000), 44.4 grams of Ludox (SiO 2content 50wt%), 10 grams of deionized waters and 30 grams of Span80, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, then roasting obtains catalyst finished product for 2 hours, sintering temperature is 400 DEG C, and the composition of catalyst and main preparation condition are listed in to table 1, and reaction appraisal result is listed in to table 2.
embodiment 6
Active phase VMo is described according to document Applied Catalysis A:General 157 (1997) 363 3o 11the preparation method of powder is: by 300 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o) and 69.5 grams of ammonium metavanadate (NH 4vO 3) be dissolved in the water, then add 50.5 grams of ethylenediamines, and stir lower 2 hours, after super-dry, roasting 2 hours at 300 DEG C, cooling rear pulverizing, gets powder between 60 mesh sieves and 80 mesh sieves, obtains active phase VMo 3o 11powder, its average grain diameter is 200 microns.
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 800ml, by 49.4 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o), 34.2 grams of copper nitrate (Cu (NO 3) 23H 2o), 2.8 grams of chromium trioxides, 19.3 grams of ferric nitrate (Fe (NO 3) 39H 2o), 0.64 gram of potassium hydroxide and 30.6 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring, and at 80 DEG C, stir 2 hours, then add 144.4 grams of above-mentioned VMo 3o 11powder, continues to stir 1h, forms catalyst pulp, obtains powder after rotary evaporation, and powder after 1 hour, is obtained to active component (I) through 250 DEG C of preroasts.
From the active component (I) obtaining, take out 200 grams for moulding, wherein add 10 grams of methylcellulose (weight average molecular weight 20000), 44.4 grams of Ludox (SiO 2content 50wt%), 10 grams of deionized waters and 30 grams of Span80, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, then roasting obtains catalyst finished product for 2 hours, sintering temperature is 400 DEG C, and the composition of catalyst and main preparation condition are listed in to table 1, and reaction appraisal result is listed in to table 2.
embodiment 7
Active phase VMo is described according to document Applied Catalysis A:General 157 (1997) 363 3o 11the preparation method of powder is: by 300 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o) and 69.5 grams of ammonium metavanadate (NH 4vO 3) be dissolved in the water, then add 50.5 grams of ethylenediamines, and stir lower 2 hours, after super-dry, roasting 2 hours at 300 DEG C, cooling rear pulverizing, gets powder between 100 mesh sieves and 120 mesh sieves, obtains active phase VMo 3o 11powder, its average grain diameter is 130 microns.
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 800ml, by 49.4 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o), 34.2 grams of copper nitrate (Cu (NO 3) 23H 2o), 4.2 grams of antimony oxides, 19.3 grams of ferric nitrate (Fe (NO 3) 39H 2o), 0.64 gram of potassium hydroxide and 30.6 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring, and at 80 DEG C, stir 2 hours, then add 144.4 grams of above-mentioned VMo 3o 11powder, continues to stir 1h, forms catalyst pulp, obtains powder after rotary evaporation, and powder after 1 hour, is obtained to active component (I) through 250 DEG C of preroasts.
From the active component (I) obtaining, take out 200 grams for moulding, wherein add 10 grams of methylcellulose (weight average molecular weight 20000), 44.4 grams of Ludox (SiO 2content 50wt%), 10 grams of deionized waters and 30 grams of Span80, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, then roasting obtains catalyst finished product for 2 hours, sintering temperature is 400 DEG C, and the composition of catalyst and main preparation condition are listed in to table 1, and reaction appraisal result is listed in to table 2.
embodiment 8
Active phase VMo is described according to document Applied Catalysis A:General 157 (1997) 363 3o 11the preparation method of powder is: by 300 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o) and 69.5 grams of ammonium metavanadate (NH 4vO 3) be dissolved in the water, then add 50.5 grams of ethylenediamines, and stir lower 2 hours, after super-dry, roasting 2 hours at 300 DEG C, cooling rear pulverizing, gets powder between 100 mesh sieves and 120 mesh sieves, obtains active phase VMo 3o 11powder, its average grain diameter is 130 microns.
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 800ml, by 49.4 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o), 34.2 grams of copper nitrate (Cu (NO 3) 23H 2o), 7.0 grams of antimony oxides, 19.3 grams of ferric nitrate (Fe (NO 3) 39H 2o), 0.64 gram of potassium hydroxide and 30.6 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring, and at 80 DEG C, stir 2 hours, then add 144.4 grams of above-mentioned VMo 3o 11powder, continues to stir 1h, forms catalyst pulp, obtains powder after rotary evaporation, and powder after 1 hour, is obtained to active component (I) through 250 DEG C of preroasts.
From the active component (I) obtaining, take out 200 grams for moulding, wherein add 10 grams of methylcellulose (weight average molecular weight 20000), 44.4 grams of Ludox (SiO 2content 50wt%), 10 grams of deionized waters and 30 grams of Span80, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, then roasting obtains catalyst finished product for 2 hours, sintering temperature is 400 DEG C, and the composition of catalyst and main preparation condition are listed in to table 1, and reaction appraisal result is listed in to table 2.
embodiment 9
Active phase VMo is described according to document Applied Catalysis A:General 157 (1997) 363 3o 11the preparation method of powder is: by 300 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o) and 69.5 grams of ammonium metavanadate (NH 4vO 3) be dissolved in the water, then add 50.5 grams of ethylenediamines, and stir lower 2 hours, after super-dry, roasting 2 hours at 300 DEG C, cooling rear pulverizing, gets powder between 100 mesh sieves and 120 mesh sieves, obtains active phase VMo 3o 11powder, its average grain diameter is 130 microns.
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 800ml, by 49.4 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o), 34.2 grams of copper nitrate (Cu (NO 3) 23H 2o), 9.7 grams of antimony oxides, 19.3 grams of ferric nitrate (Fe (NO 3) 39H 2o), 0.64 gram of potassium hydroxide and 30.6 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring, and at 80 DEG C, stir 2 hours, then add 144.4 grams of above-mentioned VMo 3o 11powder, continues to stir 1h, forms catalyst pulp, obtains powder after rotary evaporation, and powder after 1 hour, is obtained to active component (I) through 250 DEG C of preroasts.
From the active component (I) obtaining, take out 200 grams for moulding, wherein add 10 grams of methylcellulose (weight average molecular weight 20000), 44.4 grams of Ludox (SiO 2content 50wt%), 10 grams of deionized waters and 30 grams of Span80, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, then roasting obtains catalyst finished product for 2 hours, sintering temperature is 400 DEG C, and the composition of catalyst and main preparation condition are listed in to table 1, and reaction appraisal result is listed in to table 2.
embodiment 10
Active phase VMo is described according to document Applied Catalysis A:General 157 (1997) 363 3o 11the preparation method of powder is: by 300 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o) and 69.5 grams of ammonium metavanadate (NH 4vO 3) be dissolved in the water, then add 50.5 grams of ethylenediamines, and stir lower 2 hours, after super-dry, roasting 2 hours at 300 DEG C, cooling rear pulverizing, gets powder between 30 mesh sieves and 40 mesh sieves, obtains active phase VMo 3o 11powder, its average grain diameter is 400 microns.
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 800ml, 41.1 grams of copper nitrate (Cu (NO 3) 23H 2o), 42.5 grams of antimony oxide (Sb 2o 3), 70.2 grams of niobium pentaoxides, 47.0 grams of lanthanum nitrate (La (NO 3) 36H 2o), 4.77 potassium nitrate (KNO 3), 48.6 grams of zirconium nitrate (Zr (NO 3) 45H 20), 18.3 grams of cesium nitrate (CsNO 3) and 50.9 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring, and at 80 DEG C, stir 2 hours, then add 192.2 grams of above-mentioned VMo 3o 11powder, continues to stir 1h, forms catalyst pulp, obtains powder after rotary evaporation, and powder after 24 hours, is obtained to active component (I) through 150 DEG C of preroasts.
From the active component (I) obtaining, take out 200 grams for moulding, wherein add 30 grams of methylcellulose (weight average molecular weight 20000), 10 grams of deionized waters and 33.3 grams of titanium dioxide, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, and then roasting obtains catalyst finished product for 24 hours, and sintering temperature is 350 DEG C, the composition of catalyst and main preparation condition are listed in to table 1, reaction appraisal result is listed in to table 2.
embodiment 11
Active phase VMo is described according to document Applied Catalysis A:General 157 (1997) 363 3o 11the preparation method of powder is: by 300 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o) and 69.5 grams of ammonium metavanadate (NH 4vO 3) be dissolved in the water, then add 50.5 grams of ethylenediamines, and stir lower 2 hours, after super-dry, roasting 2 hours at 300 DEG C, cooling rear pulverizing, gets powder between 250 mesh sieves and 300 mesh sieves, obtains active phase VMo 3o 11powder, its average grain diameter is 50 microns.
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 800ml, by 49.4 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o), 41.1 grams of copper nitrate (Cu (NO 3) 23H 2o), 15.3 grams of antimony oxides, 104.0 grams of ferric nitrate (Fe (NO 3) 39H 2o), 58.5 grams of niobium pentaoxides, 40.0 grams of strontium nitrate (Sr (NO 3) 2), 65.6 cerous nitrates (Ce (NO 3) 36H 2o), 29.0 grams of calcium nitrate (Ca (NO 3) 24H 2o), 17.1 grams of barium nitrate (Ba (NO 3) 2), 16.5 grams of cesium nitrate (CsNO 3) and 45.8 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring, and at 80 DEG C, stir 2 hours, then add 144.4 grams of above-mentioned VMo 3o 11powder, continues to stir 1h, forms catalyst pulp, obtains powder after rotary evaporation, and powder after 0.5 hour, is obtained to active component (I) through 400 DEG C of preroasts.
From the active component (I) obtaining, take out 200 grams for moulding, wherein add 14 grams of hydroxypropyl celluloses (weight average molecular weight 150000), 133.2 grams of Ludox (SiO 2content 50wt%), 10 grams of deionized waters and 6 grams of polyethylene glycol (weight average molecular weight 6000), mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, then roasting obtains catalyst finished product for 0.5 hour, sintering temperature is 600 DEG C, and the composition of catalyst and main preparation condition are listed in to table 1, and reaction appraisal result is listed in to table 2.
embodiment 12
Active phase VMo is described according to document Applied Catalysis A:General 157 (1997) 363 3o 11the preparation method of powder is: by 300 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o) and 69.5 grams of ammonium metavanadate (NH 4vO 3) be dissolved in the water, then add 50.5 grams of ethylenediamines, and stir lower 2 hours, after super-dry, roasting 2 hours at 300 DEG C, cooling rear pulverizing, gets powder between 100 mesh sieves and 120 mesh sieves, obtains active phase VMo 3o 11powder, its average grain diameter is 130 microns.
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 800ml, 2.3 grams of copper nitrate (Cu (NO 3) 23H 2o), 69.5 grams of antimony oxides, 13.9 rubidium nitrate (RbNO 3), 205.0 grams of cerous nitrate (Ce (NO 3) 36H 2o) and 127.3 grams of ammonium tungstate ((NH 4) 6h 5[H 2(WO 4) 6]) dissolve and vigorous stirring, and at 80 DEG C, stir 2 hours, then add 192.2 grams of above-mentioned VMo 3o 11powder, continues to stir 1h, forms catalyst pulp, obtains powder after rotary evaporation, and powder after 1 hour, is obtained to active component (I) through 250 DEG C of preroasts.
From the active component (I) obtaining, take out 200 grams for moulding, wherein add 22.2 grams of Ludox (SiO 2content 50wt%), 10 grams of deionized waters and 20 grams of Span80, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, then roasting obtains catalyst finished product for 2 hours, sintering temperature is 400 DEG C, and the composition of catalyst and main preparation condition are listed in to table 1, and reaction appraisal result is listed in to table 2.
embodiment 13
Active phase VMo is described according to document Applied Catalysis A:General 157 (1997) 363 3o 11the preparation method of powder is: by 300 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o) and 69.5 grams of ammonium metavanadate (NH 4vO 3) be dissolved in the water, then add 50.5 grams of ethylenediamines, and stir lower 2 hours, after super-dry, roasting 2 hours at 300 DEG C, cooling rear pulverizing, gets powder between 100 mesh sieves and 120 mesh sieves, obtains active phase VMo 3o 11powder, its average grain diameter is 130 microns.
Fill with in A in the batching that stirring motor is housed, add 100 DEG C of deionized waters of 800ml, 175.0 grams of ammonium molybdate ((NH 4) 6mo 7o 244H 2o) and 114.0 grams of copper nitrate (Cu (NO 3) 23H 2o) dissolve also vigorous stirring, and at 80 DEG C, stir 2 hours, then add 24.0 grams of above-mentioned VMo 3o 11powder, continues to stir 1h, forms catalyst pulp, obtains powder after rotary evaporation, and powder after 1 hour, is obtained to active component (I) through 250 DEG C of preroasts.
From the active component (I) obtaining, take out 100 grams for moulding, wherein add 12 grams of methylcellulose (weight average molecular weight 300000), 57.7 grams of alundum (Al2O3)s, 86.6 grams of titanium dioxide, 10 grams of deionized waters and 7 grams of sesbania powder, mediate agent after 2 hours and go out moulding, obtaining external diameter is 5mm, internal diameter is that 1.5mm length is the Raschig ring of 5mm, then roasting obtains catalyst finished product for 2 hours, sintering temperature is 400 DEG C, the composition of catalyst and main preparation condition are listed in to table 1, reaction appraisal result is listed in to table 2.
As can be seen from Table 1 and Table 2, VMo 3o 11can obviously improve the adding of powder the conversion ratio of catalyst and selective, particularly VMo 3o 11particle diameter is in the time of 100～200 microns, and conversion ratio is best, and this can find out from comparative example 1,2 and embodiment 1～5; In the time that X is Sb, catalyst selectivity is significantly improved, and this can find out from embodiment 7～9.
Table 1, catalyst composition and preparation condition
Table 1(is continuous)
Preformed catalyst sintering temperature/time Pore creating material (wt%) Adhesive (wt%)
Comparative example 1 400℃/2h 5% methylcellulose 15% Span80
Comparative example 2 400℃/2h 5% methylcellulose 15% Span80
Comparative example 3 400℃/2h 5% methylcellulose 15% Span80
Comparative example 4 400℃/2h 5% methylcellulose 15% Span80
Embodiment 1 400℃/2h 5% methylcellulose 15% Span80
Embodiment 2 400℃/2h 5% methylcellulose 15% Span80
Embodiment 3 400℃/2h 5% methylcellulose 15% Span80
Embodiment 4 400℃/2h 5% methylcellulose 15% Span80
Embodiment 5 400℃/2h 5% methylcellulose 15% Span80
Embodiment 6 400℃/2h 5% methylcellulose 15% Span80
Embodiment 7 400℃/2h 5% methylcellulose 15% Span80
Embodiment 8 400℃/2h 5% methylcellulose 15% Span80
Embodiment 9 400℃/2h 5% methylcellulose 15% Span80
Embodiment 10 350℃/24h 15% methylcellulose 0
Embodiment 11 600℃/0.5h 7% hydroxypropyl cellulose 3% Macrogol 6000
Embodiment 12 400℃/2h 0 10% Span80
Embodiment 13 400℃/2h 12% methylcellulose 7% sesbania powder
Table 2, comparative example and embodiment investigate result
Reaction temperature Methacrylaldehyde: air: water vapour Volume space velocity Acrylic acid yield (%) Acrylic acid selective (%) Acrolein conversion rate (%)
Comparative example 1 260 1:3.2:2.1 1400 77.3 85.6 90.3
Comparative example 2 260 1:3.2:2.1 1400 78.2 88.6 88.3
Comparative example 3 260 1:3.2:2.1 1400 70.8 75.6 93.6
Comparative example 4 260 1:3.2:2.1 1400 71.9 78.6 91.5
Embodiment 1 260 1:3.2:2.1 1400 88.7 89.7 98.9
Embodiment 2 260 1:3.2:2.1 1400 85.2 89.1 95.6
Embodiment 3 260 1:3.2:2.1 1400 87.0 90.3 96.4
Embodiment 4 260 1:3.2:2.1 1400 83.2 89.4 93.1
Embodiment 5 260 1:3.2:2.1 1400 82.9 90.3 91.8
Embodiment 6 260 1:3.2:2.1 1400 86.1 88.9 96.8
Embodiment 7 260 1:3.2:2.1 1400 92.6 93.3 99.2
Embodiment 8 260 1:3.2:2.1 1400 93.6 94.3 99.3
Embodiment 9 260 1:3.2:2.1 1400 91.5 91.8 99.7
Embodiment 10 260 1:3.2:2.1 1400 91.2 92.9 98.2
Embodiment 11 260 1:3.2:2.1 1400 84.1 89.2 94.3
Embodiment 12 240 1:2.5:1 1600 82.7 91.2 90.7
Embodiment 13 320 1:5:3 1000 82.3 83.1 99.0

Claims (10)

1. a catalyst, its active component formation is represented by following formula (I):
Mo 12V aCu bW cX dY eZ fO g (I)
Wherein Mo, V, Cu, W and O represent molybdenum, vanadium, copper, tungsten and oxygen; X represents at least one element in Cr, Mn, Sb; Y be selected from Fe, Bi, Co, Ni,, at least one element in Ge, Ga, Nb, Ce, La, Zr, Sr; Z is at least one element being selected from alkali metal or alkaline-earth metal; A, b, c, d, e, f and g represent their atomic ratios of element separately, atomic ratio based on Mo element is 12, the span of a is 0.5～4.0, the span of b is that the span that the span of 0.1～5.0, c is 0～5.0, d is 0～5.0, the span of e is 0～5.0, the span of f is that 0～1.0, g is the number that meets the total valent required oxygen atom of other element, and described active component is by previously prepared good active phase VMo 3o 11in powder, add the aqueous dispersion of the compound that contains Mo, Cu, W, X, Y and Z, stir 1～24 hour, obtain through super-dry and preroast, wherein 150～400 DEG C of pre-calcination temperatures, the time of roasting is 0.5～24 hour, described active phase VMo 3o 11the average grain diameter of powder is 50～400 microns.
2. catalyst according to claim 1, is characterized in that described active phase VMo 3o 11the average grain diameter of powder is 100～200 microns.
3. catalyst according to claim 1, is characterized in that X is Sb.
4. catalyst according to claim 1, is characterized in that described catalyst comprises at least one carrier being selected from SiO2, Al2O3 and TiO2.
5. catalyst according to claim 4, is characterized in that the mass fraction scope of described carrier is 5%～65%.
6. catalyst according to claim 4, is characterized in that the Raschig ring that is shaped as of described catalyst, and external diameter is 4-7mm, and internal diameter is 1.5-3mm.
7. the preparation method of catalyst described in claim 4, comprises the following steps:
(a) active phase VMo 3o 11in powder, add the aqueous dispersion of the compound that contains aequum Mo, Cu, W, X, Y and Z, stir 1～24 hour, obtain active component (I) through super-dry and preroast, wherein 150～400 DEG C of pre-calcination temperatures, the time of roasting is 0.5～24 hour;
(b) by described active component (I), described carrier, be selected from Span80, sesbania powder or at least one organic binder bond of polyethylene glycol and be selected from hydroxypropyl cellulose or methylcellulose at least one cellulose derivative pore creating material together mediate and moulding, within 0.5～24 hour, obtain described catalyst through super-dry with 350～600 DEG C of roastings.
8. according to the preparation method of catalyst described in claims 7, it is characterized in that described organic binder bond, addition accounts for the 0-15% of added active component (I) weight.
9. according to the preparation method of catalyst described in claims 7, it is characterized in that described cellulose derivative weight average molecular weight range is 10,000 to 300,000, addition accounts for the 0-15% of added active component (I) weight.
10. method for producing propenoic acid, under catalyst as claimed in claim 4 exists, 240～350 DEG C of reaction temperatures, consists of methacrylaldehyde in volume ratio reaction raw materials: air: water vapour=1:2.5 ~ 5:1 ~ 3, reaction raw materials volume space velocity is 1000～1600 hours -1.
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CN105664961A (en) * 2014-11-20 2016-06-15 中国石油化工股份有限公司 Acrylic acid catalyst
CN106423188A (en) * 2015-08-12 2017-02-22 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method thereof
CN106423186A (en) * 2015-08-12 2017-02-22 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method thereof
CN115487817A (en) * 2021-06-18 2022-12-20 中国石油化工股份有限公司 Catalyst for acrylic acid synthesis and preparation method thereof, molded catalyst for acrylic acid synthesis and preparation method thereof, and acrylic acid synthesis method

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CN102371158A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Catalyst of acrylic acid prepared by oxidation process and its preparation method
CN102451702A (en) * 2010-10-21 2012-05-16 中国石油化工股份有限公司 Acrylic acid catalyst prepared by acrolein oxidation and preparation method thereof

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CN1130172A (en) * 1994-11-14 1996-09-04 株式会社日本触媒 Method for preparing propenoic acid
US5739392A (en) * 1994-11-14 1998-04-14 Nippon Shokubai Co., Ltd. Process for production of acrylic acid
CN102371158A (en) * 2010-08-23 2012-03-14 中国石油化工股份有限公司 Catalyst of acrylic acid prepared by oxidation process and its preparation method
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Publication number Priority date Publication date Assignee Title
CN105664961A (en) * 2014-11-20 2016-06-15 中国石油化工股份有限公司 Acrylic acid catalyst
CN106423188A (en) * 2015-08-12 2017-02-22 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method thereof
CN106423186A (en) * 2015-08-12 2017-02-22 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method thereof
CN106423188B (en) * 2015-08-12 2018-07-13 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method
CN106423186B (en) * 2015-08-12 2018-07-17 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method thereof
CN115487817A (en) * 2021-06-18 2022-12-20 中国石油化工股份有限公司 Catalyst for acrylic acid synthesis and preparation method thereof, molded catalyst for acrylic acid synthesis and preparation method thereof, and acrylic acid synthesis method
CN115487817B (en) * 2021-06-18 2024-01-26 中国石油化工股份有限公司 Catalyst for acrylic acid synthesis, preparation method thereof, molding catalyst for acrylic acid synthesis, preparation method thereof and acrylic acid synthesis method

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