CN105080558A - Catalyst for acrylic acid synthesis and preparation method thereof - Google Patents
Catalyst for acrylic acid synthesis and preparation method thereof Download PDFInfo
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- CN105080558A CN105080558A CN201410203026.6A CN201410203026A CN105080558A CN 105080558 A CN105080558 A CN 105080558A CN 201410203026 A CN201410203026 A CN 201410203026A CN 105080558 A CN105080558 A CN 105080558A
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Abstract
The invention relates to a catalyst for acrylic acid synthesis, preparation method thereof, and a synthesis method for acrylic acid, mainly solves problems of low activity and selectivity of catalysts in the prior art. The invention adopts catalyst that is used in acrylic acid synthesis by acrolein oxidation and includes following ingredients by weight: A: 20-60 parts of hydrotalcite-like carrier, B: 5-40 parts of active ingredients Mo12VaCuWcXdYeZfOg carried on the A, and C: 5-40 parts of VMo2O8, wherein x represents at least one element of Cr, Mn, Sb; Y represents at least one element selected from Fe, Bi, Co, Ge, Ga, Nb, Ce, La, Zr, Sr; Z represents at least one element selected from alkali metals or alkaline earth metals. The acrylic acid catalyst solves the problem and can be used in industrial production for acrylic acid.
Description
Technical field
The present invention relates to catalyst, preparation method and the acrylic acid synthetic method of synthesizing for acrylic acid.
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.Acrylic acid is mainly used in synthesizing senior water-absorbing resins and water treatment agent etc., part acrylic acid is used for esterification in order to manufacture the esters of acrylic acids such as methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-EHA, and acrylate polymer is mainly used in the fields such as adhesive, coating, weaving, plastics, leather, papermaking.
Acrylic acid and series of products thereof, in recent years developed rapidly, 2011, acrylicacidandesters class whole world total output has reached 537.9 ten thousand t/a, 4.3% is increased compared with 515.6 ten thousand t/a in the end of the year in 2010, current acrylic acid process units mainly concentrates on the U.S., Europe, Japan and Chinese, and wherein China is the country that acrylic acid production capacity is with fastest developing speed in recent years, and expecting the end of the year in 2012 China will become the maximum country of global acrylic acid production capacity.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 makes its production technology be gradually improved.
Up to now, many patent authorizings is for the relevant invention of the catalyst of producing acrylic acid method from methacrylaldehyde, wherein great majority are the catalyst containing molybdenum-vanadium (Mo-V), as Chinese patent CN1070468C, CN1031488A, CN1146438A, CN100378058C, CN1031050C, CN1169619C, CN1583261A and CN1146439A etc., catalyst described by these patents, its preparation method mostly is many metallic compounds and makes solution under solvent or water exists, adding insoluble oxide again evaporates dry under heating and stirring, then calcine, pulverize and shaping preparation method.And disclosed element composition described in patent differs greatly at present, disclosed in Chinese patent CN1169619C, catalyst principal component is molybdenum, vanadium and copper, add necessary tellurium again, think tellurium can make the active phase oxidation molybdenum of this catalyst and copper molybdate more stable, can delay catalyst because of Mo run off cause inactivation; Catalyst disclosed in Chinese patent CN1583261A is main active component by 1. molybdenum, vanadium, copper, 2. requisite at least by stable component and the 3. complex chemical compound that forms of nickel, iron, silicon, aluminium, alkali metal alkaline earth metal of titanium and antimony; Its basic composition of catalyst disclosed in Chinese patent CN1050779C comprises molybdenum, vanadium, tungsten, the copper and mickel element of oxide form; Catalyst disclosed in Chinese patent CN1146439A contains molybdenum, vanadium, copper also containing one or more elements in elemental tungsten, niobium, tantalum, chromium and cerium, and is selected from the oxo metal oxide of the HT copper molybdate structure type of element in elemental tungsten, vanadium, niobium and tantalum containing copper, molybdenum and at least one.
But low, the acrylic acid yield of the catalyst activity of prior art is low.
Summary of the invention
One of technical problem to be solved by this invention is the existing problem that acrolein conversion rate is low and acrylic acid yield is low of producing existence in acrylic acid reaction in the art at acrolein oxidation, is provided for the catalyst of acrylic acid synthesis.This catalyst is used for acrolein oxidation synthesizing propylene acid reaction, has the advantages that acrolein conversion rate is high and acrylic acid yield is high.
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 the synthesis of conjugated carboxylic alkeneacid adopting one of above-mentioned technical problem described catalyst.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: acrylic acid catalyst, comprises following component with weight parts:
The houghite carrier of 20-60 part; Carry the active component Mo of 5-40 part thereon
12v
acu
bw
cx
dy
ez
fo
gwith 5-40 part help active component VMo
2o
8;
Wherein houghite carrier structure formula is M
2+ 1-Qm
3+ q(OH)
2(A
n-)
q/nmH
2the non-stoichiometric compound that O represents, M
2+represent divalent metal, M
3+represent trivalent metal, A
n-represent anion;
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 is at least one element be selected from Fe, Bi, Co, Ni, Ge, Ga, Nb, Ce, La, Zr, Sr; Z is at least one element be selected from alkali metal or alkaline-earth metal; A, b, c, d, e, f and g represent the atomic ratio of their elements separately, atomic ratio based on Mo element is 12, the span of a is 0.5 ~ 4.0, the span of b is 0.1 ~ 5.0, the span of the span of c to be the span of 0 ~ 5.0, d be 0 ~ 5.0, e is 0 ~ 5.0, the span of f is 0 ~ 1.0, g is the number meeting the total valent required oxygen atom of other element; Q is 0.3 ~ 0.9, n=1 or 2, m=0 ~ 2.A
n-preferably from Cl
-, NO
3 -, CO
3 2-, SO
4 2-in at least one.M
2+preferably from Co
2+, Mg
2+, Ni
2+, Cu
2+, Zn
2+, Ca
2+and Fe
2+in at least one.M
3+preferably from Al
3+, Fe
3+and Mn
3+in at least one.
For solve the problems of the technologies described above two, technical scheme of the present invention is as follows: the preparation method of catalyst described in the technical scheme of one of above-mentioned technical problem, comprises the following steps:
A the compound of following elements is distributed in water and obtains hybrid dispersions by (), then dry and roasting obtains described active component: Mo, V, Cu, W, X, Y and Z;
B () is by the powder of the active component obtained in houghite carrier, step (a), the powder helping active component and binding agent and pore creating material mixing, shaping, dry and roasting obtains described catalyst.
In technique scheme, described in help the synthetic method of active component to be preferably as follows: the ammonium molybdate of required ratio and ammonium metavanadate are dissolved in required water, then add ethylenediamine, stir lower aging 1 ~ 24 hour, through super-dry, roasting and obtaining.The mol ratio of wherein ethylenediamine: V is preferably 2:1 ~ 6:1.The time of roasting is preferably 0.5 ~ 24 hour.The temperature of roasting is preferably 200 ~ 400 DEG C.
In technique scheme, what step (b) adopted helps the average grain diameter of active component to be preferably 40-150 order.
In technique scheme, pore creating material described in step (b) is preferably avicel cellulose or PEG, and weight average molecular weight range is preferably 4000 to 15 ten thousand.Addition preferably accounts for the 0-10% of catalyst weight.
In technique scheme, the one of binding agent described in step (b) preferably in Ludox, Alumina gel, titanium colloidal sol, montmorillonite and kaolin.Addition preferably accounts for the 0-10% of catalyst weight.
In technique scheme, the temperature of roasting described in step (b) is 300 ~ 500 DEG C.
For solve the problems of the technologies described above three, technical scheme of the present invention is as follows: method for producing propenoic acid, to comprise the material of methacrylaldehyde, air and water vapour for reaction raw materials, under catalyst described in the technical scheme of one of above-mentioned technical problem exists, reaction generates acrylic acid.
In technique scheme, the temperature of described reaction is preferably 240 ~ 350 DEG C.
In technique scheme, with methacrylaldehyde in reaction raw materials described in volume basis: air: water vapour is preferably 1:(2.5 ~ 8): (1 ~ 3).
In technique scheme, reaction raw materials volume space velocity is preferably 800 ~ 1600 hours
-1.
The key point of catalyst of the present invention does not lie in geometry and the size of catalyst, is therefore not particularly limited the shape and size of catalyst, and the various shape and size of existing carrier all can be used for the present invention and obtain result on year-on-year basis.Such as carrier of the present invention can take spherical, Raschig ring or cylindrical etc.Spherical diameter can preferred 3 ~ 5mm; Raschig ring external diameter can preferred 4 ~ 7mm, and internal diameter is 1.5 ~ 3mm preferably, and length is 3 ~ 5mm preferably; Cylindrical outer diameter can preferred 4 ~ 7mm, and length is 3 ~ 5mm preferably.
Described molding mode is not key of the present invention, and the molding mode known to those skilled in the art all can be used for the present invention.Such as extrusion molding, compressing, rolling is shaping.
Use catalyst of the present invention to prepare acrylic acid for methacrylaldehyde selective oxidation, reaction temperature be 260 DEG C, reaction velocity is 1400 hours
-1condition under, after 1000 hours, its acrolein conversion rate can reach 98.8%, product propylene acid yield can reach 88.2%, achieves good technique effect.
In the following embodiment provided, to the investigation appreciation condition of catalyst be:
Reactor: fixed bed reactors, internal diameter 25.4 millimeters, reactor length 750 millimeters
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 air speed: 1000 ~ 1600 hours
-1
Product 0 DEG C of diluted acid absorbs, and 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:
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)
5h
5[H
2(WO
4)
6] H
2o) also vigorous stirring is dissolved.In mixer B in 200ml deionized water, add the manganese nitrate aqueous solution (Mn (NO that 10 grams of concentration are 50wt%
3)
2), 19.3 grams of ferric nitrate (Fe (NO
3)
39H
2o) and 0.64 gram of potassium hydroxide (KOH), and obtained aqueous dispersion is added in batching filling A, and stir 2 hours at 80 DEG C, form catalyst pulp, after rotary evaporation, obtain powder.
Again the powder of acquisition is obtained active component through 250 DEG C of preroasts after 1 hour, from the active component obtained (I), take out 200 grams for shaping, wherein add 133 grams of SiO
2powder, 10 grams of methylcellulose (weight average molecular weight 20000), 44.4 grams of Ludox (SiO
2content 50wt%), 10 grams of deionized waters, mediate agent after 2 hours and go out shaping, obtaining external diameter is 5mm, and the Raschig ring of internal diameter to be 1.5mm length be 5mm, then roasting obtains finished catalyst in 2 hours, and sintering temperature is 400 DEG C, and reaction appraisal result lists in 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)
5h
5[H
2(WO
4)
6] H
2o) dissolve also vigorous stirring, continue to add the manganese nitrate aqueous solution (Mn (NO that 10 grams of concentration are 50wt%
3)
2), 19.3 grams of ferric nitrate (Fe (NO
3)
39H
2o) and 0.64 gram of potassium hydroxide (KOH), and stir 2 hours at 80 DEG C, form catalyst pulp, obtain powder after spraying dry, spray drying condition is: inlet temperature 250 DEG C, outlet temperature 120 DEG C, atomizing disk rotating speed 20000rpm/min.
Again the powder of acquisition is obtained active component through 250 DEG C of preroasts after 1 hour, from the active component obtained, take out 200 grams for shaping, wherein add 133 grams of SiO
2powder, 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 shaping, obtaining external diameter is 5mm, the Raschig ring of internal diameter to be 1.5mm length be 5mm, then roasting obtains finished catalyst in 2 hours, sintering temperature is 400 DEG C, and reaction appraisal result lists in table 2.
Comparative example 3
In the batching that stirring motor is housed is filled with, add 100 DEG C of deionized waters of 742.4ml, by 200 grams of ammonium molybdate ((NH
4)
6mo
7o
244H
2o), 31.9 grams of copper nitrate (Cu (NO
3)
23H
2o), 32.9 grams of ammonium metavanadate (NH
4vO
3), 30.6 grams of ammonium tungstate ((NH
4)
5h
5[H
2(WO
4)
6] H
2o) 10 grams of concentration is the manganese nitrate aqueous solution (Mn (NO of 50wt%
3)
2), 19.3 grams of ferric nitrate (Fe (NO
3)
39H
2o) and 0.64 gram of potassium hydroxide (KOH) is dissolved and vigorous stirring, and at 80 DEG C Keep agitation 1 hour, obtain aqueous dispersion.
By shaping SiO
2carrier (spherical, 3mm diameter, water absorption rate 80V%) oven dry of spending the night in advance, then by 320 grams of shaping SiO
2carrier drops in the aqueous dispersion prepared, and floods after 24 hours, and after oven dry, then roasting 2 hours at 500 DEG C, finally obtains finished catalyst.The main preparation condition of catalyst and catalyst composition are in table 1, and the investigation of catalyst the results are shown in table 2.
Embodiment 1
In the batching that stirring motor is housed is filled with, 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)
5h
5[H
2(WO
4)
6] H
2o) dissolve also vigorous stirring, continue to add the manganese nitrate aqueous solution (Mn (NO that 10 grams of concentration are 50wt%
3)
2), 19.3 grams of ferric nitrate (Fe (NO
3)
39H
2o) and 0.64 gram of potassium hydroxide (KOH), and stir 2 hours at 80 DEG C, form catalyst pulp, obtain powder after spraying dry, spray drying condition is: inlet temperature 250 DEG C, outlet temperature 120 DEG C, atomizing disk rotating speed 20000rpm/min.Again the powder of acquisition is obtained active component after 1 hour, from the active component Mo obtained through 250 DEG C of preroasts
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g.
The 200g ammonium molybdate of required ratio and 65.9g ammonium metavanadate are dissolved in 1000 water, then add 107.1 grams of ethylenediamines, stir lower aging 24 hours, through super-dry, roasting with obtain active phase VMo after pulverizing and sieving
2o
8powder, under 400 degree, roasting 3 hours.Pulverize and sieve before using and get 80-100 order.
Get 200 grams of active component Mo
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g, 80 grams of active phase VMo
2o
8powder, 200 grams of Mg
2+ 2/3al
3+ 1/3(OH)
2(CO
3 2-)
1/6powder (preparation method is shown in " Guangdong chemical industry " 2009 the 8th phase 13 pages), 14.4 grams of methylcellulose (weight average molecular weight 20000), 64 grams of Ludox (SiO
2content 50wt%), 14.4 grams of deionized waters, mediate agent after 2 hours and go out shaping, obtaining external diameter is 5mm, the Raschig ring of internal diameter to be 1.5mm length be 5mm, then roasting obtains finished catalyst in 2 hours, sintering temperature is 400 DEG C, and reaction appraisal result lists in table 2.
Embodiment 2
In the batching that stirring motor is housed is filled with, 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)
5h
5[H
2(WO
4)
6] H
2o) dissolve also vigorous stirring, continue to add the manganese nitrate aqueous solution (Mn (NO that 10 grams of concentration are 50wt%
3)
2), 19.3 grams of ferric nitrate (Fe (NO
3)
39H
2o) and 0.64 gram of potassium hydroxide (KOH), and stir 2 hours at 80 DEG C, form catalyst pulp, obtain powder after spraying dry, spray drying condition is: inlet temperature 250 DEG C, outlet temperature 120 DEG C, atomizing disk rotating speed 20000rpm/min.Again the powder of acquisition is obtained active component after 1 hour, from the active component Mo obtained through 250 DEG C of preroasts
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g.
The 200g ammonium molybdate of required ratio and 65.9g ammonium metavanadate are dissolved in 1000 water, then add 107.1 grams of ethylenediamines, stir lower aging 24 hours, through super-dry, roasting with obtain active phase VMo after pulverizing and sieving
2o
8powder, under 400 degree, roasting 3 hours.Pulverize and sieve before using and get 80-100 order.
Get 200 grams of active component Mo
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g, 80 grams of active phase VMo
2o
8powder, 400 grams of Co
2+ 2/3al
3+ 1/3(OH)
2(CO
3 2-)
1/6powder (preparation method is shown in " synthetic chemistry " 2007 15 volumes the 5th volume 585 pages), 14.4 grams of methylcellulose (weight average molecular weight 20000), 64 grams of Ludox (SiO
2content 50wt%), 14.4 grams of deionized waters, mediate agent after 2 hours and go out shaping, obtaining external diameter is 5mm, the Raschig ring of internal diameter to be 1.5mm length be 5mm, then roasting obtains finished catalyst in 2 hours, sintering temperature is 400 DEG C, and reaction appraisal result lists in table 2.
Embodiment 3
In the batching that stirring motor is housed is filled with, 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)
5h
5[H
2(WO
4)
6] H
2o) dissolve also vigorous stirring, continue to add the manganese nitrate aqueous solution (Mn (NO that 10 grams of concentration are 50wt%
3)
2), 19.3 grams of ferric nitrate (Fe (NO
3)
39H
2o) and 0.64 gram of potassium hydroxide (KOH), and stir 2 hours at 80 DEG C, form catalyst pulp, obtain powder after spraying dry, spray drying condition is: inlet temperature 250 DEG C, outlet temperature 120 DEG C, atomizing disk rotating speed 20000rpm/min.Again the powder of acquisition is obtained active component after 1 hour, from the active component Mo obtained through 250 DEG C of preroasts
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g.
The 200g ammonium molybdate of required ratio and 65.9g ammonium metavanadate are dissolved in 1000 water, then add 107.1 grams of ethylenediamines, stir lower aging 24 hours, through super-dry, roasting with obtain active phase VMo after pulverizing and sieving
2o
8powder, under 400 degree, roasting 3 hours.Pulverize and sieve before using and get 80-100 order.
Get 200 grams of active component Mo
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g, 80 grams of active phase VMo
2o
8powder, 400 grams of Ni
2+ 2/3al
3+ 1/3(OH)
2(CO
3 2-)
1/6powder (preparation method is shown in " Chinese Journal of Inorganic Chemistry " 2005 21 volumes the 8th phase 1181 pages), 14.4 grams of methylcellulose (weight average molecular weight 20000), 64 grams of Ludox (SiO
2content 50wt%), 14.4 grams of deionized waters, mediate agent after 2 hours and go out shaping, obtaining external diameter is 5mm, the Raschig ring of internal diameter to be 1.5mm length be 5mm, then roasting obtains finished catalyst in 2 hours, sintering temperature is 400 DEG C, and reaction appraisal result lists in table 2.
Embodiment 4
In the batching that stirring motor is housed is filled with, 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)
5h
5[H
2(WO
4)
6] H
2o) dissolve also vigorous stirring, continue to add the manganese nitrate aqueous solution (Mn (NO that 10 grams of concentration are 50wt%
3)
2), 19.3 grams of ferric nitrate (Fe (NO
3)
39H
2o) and 0.64 gram of potassium hydroxide (KOH), and stir 2 hours at 80 DEG C, form catalyst pulp, obtain powder after spraying dry, spray drying condition is: inlet temperature 250 DEG C, outlet temperature 120 DEG C, atomizing disk rotating speed 20000rpm/min.Again the powder of acquisition is obtained active component after 1 hour, from the active component Mo obtained through 250 DEG C of preroasts
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g.
The 200g ammonium molybdate of required ratio and 65.9g ammonium metavanadate are dissolved in 1000 water, then add 107.1 grams of ethylenediamines, stir lower aging 24 hours, through super-dry, roasting with obtain active phase VMo after pulverizing and sieving
2o
8powder, under 400 degree, roasting 3 hours.Pulverize and sieve before using and get 80-100 order.
Get 200 grams of active component Mo
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g, 80 grams of active phase VMo
2o
8powder, 400 grams of Zn
2+ 2/3al
3+ 1/3(OH)
2(CO
3 2-)
1/6powder (preparation method is shown in " synthetic chemistry " 2007 15 volumes the 5th phase 585 pages), 14.4 grams of methylcellulose (weight average molecular weight 20000), 64 grams of Ludox (SiO
2content 50wt%), 14.4 grams of deionized waters, mediate agent after 2 hours and go out shaping, obtaining external diameter is 5mm, the Raschig ring of internal diameter to be 1.5mm length be 5mm, then roasting obtains finished catalyst in 2 hours, sintering temperature is 400 DEG C, and reaction appraisal result lists in table 2.
Embodiment 5
In the batching that stirring motor is housed is filled with, 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)
5h
5[H
2(WO
4)
6] H
2o) dissolve also vigorous stirring, continue to add the manganese nitrate aqueous solution (Mn (NO that 10 grams of concentration are 50wt%
3)
2), 19.3 grams of ferric nitrate (Fe (NO
3)
39H
2o) and 0.64 gram of potassium hydroxide (KOH), and stir 2 hours at 80 DEG C, form catalyst pulp, obtain powder after spraying dry, spray drying condition is: inlet temperature 250 DEG C, outlet temperature 120 DEG C, atomizing disk rotating speed 20000rpm/min.Again the powder of acquisition is obtained active component after 1 hour, from the active component Mo obtained through 250 DEG C of preroasts
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g.
The 200g ammonium molybdate of required ratio and 65.9g ammonium metavanadate are dissolved in 1000 water, then add 107.1 grams of ethylenediamines, stir lower aging 24 hours, through super-dry, roasting with obtain active phase VMo after pulverizing and sieving
2o
8powder, under 400 degree, roasting 3 hours.Pulverize and sieve before using and get 80-100 order.
Get 200 grams of active component Mo
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g, 80 grams of active phase VMo
2o
8powder, 400 grams of Ca
2+ 2/3al
3+ 1/3(OH)
2(CO
3 2-)
1/6powder (preparation method is shown in " plastics " 2009 38 volumes the 3rd phase 52 pages), 14.4 grams of methylcellulose (weight average molecular weight 20000), 64 grams of Ludox (SiO
2content 50wt%), 14.4 grams of deionized waters, mediate agent after 2 hours and go out shaping, obtaining external diameter is 5mm, the Raschig ring of internal diameter to be 1.5mm length be 5mm, then roasting obtains finished catalyst in 2 hours, sintering temperature is 400 DEG C, and reaction appraisal result lists in table 2.
Embodiment 6
In the batching that stirring motor is housed is filled with, 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)
5h
5[H
2(WO
4)
6] H
2o) dissolve also vigorous stirring, continue to add the manganese nitrate aqueous solution (Mn (NO that 10 grams of concentration are 50wt%
3)
2), 19.3 grams of ferric nitrate (Fe (NO
3)
39H
2o) and 0.64 gram of potassium hydroxide (KOH), and stir 2 hours at 80 DEG C, form catalyst pulp, obtain powder after spraying dry, spray drying condition is: inlet temperature 250 DEG C, outlet temperature 120 DEG C, atomizing disk rotating speed 20000rpm/min.Again the powder of acquisition is obtained active component after 1 hour, from the active component Mo obtained through 250 DEG C of preroasts
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g.
The 200g ammonium molybdate of required ratio and 65.9g ammonium metavanadate are dissolved in 1000 water, then add 107.1 grams of ethylenediamines, stir lower aging 24 hours, through super-dry, roasting with obtain active phase VMo after pulverizing and sieving
2o
8powder, under 400 degree, roasting 3 hours.Pulverize and sieve before using and get 80-100 order.
Get 200 grams of active component Mo
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g, 80 grams of active phase VMo
2o
8powder, 100 grams of Ni
2+ 2/3al
3+ 1/3(OH)
2(CO
3 2-)
1/6powder (preparation method is shown in " Chinese Journal of Inorganic Chemistry " 2005 21 volumes the 8th phase 1181 pages), 11.4 grams of methylcellulose (weight average molecular weight 20000), 50.7 grams of Ludox (SiO
2content 50wt%), 11.4 grams of deionized waters, mediate agent after 2 hours and go out shaping, obtaining external diameter is 5mm, the Raschig ring of internal diameter to be 1.5mm length be 5mm, then roasting obtains finished catalyst in 2 hours, and sintering temperature is 400 DEG C, and reaction appraisal result lists in table 2.
Embodiment 7
In the batching that stirring motor is housed is filled with, 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)
5h
5[H
2(WO
4)
6] H
2o) dissolve also vigorous stirring, continue to add the manganese nitrate aqueous solution (Mn (NO that 10 grams of concentration are 50wt%
3)
2), 19.3 grams of ferric nitrate (Fe (NO
3)
39H
2o) and 0.64 gram of potassium hydroxide (KOH), and stir 2 hours at 80 DEG C, form catalyst pulp, obtain powder after spraying dry, spray drying condition is: inlet temperature 250 DEG C, outlet temperature 120 DEG C, atomizing disk rotating speed 20000rpm/min.Again the powder of acquisition is obtained active component after 1 hour, from the active component Mo obtained through 250 DEG C of preroasts
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g.
The 200g ammonium molybdate of required ratio and 65.9g ammonium metavanadate are dissolved in 1000 water, then add 107.1 grams of ethylenediamines, stir lower aging 24 hours, through super-dry, roasting with obtain active phase VMo after pulverizing and sieving
2o
8powder, under 400 degree, roasting 3 hours.Pulverize and sieve before using and get 80-100 order.
Get 200 grams of active component Mo
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g, 80 grams of active phase VMo
2o
8powder, 150 grams of Ni
2+ 2/3al
3+ 1/3(OH)
2(CO
3 2-)
1/6powder (preparation method is shown in " Chinese Journal of Inorganic Chemistry " 2005 21 volumes the 8th phase 1181 pages), 12.9 grams of methylcellulose (weight average molecular weight 20000), 57.3 grams of Ludox (SiO
2content 50wt%), 12.9 grams of deionized waters, mediate agent after 2 hours and go out shaping, obtaining external diameter is 5mm, the Raschig ring of internal diameter to be 1.5mm length be 5mm, then roasting obtains finished catalyst in 2 hours, sintering temperature is 400 DEG C, and reaction appraisal result lists in table 2.
Embodiment 8
In the batching that stirring motor is housed is filled with, 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)
5h
5[H
2(WO
4)
6] H
2o) dissolve also vigorous stirring, continue to add the manganese nitrate aqueous solution (Mn (NO that 10 grams of concentration are 50wt%
3)
2), 19.3 grams of ferric nitrate (Fe (NO
3)
39H
2o) and 0.64 gram of potassium hydroxide (KOH), and stir 2 hours at 80 DEG C, form catalyst pulp, obtain powder after spraying dry, spray drying condition is: inlet temperature 250 DEG C, outlet temperature 120 DEG C, atomizing disk rotating speed 20000rpm/min.Again the powder of acquisition is obtained active component after 1 hour, from the active component Mo obtained through 250 DEG C of preroasts
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g.
The 200g ammonium molybdate of required ratio and 65.9g ammonium metavanadate are dissolved in 1000 water, then add 107.1 grams of ethylenediamines, stir lower aging 24 hours, through super-dry, roasting with obtain active phase VMo after pulverizing and sieving
2o
8powder, under 400 degree, roasting 3 hours.Pulverize and sieve before using and get 80-100 order.
Get 200 grams of active component Mo
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g, 80 grams of active phase VMo
2o
8powder, 250 grams of Ni
2+ 2/3al
3+ 1/3(OH)
2(CO
3 2-)
1/6powder (preparation method is shown in " Chinese Journal of Inorganic Chemistry " 2005 21 volumes the 8th phase 1181 pages), 15.9 grams of methylcellulose (weight average molecular weight 20000), 70.7 grams of Ludox (SiO
2content 50wt%), 15.9 grams of deionized waters, mediate agent after 2 hours and go out shaping, obtaining external diameter is 5mm, the Raschig ring of internal diameter to be 1.5mm length be 5mm, then roasting obtains finished catalyst in 2 hours, sintering temperature is 400 DEG C, and reaction appraisal result lists in table 2.
Embodiment 9
In the batching that stirring motor is housed is filled with, 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)
5h
5[H
2(WO
4)
6] H
2o) dissolve also vigorous stirring, continue to add the manganese nitrate aqueous solution (Mn (NO that 10 grams of concentration are 50wt%
3)
2), 19.3 grams of ferric nitrate (Fe (NO
3)
39H
2o) and 0.64 gram of potassium hydroxide (KOH), and stir 2 hours at 80 DEG C, form catalyst pulp, obtain powder after spraying dry, spray drying condition is: inlet temperature 250 DEG C, outlet temperature 120 DEG C, atomizing disk rotating speed 20000rpm/min.Again the powder of acquisition is obtained active component after 1 hour, from the active component Mo obtained through 250 DEG C of preroasts
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g.
The 200g ammonium molybdate of required ratio and 65.9g ammonium metavanadate are dissolved in 1000 water, then add 107.1 grams of ethylenediamines, stir lower aging 24 hours, through super-dry, roasting with obtain active phase VMo after pulverizing and sieving
2o
8powder, under 400 degree, roasting 3 hours.Pulverize and sieve before using and get 80-100 order.
Get 200 grams of active component Mo
12v
3cu
1.5w
1.2mn
0.3fe
0.5k
0.1o
g, 80 grams of active phase VMo
2o
8powder, 300 grams of Ni
2+ 2/3al
3+ 1/3(OH)
2(CO
3 2-)
1/6powder (preparation method is shown in " Chinese Journal of Inorganic Chemistry " 2005 21 volumes the 8th phase 1181 pages), 17.4 grams of methylcellulose (weight average molecular weight 20000), 77.3 grams of Ludox (SiO
2content 50wt%), 17.4 grams of deionized waters, mediate agent after 2 hours and go out shaping, obtaining external diameter is 5mm, the Raschig ring of internal diameter to be 1.5mm length be 5mm, then roasting obtains finished catalyst in 2 hours, sintering temperature is 400 DEG C, and reaction appraisal result lists in table 2.
Table 1, catalyst composition and preparation condition
Note: the A representation class hydrotalcite supports of A:B:C in table, B represents Mo
12v
acu
bw
cx
dy
ez
fo
gshown active component, C represents and helps active component VMo
2o
8.
Table 2, comparative example and embodiment investigate result
Claims (10)
1. acrylic acid catalyst, comprises following component with weight parts:
The houghite carrier of 20-60 part; Carry the active component Mo of 5-40 part thereon
12v
acu
bw
cx
dy
ez
fo
gwith 5-40 part help active component VMo
2o
8;
Wherein houghite carrier structure formula is M
2+ 1-Qm
3+ q(OH)
2(A
n-)
q/nmH
2the non-stoichiometric compound that O represents, M
2+represent divalent metal, M
3+represent trivalent metal, A
n-represent anion;
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 is at least one element be selected from Fe, Bi, Co, Ni, Ge, Ga, Nb, Ce, La, Zr, Sr; Z is at least one element be selected from alkali metal or alkaline-earth metal; A, b, c, d, e, f and g represent the atomic ratio of their elements separately, atomic ratio based on Mo element is 12, the span of a is 0.5 ~ 4.0, the span of b is 0.1 ~ 5.0, the span of the span of c to be the span of 0 ~ 5.0, d be 0 ~ 5.0, e is 0 ~ 5.0, the span of f is 0 ~ 1.0, g is the number meeting the total valent required oxygen atom of other element; Q is 0.3 ~ 0.9, n=1 or 2, m=0 ~ 2.
2. the preparation method of catalyst described in claim 1, comprises the following steps:
A the compound of following elements is distributed in water and obtains hybrid dispersions by (), then dry and roasting obtains described active component: Mo, V, Cu, W, X, Y and Z;
B () is by the powder of the active component obtained in houghite carrier, step (a), the powder helping active component and binding agent and pore creating material mixing, shaping, dry and roasting obtains described catalyst.
3. preparation method according to claim 2, helps the synthetic method of active component as follows described in it is characterized in that:
The ammonium molybdate of required ratio and ammonium metavanadate are dissolved in required water, then add ethylenediamine, stir lower aging 1 ~ 24 hour, through super-dry, roasting and obtaining.
4. the preparation method of catalyst according to claim 2, it is characterized in that pore creating material described in step (b) is avicel cellulose or PEG, weight average molecular weight range is 4000 to 15 ten thousand.
5. the preparation method of catalyst according to claim 2, is characterized in that binding agent described in step (b) is selected from the one in Ludox, Alumina gel, titanium colloidal sol, montmorillonite and kaolin.
6. the preparation method of catalyst according to claim 2, is characterized in that the temperature of roasting described in step (b) is 300 ~ 500 DEG C.
7. method for producing propenoic acid, to comprise the material of methacrylaldehyde, air and water vapour for reaction raw materials, under catalyst as claimed in claim 1 exists, reaction generates acrylic acid.
8. production method according to claim 7, is characterized in that the temperature of reacting is 240 ~ 350 DEG C.
9. production method according to claim 7, is characterized in that with methacrylaldehyde in reaction raw materials described in volume basis: air: water vapour is preferably 1:(2.5 ~ 8): (1 ~ 3).
10. production method according to claim 7, is characterized in that reaction raw materials volume space velocity is 800 ~ 1600 hours
-1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110586121A (en) * | 2018-06-12 | 2019-12-20 | 中国石油化工股份有限公司 | Supported acrylic acid catalyst |
| CN111068675A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Supported catalyst for preparing acrylic acid from acrolein and application thereof |
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| CN1204966C (en) * | 1999-02-19 | 2005-06-08 | 株式会社日本触媒 | Gas-phase partial oxidation catalytic agent |
| CN103521234A (en) * | 2012-07-03 | 2014-01-22 | 中国石油化工股份有限公司 | Catalyst for preparing acrylic acid through acrolein oxidation and preparation method thereof |
| CN103769161A (en) * | 2012-10-25 | 2014-05-07 | 中国石油化工股份有限公司 | Acrolein catalyst and preparation method thereof |
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2014
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| CN1204966C (en) * | 1999-02-19 | 2005-06-08 | 株式会社日本触媒 | Gas-phase partial oxidation catalytic agent |
| DE102004021763A1 (en) * | 2004-04-30 | 2005-05-25 | Basf Ag | Extended gas-phase oxidation of acrolein to acrylic acid for use in polymer production, involves using an isothermal reactor followed by an adiabatic reactor, both with a multi-metal oxide molybdenum-vanadium catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110586121A (en) * | 2018-06-12 | 2019-12-20 | 中国石油化工股份有限公司 | Supported acrylic acid catalyst |
| CN111068675A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Supported catalyst for preparing acrylic acid from acrolein and application thereof |
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