CN105080558B - Acrylic acid catalyst and preparation method thereof - Google Patents
Acrylic acid catalyst and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to acrylic acid catalyst, preparation method and acrylic acid synthetic method, the problem of catalyst activity and selectivity is relatively low in the prior art is mainly solved.Catalyst of the invention by using acrolein oxidation acrylic acid synthesizing, including following components in terms of parts by weight：A：20 60 parts of houghite carrier；B thereon is loaded in it：5 40 parts of active component Mo12VaCubWcXdYeZfOgAnd C：5 40 parts of VMo2O8；Wherein X represents at least one of Cr, Mn, Sb element；Y is selected from least one of Fe, Bi, Co, Ni, Ge, Ga, Nb, Ce, La, Zr, Sr element；Z is the technical scheme selected from least one of alkali metal or alkaline-earth metal element, the problem is preferably solved, available in the industrial production of acrylic acid.
Description
Technical field
The present invention relates to the catalyst synthesized for acrylic acid, preparation method and acrylic acid synthetic method.
Background technology
Acrylic acid (CH2=CH-COOH) it is simplest unsaturated carboxylic acid, it is important organic synthesis raw material and synthesis
Resin monomer.Acrylic acid is mainly used in synthesizing senior water-absorbing resins and water treatment agent etc., and a part of acrylic acid, which is used to be esterified, to be used
To manufacture the esters of acrylic acids such as methyl acrylate, ethyl acrylate, n-butyl acrylate and 2-EHA, and propylene
Acid ester polymer is mainly used in the fields such as adhesive, coating, weaving, plastics, leather, papermaking.
Acrylic acid and its series of products, are developed rapidly in recent years, 2011, acrylicacidandesters class whole world total output
537.9 ten thousand t/a are reached, 515.6 ten thousand t/a compared with the end of the year in 2010 increase 4.3%, and the process units of current acrylic acid is main
The U.S., Europe, Japan and China are concentrated on, wherein China is acrylic acid production capacity country with fastest developing speed in recent years, it is contemplated that arrive
China will be by as the maximum country of global acrylic acid production capacity the end of the year in 2012.The large-scale plant of whole world industrial production acrylic acid is all
Using propylene oxidation technology, the technology has had the history of decades, and substantial amounts of technological development makes its production technology be gradually improved.
Up to now, the relevant invention of many patent authorizings are used to producing acrylic acid method from methacrylaldehyde catalyst,
Wherein most of is the catalyst containing molybdenum-vanadium (Mo-V), such as Chinese patent CN1070468C, CN1031488A,
CN1146438A, CN100378058C, CN1031050C, CN1169619C, CN1583261A and CN1146439A etc., these are special
Catalyst described by profit, its preparation method is generally that solution is made in the presence of solvent or water in many metallic compounds, is added
Insoluble oxide evaporates dry under heating and stirring, the preparation method then calcined, crush and be molded.And it is presently disclosed special
Described in profit element composition differs greatly, as disclosed in Chinese patent CN1169619C catalyst principal component be molybdenum, vanadium and copper, then
Add necessary tellurium, it is believed that tellurium can be such that the active phase oxidation molybdenum and copper molybdate of this catalyst more stablizes, and can delay to urge
Agent causes inactivation because Mo is lost in；Catalyst disclosed in Chinese patent CN1583261A be by 1. molybdenum, vanadium, copper be main activearm
Point, 2. essential stable component and 3. answering of constituting of nickel, iron, silicon, aluminium, alkali metal alkaline earth metal at least by titanium and antimony
Polymerisable compounds；Catalyst disclosed in Chinese patent CN1050779C its constitute the molybdenum including oxide form, vanadium, tungsten, copper substantially
And nickel element；Catalyst disclosed in Chinese patent CN1146439A contains molybdenum, vanadium, copper and contains elemental tungsten, niobium, tantalum, chromium and cerium
In one or more kinds of elements, and HT molybdenums containing copper, molybdenum and at least one element in elemental tungsten, vanadium, niobium and tantalum
The oxo metal oxide of sour steel structure type.
But the catalyst activity of prior art is low, acrylic acid yield is low.
The content of the invention
One of technical problems to be solved by the invention are showed in the art in acrolein oxidation production propylene acid reaction
The acrolein conversion rate of presence is low and there is provided the catalyst synthesized for acrylic acid the problem of low acrylic acid yield.The catalyst
For the reaction of acrolein oxidation acrylic acid synthesizing, with acrolein conversion rate is high and the characteristics of acrylic acid high income.
The two of the technical problems to be solved by the invention are to provide the preparation side of one of above-mentioned technical problem catalyst
Method.
The three of the technical problems to be solved by the invention are to provide third using one of the above-mentioned technical problem catalyst
The synthetic method of olefin(e) acid.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Acrylic acid catalyst, with parts by weight
Number meter includes following components：
20-60 parts of houghite carrier；It is loaded in the active component Mo of 5-40 parts thereon12VaCubWcXdYeZfOgAnd 5-
40 parts are helped active component VMo2O8；
Wherein houghite carrier structure formula is M2+ 1-QM3+ Q(OH)2(An-)Q/n·mH2The non-stoichiometry chemical combination that O is represented
Thing, M2+Represent divalent metal, M3+Represent trivalent metal, An-Represent anion；
Wherein Mo, V, Cu, W and O represent molybdenum, vanadium, copper, tungsten and oxygen；X represents at least one of Cr, Mn, Sb member
Element；Y is selected from least one of Fe, Bi, Co, Ni, Ge, Ga, Nb, Ce, La, Zr, Sr element；Z is selected from alkali metal or alkali
At least one of earth metal element；A, b, c, d, e, f and g represent the atomic ratio of each of which element, the original based on Mo elements
Son is 0.5~4.0 than the span for being 12, a, and the span that b span is 0.1~5.0, c is 0~5.0, d's
The span that the span that span is 0~5.0, e is 0~5.0, f is that 0~1.0, g is to meet other elements always to change
The number of the required oxygen atom of conjunction valency；Q is 0.3~0.9, n=1 or 2, m=0~2.An-It preferably is selected from Cl-、NO3 -、CO3 2-、
SO4 2-At least one of.M2+It preferably is selected from Co2+、Mg2+、Ni2+、Cu2+、Zn2+、Ca2+And Fe2+At least one of.M3+It preferably is selected from
Al3+、Fe3+And Mn3+At least one of.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The technical side of one of above-mentioned technical problem
The preparation method of catalyst described in case, comprises the following steps：
(a) compound of following elements is distributed in water and obtains hybrid dispersions, then dried and roasting obtains described
Active component：Mo, V, Cu, W, X, Y and Z；
(b) by the powder of the active component obtained in houghite carrier, step (a), help active component powder and
Binding agent and pore creating material mixing, shaping, dry and roasting obtain the catalyst.
In above-mentioned technical proposal, the synthetic method for helping active component is preferably as follows：By the ammonium molybdate of required ratio and
In water needed for ammonium metavanadate is dissolved in, ethylenediamine is added, the lower aging of stirring 1~24 hour is obtained by drying, roasting.Its
Middle ethylenediamine:V mol ratio 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 above-mentioned technical proposal, the average grain diameter for helping active component that step (b) is used is preferably 40-150 mesh.
In above-mentioned technical proposal, pore creating material described in step (b) is preferably avicel cellulose or PEG, weight average molecular weight model
Enclose preferably 4000 to 150,000.Addition preferably accounts for the 0-10% of catalyst weight.
In above-mentioned technical proposal, binding agent described in step (b) preferably be selected from Ludox, Alumina gel, titanium colloidal sol, montmorillonite and
One kind in kaolin.Addition preferably accounts for the 0-10% of catalyst weight.
In above-mentioned technical proposal, the temperature being calcined described in step (b) is 300~500 DEG C.
To solve the three of above-mentioned technical problem, technical scheme is as follows：Method for producing propenoic acid, with including third
The material of olefine aldehydr, air and water vapour is reaction raw materials, and catalyst described in the technical scheme in one of above-mentioned technical problem is present
Lower reaction generation acrylic acid.
In above-mentioned technical proposal, the temperature of the reaction is preferably 240~350 DEG C.
In above-mentioned technical proposal, with methacrylaldehyde in reaction raw materials described in volume basis:Air:Water vapour is preferably 1:(2.5
~8):(1~3).
In above-mentioned technical proposal, 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 the geometry and size of catalyst, thus shape to catalyst and
Size is not particularly limited, and the variously-shaped and size of existing carrier is used equally for the present invention and obtains year-on-year result.For example
The carrier of the present invention can take spherical, Raschig ring or cylinder etc..Preferable 3~the 5mm of spherical diameter；Raschig ring external diameter can be excellent
Select 4~7mm, internal diameter preferably 1.5~3mm, length preferably 3~5mm；Preferable 4~the 7mm of cylindrical outer diameter, length preferably 3~
5mm。
Described molding mode is not the key of the present invention, and molding mode known to those skilled in the art is used equally for this
Invention.Such as extrusion molding, compressing, rolling shaping.
Acrylic acid is prepared for methacrylaldehyde selective oxidation using the catalyst of the present invention, is 260 DEG C, reaction in reaction temperature
Air speed is 1400 hours-1Under conditions of, after 1000 hours, its acrolein conversion rate can up to the sour yield of 98.8%, product propylene
Up to 88.2%, preferable technique effect is achieved.
In embodiments given below, it is to the investigation appreciation condition of catalyst：
Reactor：Fixed bed reactors, 25.4 millimeters of internal diameter, 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 air speed：1000~1600 hours-1
Reaction product is absorbed with 0 DEG C of diluted acid, uses gas chromatographic analysis product.And calculate Carbon balance, when Carbon balance 95~
It is valid data when 105%.
Acrolein conversion rate, the definition of product yield and selectivity are：
Below by embodiment, the present invention is further elaborated：
Embodiment
Comparative example 1
In the dispensing equipped with stirring motor fills A, 1000ml 100 DEG C of deionized waters are added, by 200 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 34.2 grams of copper nitrate (Cu (NO3)2·3H2O), 32.9 grams of ammonium metavanadate (NH4VO3) and 30.6 grams
Ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O) dissolve and be stirred vigorously.In mixer B in 200ml deionized waters, 10 are added
Gram concentration is 50wt% manganese nitrate aqueous solution (Mn (NO3)2), 19.3 grams of ferric nitrate (Fe (NO3)3·9H2) and 0.64 gram of hydrogen-oxygen O
Change potassium (KOH), and the aqueous dispersion obtained is added into dispensing and fill in A, and stirred 2 hours at 80 DEG C, form catalyst slurry
Powder is obtained after material, rotary evaporation.
The powder of acquisition is obtained into active component after 1 hour by 250 DEG C of preroast again, from obtained active component (I)
It is middle to take out 200 grams for being molded, wherein adding 133 grams of SiO2Powder, 10 grams of methylcellulose (weight average molecular weight 20000),
44.4 grams of Ludox (SiO2Content 50wt%), 10 grams of deionized waters, agent goes out shaping after mediating 2 hours, obtains external diameter for 5mm,
Internal diameter is the Raschig ring that 1.5mm length is 5mm, and then roasting obtains finished catalyst for 2 hours, and sintering temperature is 400 DEG C, reaction
Appraisal result is listed in table 2.
Comparative example 2
In the dispensing equipped with stirring motor fills A, 1000ml 100 DEG C of deionized waters are added, by 200 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 34.2 grams of copper nitrate (Cu (NO3)2·3H2O), 32.9 grams of ammonium metavanadate (NH4VO3) and 30.6 grams
Ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O) dissolve and be stirred vigorously, continuously add the manganese nitrate that 10 grams of concentration are 50wt%
The aqueous solution (Mn (NO3)2), 19.3 grams of ferric nitrate (Fe (NO3)3·9H2O) and 0.64 gram of potassium hydroxide (KOH), and stirred at 80 DEG C
Mix 2 hours, form catalyst pulp, powder is obtained after spray drying, spray drying condition is：250 DEG C of inlet temperature, outlet temperature
120 DEG C of degree, atomizing disk rotating speed 20000rpm/min.
The powder of acquisition is obtained into active component after 1 hour by 250 DEG C of preroast again, taken from obtained active component
Going out 200 grams is used to be molded, wherein adding 133 grams of SiO2Powder, 10 grams of methylcellulose (weight average molecular weight 20000), 44.4 grams
Ludox (SiO2Content 50wt%), 10 grams of deionized waters and 30 grams of Span80, agent goes out shaping after mediating 2 hours, obtains external diameter
For 5mm, internal diameter is the Raschig ring that 1.5mm length is 5mm, then roasting obtains finished catalyst for 2 hours, and sintering temperature is 400
DEG C, reaction appraisal result is listed in table 2.
Comparative example 3
In the dispensing equipped with stirring motor is filled, 742.4ml 100 DEG C of deionized waters are added, by 200 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 31.9 grams of copper nitrate (Cu (NO3)2·3H2O), 32.9 grams of ammonium metavanadate (NH4VO3), 30.6 grams of tungsten
Sour ammonium ((NH4)5H5[H2(WO4)6]·H2O) manganese nitrate aqueous solution (Mn (the NO that 10 grams of concentration are 50wt%3)2), 19.3 grams of nitric acid
Iron (Fe (NO3)3·9H2O) dissolve and be stirred vigorously with 0.64 gram of potassium hydroxide (KOH), and persistently stirred 1 hour at 80 DEG C,
Obtain aqueous dispersion.
SiO will be molded2Carrier (spherical, 3mm diameters, water absorption rate 80V%) is dried overnight in advance, then by 320 grams of shapings
SiO2In the aqueous dispersion that carrier input is prepared, dipping is after 24 hours, after drying, then roasting 2 hours at 500 DEG C, most
After obtain finished catalyst.Main preparation condition and the catalyst composition of catalyst are shown in Table 1, and the investigation result of catalyst is listed in table
2。
Embodiment 1
In the dispensing equipped with stirring motor is filled, 1000ml 100 DEG C of deionized waters are added, by 200 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 34.2 grams of copper nitrate (Cu (NO3)2·3H2O), 32.9 grams of ammonium metavanadate (NH4VO3) and 30.6 grams
Ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O) dissolve and be stirred vigorously, continuously add the manganese nitrate that 10 grams of concentration are 50wt%
The aqueous solution (Mn (NO3)2), 19.3 grams of ferric nitrate (Fe (NO3)3·9H2O) and 0.64 gram of potassium hydroxide (KOH), and stirred at 80 DEG C
Mix 2 hours, form catalyst pulp, powder is obtained after spray drying, spray drying condition is：250 DEG C of inlet temperature, outlet temperature
120 DEG C of degree, atomizing disk rotating speed 20000rpm/min.The powder of acquisition is obtained into activearm after 1 hour by 250 DEG C of preroast again
Point, from obtained active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og。
The 200g ammonium molybdates and 65.9g ammonium metavanadates of required ratio are dissolved in 1000 water, 107.1 grams of second two are added
Amine, the lower aging of stirring 24 hours, by drying, be calcined and pulverize and sieve after obtain active phase VMo2O8Powder, under 400 degree, roasting
3 hours.Pulverized and sieved before use and take 80-100 mesh.
Take 200 grams of active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og, 80 grams of active phase VMo2O8Powder, 200 grams of Mg2 + 2/3Al3+ 1/3(OH)2(CO3 2-)1/6Powder (be shown in by preparation method《Guangdong chemical industry》8th phase page 13 in 2009), 14.4 grams of Methyl celluloses
Plain (weight average molecular weight 20000), 64 grams of Ludox (SiO2Content 50wt%), 14.4 grams of deionized waters, mediate 2 hours after agent go out
Shaping, obtains external diameter for 5mm, internal diameter is the Raschig ring that 1.5mm length is 5mm, then roasting obtains finished catalyst in 2 hours,
Sintering temperature is 400 DEG C, and reaction appraisal result is listed in table 2.
Embodiment 2
In the dispensing equipped with stirring motor is filled, 1000ml 100 DEG C of deionized waters are added, by 200 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 34.2 grams of copper nitrate (Cu (NO3)2·3H2O), 32.9 grams of ammonium metavanadate (NH4VO3) and 30.6 grams
Ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O) dissolve and be stirred vigorously, continuously add the manganese nitrate that 10 grams of concentration are 50wt%
The aqueous solution (Mn (NO3)2), 19.3 grams of ferric nitrate (Fe (NO3)3·9H2O) and 0.64 gram of potassium hydroxide (KOH), and stirred at 80 DEG C
Mix 2 hours, form catalyst pulp, powder is obtained after spray drying, spray drying condition is：250 DEG C of inlet temperature, outlet temperature
120 DEG C of degree, atomizing disk rotating speed 20000rpm/min.The powder of acquisition is obtained into activearm after 1 hour by 250 DEG C of preroast again
Point, from obtained active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og。
The 200g ammonium molybdates and 65.9g ammonium metavanadates of required ratio are dissolved in 1000 water, 107.1 grams of second two are added
Amine, the lower aging of stirring 24 hours, by drying, be calcined and pulverize and sieve after obtain active phase VMo2O8Powder, under 400 degree, roasting
3 hours.Pulverized and sieved before use and take 80-100 mesh.
Take 200 grams of active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og, 80 grams of active phase VMo2O8Powder, 400 grams of Co2 + 2/3Al3+ 1/3(OH)2(CO3 2-)1/6Powder (be shown in by preparation method《Synthesis chemistry》2007 volume 5 page 585 of volume 15), 14.4 grams of first
Base cellulose (weight average molecular weight 20000), 64 grams of Ludox (SiO2Content 50wt%), 14.4 grams of deionized waters, mediate 2 hours
Agent goes out shaping afterwards, obtains external diameter for 5mm, internal diameter is the Raschig ring that 1.5mm length is 5mm, then roasting is catalyzed for 2 hours
Agent finished product, sintering temperature is 400 DEG C, and reaction appraisal result is listed in table 2.
Embodiment 3
In the dispensing equipped with stirring motor is filled, 1000ml 100 DEG C of deionized waters are added, by 200 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 34.2 grams of copper nitrate (Cu (NO3)2·3H2O), 32.9 grams of ammonium metavanadate (NH4VO3) and 30.6 grams
Ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O) dissolve and be stirred vigorously, continuously add the manganese nitrate that 10 grams of concentration are 50wt%
The aqueous solution (Mn (NO3)2), 19.3 grams of ferric nitrate (Fe (NO3)3·9H2O) and 0.64 gram of potassium hydroxide (KOH), and stirred at 80 DEG C
Mix 2 hours, form catalyst pulp, powder is obtained after spray drying, spray drying condition is：250 DEG C of inlet temperature, outlet temperature
120 DEG C of degree, atomizing disk rotating speed 20000rpm/min.The powder of acquisition is obtained into activearm after 1 hour by 250 DEG C of preroast again
Point, from obtained active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og。
The 200g ammonium molybdates and 65.9g ammonium metavanadates of required ratio are dissolved in 1000 water, 107.1 grams of second two are added
Amine, the lower aging of stirring 24 hours, by drying, be calcined and pulverize and sieve after obtain active phase VMo2O8Powder, under 400 degree, roasting
3 hours.Pulverized and sieved before use and take 80-100 mesh.
Take 200 grams of active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og, 80 grams of active phase VMo2O8Powder, 400 grams of Ni2 + 2/3Al3+ 1/3(OH)2(CO3 2-)1/6Powder (be shown in by preparation method《Chinese Journal of Inorganic Chemistry》The 8th phases page 1181 of volume 21 in 2005), 14.4
Gram methylcellulose (weight average molecular weight 20000), 64 grams of Ludox (SiO2Content 50wt%), 14.4 grams of deionized waters, mediate 2
Agent goes out shaping after hour, obtains external diameter for 5mm, internal diameter is the Raschig ring that 1.5mm length is 5mm, then roasting is obtained for 2 hours
Finished catalyst, sintering temperature is 400 DEG C, and reaction appraisal result is listed in table 2.
Embodiment 4
In the dispensing equipped with stirring motor is filled, 1000ml 100 DEG C of deionized waters are added, by 200 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 34.2 grams of copper nitrate (Cu (NO3)2·3H2O), 32.9 grams of ammonium metavanadate (NH4VO3) and 30.6 grams
Ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O) dissolve and be stirred vigorously, continuously add the manganese nitrate that 10 grams of concentration are 50wt%
The aqueous solution (Mn (NO3)2), 19.3 grams of ferric nitrate (Fe (NO3)3·9H2O) and 0.64 gram of potassium hydroxide (KOH), and stirred at 80 DEG C
Mix 2 hours, form catalyst pulp, powder is obtained after spray drying, spray drying condition is：250 DEG C of inlet temperature, outlet temperature
120 DEG C of degree, atomizing disk rotating speed 20000rpm/min.The powder of acquisition is obtained into activearm after 1 hour by 250 DEG C of preroast again
Point, from obtained active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og。
The 200g ammonium molybdates and 65.9g ammonium metavanadates of required ratio are dissolved in 1000 water, 107.1 grams of second two are added
Amine, the lower aging of stirring 24 hours, by drying, be calcined and pulverize and sieve after obtain active phase VMo2O8Powder, under 400 degree, roasting
3 hours.Pulverized and sieved before use and take 80-100 mesh.
Take 200 grams of active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og, 80 grams of active phase VMo2O8Powder, 400 grams of Zn2 + 2/3Al3+ 1/3(OH)2(CO3 2-)1/6Powder (be shown in by preparation method《Synthesis chemistry》The 5th phases page 585 of volume 15 in 2007), 14.4 grams of first
Base cellulose (weight average molecular weight 20000), 64 grams of Ludox (SiO2Content 50wt%), 14.4 grams of deionized waters, mediate 2 hours
Agent goes out shaping afterwards, obtains external diameter for 5mm, internal diameter is the Raschig ring that 1.5mm length is 5mm, then roasting is catalyzed for 2 hours
Agent finished product, sintering temperature is 400 DEG C, and reaction appraisal result is listed in table 2.
Embodiment 5
In the dispensing equipped with stirring motor is filled, 1000ml 100 DEG C of deionized waters are added, by 200 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 34.2 grams of copper nitrate (Cu (NO3)2·3H2O), 32.9 grams of ammonium metavanadate (NH4VO3) and 30.6 grams
Ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O) dissolve and be stirred vigorously, continuously add the manganese nitrate that 10 grams of concentration are 50wt%
The aqueous solution (Mn (NO3)2), 19.3 grams of ferric nitrate (Fe (NO3)3·9H2O) and 0.64 gram of potassium hydroxide (KOH), and stirred at 80 DEG C
Mix 2 hours, form catalyst pulp, powder is obtained after spray drying, spray drying condition is：250 DEG C of inlet temperature, outlet temperature
120 DEG C of degree, atomizing disk rotating speed 20000rpm/min.The powder of acquisition is obtained into activearm after 1 hour by 250 DEG C of preroast again
Point, from obtained active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og。
The 200g ammonium molybdates and 65.9g ammonium metavanadates of required ratio are dissolved in 1000 water, 107.1 grams of second two are added
Amine, the lower aging of stirring 24 hours, by drying, be calcined and pulverize and sieve after obtain active phase VMo2O8Powder, under 400 degree, roasting
3 hours.Pulverized and sieved before use and take 80-100 mesh.
Take 200 grams of active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og, 80 grams of active phase VMo2O8Powder, 400 grams of Ca2 + 2/3Al3+ 1/3(OH)2(CO3 2-)1/6Powder (be shown in by preparation method《Plastics》The 3rd phases page 52 of volume 38 in 2009), 14.4 grams of Methyl celluloses
Plain (weight average molecular weight 20000), 64 grams of Ludox (SiO2Content 50wt%), 14.4 grams of deionized waters, mediate 2 hours after agent go out
Shaping, obtains external diameter for 5mm, internal diameter is the Raschig ring that 1.5mm length is 5mm, then roasting obtains finished catalyst in 2 hours,
Sintering temperature is 400 DEG C, and reaction appraisal result is listed in table 2.
Embodiment 6
In the dispensing equipped with stirring motor is filled, 1000ml 100 DEG C of deionized waters are added, by 200 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 34.2 grams of copper nitrate (Cu (NO3)2·3H2O), 32.9 grams of ammonium metavanadate (NH4VO3) and 30.6 grams
Ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O) dissolve and be stirred vigorously, continuously add the manganese nitrate that 10 grams of concentration are 50wt%
The aqueous solution (Mn (NO3)2), 19.3 grams of ferric nitrate (Fe (NO3)3·9H2O) and 0.64 gram of potassium hydroxide (KOH), and stirred at 80 DEG C
Mix 2 hours, form catalyst pulp, powder is obtained after spray drying, spray drying condition is：250 DEG C of inlet temperature, outlet temperature
120 DEG C of degree, atomizing disk rotating speed 20000rpm/min.The powder of acquisition is obtained into activearm after 1 hour by 250 DEG C of preroast again
Point, from obtained active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og。
The 200g ammonium molybdates and 65.9g ammonium metavanadates of required ratio are dissolved in 1000 water, 107.1 grams of second two are added
Amine, the lower aging of stirring 24 hours, by drying, be calcined and pulverize and sieve after obtain active phase VMo2O8Powder, under 400 degree, roasting
3 hours.Pulverized and sieved before use and take 80-100 mesh.
Take 200 grams of active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og, 80 grams of active phase VMo2O8Powder, 100 grams of Ni2 + 2/3Al3+ 1/3(OH)2(CO3 2-)1/6Powder (be shown in by preparation method《Chinese Journal of Inorganic Chemistry》The 8th phases page 1181 of volume 21 in 2005), 11.4
Gram methylcellulose (weight average molecular weight 20000), 50.7 grams of Ludox (SiO2Content 50wt%), 11.4 grams of deionized waters, pinch
Agent goes out shaping after closing 2 hours, obtains external diameter for 5mm, internal diameter is the Raschig ring that 1.5mm length is 5mm, is then calcined 2 hours
To finished catalyst, sintering temperature is 400 DEG C, and reaction appraisal result is listed in table 2.
Embodiment 7
In the dispensing equipped with stirring motor is filled, 1000ml 100 DEG C of deionized waters are added, by 200 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 34.2 grams of copper nitrate (Cu (NO3)2·3H2O), 32.9 grams of ammonium metavanadate (NH4VO3) and 30.6 grams
Ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O) dissolve and be stirred vigorously, continuously add the manganese nitrate that 10 grams of concentration are 50wt%
The aqueous solution (Mn (NO3)2), 19.3 grams of ferric nitrate (Fe (NO3)3·9H2O) and 0.64 gram of potassium hydroxide (KOH), and stirred at 80 DEG C
Mix 2 hours, form catalyst pulp, powder is obtained after spray drying, spray drying condition is：250 DEG C of inlet temperature, outlet temperature
120 DEG C of degree, atomizing disk rotating speed 20000rpm/min.The powder of acquisition is obtained into activearm after 1 hour by 250 DEG C of preroast again
Point, from obtained active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og。
The 200g ammonium molybdates and 65.9g ammonium metavanadates of required ratio are dissolved in 1000 water, 107.1 grams of second two are added
Amine, the lower aging of stirring 24 hours, by drying, be calcined and pulverize and sieve after obtain active phase VMo2O8Powder, under 400 degree, roasting
3 hours.Pulverized and sieved before use and take 80-100 mesh.
Take 200 grams of active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og, 80 grams of active phase VMo2O8Powder, 150 grams of Ni2 + 2/3Al3+ 1/3(OH)2(CO3 2-)1/6Powder (be shown in by preparation method《Chinese Journal of Inorganic Chemistry》The 8th phases page 1181 of volume 21 in 2005), 12.9
Gram methylcellulose (weight average molecular weight 20000), 57.3 grams of Ludox (SiO2Content 50wt%), 12.9 grams of deionized waters, pinch
Agent goes out shaping after closing 2 hours, obtains external diameter for 5mm, internal diameter is the Raschig ring that 1.5mm length is 5mm, then it is calcined 2 hours
To finished catalyst, sintering temperature is 400 DEG C, and reaction appraisal result is listed in table 2.
Embodiment 8
In the dispensing equipped with stirring motor is filled, 1000ml 100 DEG C of deionized waters are added, by 200 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 34.2 grams of copper nitrate (Cu (NO3)2·3H2O), 32.9 grams of ammonium metavanadate (NH4VO3) and 30.6 grams
Ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O) dissolve and be stirred vigorously, continuously add the manganese nitrate that 10 grams of concentration are 50wt%
The aqueous solution (Mn (NO3)2), 19.3 grams of ferric nitrate (Fe (NO3)3·9H2O) and 0.64 gram of potassium hydroxide (KOH), and stirred at 80 DEG C
Mix 2 hours, form catalyst pulp, powder is obtained after spray drying, spray drying condition is：250 DEG C of inlet temperature, outlet temperature
120 DEG C of degree, atomizing disk rotating speed 20000rpm/min.The powder of acquisition is obtained into activearm after 1 hour by 250 DEG C of preroast again
Point, from obtained active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og。
The 200g ammonium molybdates and 65.9g ammonium metavanadates of required ratio are dissolved in 1000 water, 107.1 grams of second two are added
Amine, the lower aging of stirring 24 hours, by drying, be calcined and pulverize and sieve after obtain active phase VMo2O8Powder, under 400 degree, roasting
3 hours.Pulverized and sieved before use and take 80-100 mesh.
Take 200 grams of active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og, 80 grams of active phase VMo2O8Powder, 250 grams of Ni2 + 2/3Al3+ 1/3(OH)2(CO3 2-)1/6Powder (be shown in by preparation method《Chinese Journal of Inorganic Chemistry》The 8th phases page 1181 of volume 21 in 2005), 15.9
Gram methylcellulose (weight average molecular weight 20000), 70.7 grams of Ludox (SiO2Content 50wt%), 15.9 grams of deionized waters, pinch
Agent goes out shaping after closing 2 hours, obtains external diameter for 5mm, internal diameter is the Raschig ring that 1.5mm length is 5mm, then it is calcined 2 hours
To finished catalyst, sintering temperature is 400 DEG C, and reaction appraisal result is listed in table 2.
Embodiment 9
In the dispensing equipped with stirring motor is filled, 1000ml 100 DEG C of deionized waters are added, by 200 grams of ammonium molybdates
((NH4)6Mo7O24·4H2O), 34.2 grams of copper nitrate (Cu (NO3)2·3H2O), 32.9 grams of ammonium metavanadate (NH4VO3) and 30.6 grams
Ammonium tungstate ((NH4)5H5[H2(WO4)6]·H2O) dissolve and be stirred vigorously, continuously add the manganese nitrate that 10 grams of concentration are 50wt%
The aqueous solution (Mn (NO3)2), 19.3 grams of ferric nitrate (Fe (NO3)3·9H2O) and 0.64 gram of potassium hydroxide (KOH), and stirred at 80 DEG C
Mix 2 hours, form catalyst pulp, powder is obtained after spray drying, spray drying condition is：250 DEG C of inlet temperature, outlet temperature
120 DEG C of degree, atomizing disk rotating speed 20000rpm/min.The powder of acquisition is obtained into activearm after 1 hour by 250 DEG C of preroast again
Point, from obtained active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og。
The 200g ammonium molybdates and 65.9g ammonium metavanadates of required ratio are dissolved in 1000 water, 107.1 grams of second two are added
Amine, the lower aging of stirring 24 hours, by drying, be calcined and pulverize and sieve after obtain active phase VMo2O8Powder, under 400 degree, roasting
3 hours.Pulverized and sieved before use and take 80-100 mesh.
Take 200 grams of active component Mo12V3Cu1.5W1.2Mn0.3Fe0.5K0.1Og, 80 grams of active phase VMo2O8Powder, 300 grams of Ni2 + 2/3Al3+ 1/3(OH)2(CO3 2-)1/6Powder (be shown in by preparation method《Chinese Journal of Inorganic Chemistry》The 8th phases page 1181 of volume 21 in 2005), 17.4
Gram methylcellulose (weight average molecular weight 20000), 77.3 grams of Ludox (SiO2Content 50wt%), 17.4 grams of deionized waters, pinch
Agent goes out shaping after closing 2 hours, obtains external diameter for 5mm, internal diameter is the Raschig ring that 1.5mm length is 5mm, then it is calcined 2 hours
To finished catalyst, sintering temperature is 400 DEG C, and reaction appraisal result is listed in table 2.
Table 1, catalyst composition and preparation condition
Note：A in table:B:C A represents houghite carrier, and B represents Mo12VaCubWcXdYeZfOgShown active component, C
Expression helps active component VMo2O8。
Table 2, comparative example and embodiment investigate result
Claims (10)
1. acrylic acid catalyst, including following components in terms of parts by weight：
20-60 parts of houghite carrier；It is loaded in the active component Mo of 5-40 parts thereon12VaCubWcXdYeZfOgWith 5-40 parts
Help active component VMo2O8；
Wherein houghite carrier structure formula is M2+ 1-QM3+ Q(OH)2(An-)Q/n·mH2The non-stoichiometric compound that O is represented, M2+
Represent divalent metal, M3+Represent trivalent metal, An-Represent anion；
Wherein Mo, V, Cu, W and O represent molybdenum, vanadium, copper, tungsten and oxygen；X represents at least one of Cr, Mn, Sb element；Y is
Selected from least one of Fe, Bi, Co, Ni, Ge, Ga, Nb, Ce, La, Zr, Sr element；Z is selected from alkali metal or alkaline-earth metal
At least one of element；A, b, c, d, e, f and g represent the atomic ratio of each of which element, and the atomic ratio based on Mo elements is
The span that 12, a span is 0.5~4.0, b is that 0.1~5.0, c span is 0~5.0, d value model
The span that the span enclosed for 0~5.0, e is 0~5.0, f is that 0~1.0, g meets the total chemical valence of other elements
The number of required oxygen atom；Q is 0.3~0.9, n=1 or 2, m=0~2；An-Selected from Cl-、NO3 -、CO3 2-、SO4 2-In extremely
Few one kind, M2+Selected from Co2+、Mg2+、Ni2+、Cu2+、Zn2+、Ca2+And Fe2+At least one of, M3+Selected from Al3+、Fe3+And Mn3+
At least one of.
2. the preparation method of catalyst described in claim 1, comprises the following steps：
(a) compound of following elements is distributed in water and obtains hybrid dispersions, then dried and roasting obtains the activity
Component：Mo, V, Cu, W, X, Y and Z；
(b) by the powder of the active component obtained in houghite carrier, step (a), help the powder and bonding of active component
Agent and pore creating material mixing, shaping, dry and roasting obtain the catalyst.
3. preparation method according to claim 2, it is characterised in that the synthetic method for helping active component is as follows：
In water needed for the ammonium molybdate and ammonium metavanadate of required ratio are dissolved in, ethylenediamine is added, the lower aging 1~24 of stirring is small
When, obtained by drying, roasting.
4. the preparation method of catalyst according to claim 2, it is characterised in that pore creating material described in step (b) is fine for crystallization
Dimension element or PEG, weight average molecular weight range is 4000 to 150,000.
5. the preparation method of catalyst according to claim 2, it is characterised in that it is molten that binding agent described in step (b) is selected from silicon
One kind in glue, Alumina gel, titanium colloidal sol, montmorillonite and kaolin.
6. the preparation method of catalyst according to claim 2, it is characterised in that the temperature being calcined described in step (b) is
300~500 DEG C.
7. method for producing propenoic acid, using the material including methacrylaldehyde, air and water vapour as reaction raw materials, in such as claim
Reaction generation acrylic acid in the presence of catalyst described in 1.
8. production method according to claim 7, it is characterised in that the temperature of reaction is 240~350 DEG C.
9. production method according to claim 7, it is characterised in that with methacrylaldehyde in reaction raw materials described in volume basis:It is empty
Gas:Water vapour is preferably 1:(2.5~8):(1~3).
10. production method according to claim 7, it is characterised in that reaction raw materials volume space velocity is 800~1600 small
When-1。
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| 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 |
| 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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| 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 |
| 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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