CN103769132B - low-carbon olefin oxidation catalyst and preparation method thereof - Google Patents
low-carbon olefin oxidation catalyst and preparation method thereof Download PDFInfo
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- CN103769132B CN103769132B CN201210404778.XA CN201210404778A CN103769132B CN 103769132 B CN103769132 B CN 103769132B CN 201210404778 A CN201210404778 A CN 201210404778A CN 103769132 B CN103769132 B CN 103769132B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 258
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims description 39
- 230000003647 oxidation Effects 0.000 title claims description 24
- 229910052799 carbon Inorganic materials 0.000 title claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
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- 239000010936 titanium Substances 0.000 claims abstract description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 229920000620 organic polymer Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910001427 strontium ion Inorganic materials 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- WTKKCYNZRWIVKL-UHFFFAOYSA-N tantalum Chemical compound [Ta+5] WTKKCYNZRWIVKL-UHFFFAOYSA-N 0.000 description 1
- 229910001460 tantalum ion Inorganic materials 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a multi-metal oxide catalyst, which mainly comprises the general formula MoaBibFecCodNieSbfSigAhBiOx(I) Wherein: mo is molybdenum, Bi is bismuth, Fe is iron, Co is cobalt, Ni is nickel, Sb is antimony, Si is silicon which is a carrier added in the catalyst, A is at least one element selected from magnesium, strontium, titanium and lanthanum, and B is at least one element selected from calcium, boron and zinc; o is oxygen; the catalyst of the invention is used for olefin selective oxidation reaction, and has the characteristics of high reaction activity and selectivity and long service life.
Description
Technical field
The present invention relates to multi-metal-oxide catalyst of propylene or the corresponding unsaturated aldehyde of selective isobutene oxidation production and preparation method thereof.More specifically, relate to a kind of catalyst with double-deck poly-metal deoxide, for catalyzing propone oxidation acrolein or isobutylene oxidation isobutylaldehyde.
Background technology
Propylene gas phase catalytic oxidation reaction prepares methacrylaldehyde, acrylic acid is strong exothermal reaction, a large amount of reaction heat is assembled instantaneously in reactor, form hot localised points, if reaction heat can not be removed timely and effectively, the heat gathered instantaneously is constantly accumulated, and will cause the loss of catalyst activity component, come off, to such an extent as to catalyst activity reduction, the lost of life, and cause the formation aggravating accessory substance because of over oxidation reaction, thus reduce methacrylaldehyde and acrylic acid yield.Even cause runaway reaction, make sintering of catalyst.
The appearance of " progress of oxidative synthesis acrylic acid process and catalyst " (petrochemical industry, the 39th volume the 7th phase in 2010) social focus also can make catalyst damage evil, shortens the service life of catalyst.For 80,000 tons/year of acroleic acid devices, propylene oxidation is prepared in acrolein reaction device needs more than 25000 tubulation, and acrolein oxidation is prepared in acrylic acid reactor also needs more than 25000 tubulation, loads methacrylaldehyde, acrylic acid catalyst more than 100 ton altogether.More than 50000 reaction tube, the filling of catalyst ensures that not filling sky has certain difficulty, if because focus is crossed high catalyst and sintered very soon, again change agent more in a short time, it is huge for can envisioning its economic loss; In addition, carry out under cryogenic as much as possible for methacrylaldehyde, acrylic acid production, because reaction needed salt bath heating, it maintains the energy resource consumption of producing also is huge spending; Due to the generation of focus, require high temperature resistant to reaction tube tubing, for up to ten thousand reaction tubes, tubing expense is exactly the very large cost payout of item.Therefore, if effectively suppress the generation of beds focus, huge economic benefit can be brought to large-scale industrial production.
Industrial propylene or isobutylene oxidation prepare the reaction unit mainly many reaction tubes of corresponding unsaturated aldehyde, acid, ensureing that catalyst is not sintered, under the prerequisite of long service life, improve selective and object product yield as far as possible, save the raw materials such as propylene, even if if feed stock conversion, methacrylaldehyde, acrylic acid yield improve 0.1 ~ 0.5 percentage point, the amount of the product obtained increases with the level of hundreds of ~ thousands of tons of, and its economic benefit is also very considerable.
At present, there is multiple method can reduce or avoid gathering and peroxidization of focus, as: Japanese Patent Laid-Open 04-217932 propose a kind of suppress focus appearance or focus on the method for hot polymerization collection, namely by the multiple catalyst with different possessive volume of preparation, and from the mode that unstripped gas inlet side reduces to outlet side catalyst possessive volume, fill reaction tube successively, but the possessive volume of catalyst is by the restriction of reaction tube diameter, and it is also very difficult multiple catalysts to be filled into reaction tube.CN1210511A prepares and multiplely has the catalyst-loaded of different activities arrange catalyst layer in reaction tube, according to above-mentioned several catalyst-loaded to the active order arrangement uprised of outlet from the entrance of unstripped gas.Also other method is had, such as inert substance and catalyst mix, reduce the activity of catalyst, be loaded into reactor inlet place, Japanese Unexamined Patent Publication 10614/1972 is mixed into heat resistanceheat resistant point in the catalyst and forms catalyst and inert substance with by catalyst dilution, and the method for tubulose made by catalyst by Japanese Patent Publication 36739/1987.Further, the Catalyst packing that unstrpped gas porch reduces by active component.CN01111960.8 uses fixed bed shell and tube reactor, in the presence of a catalyst, prepare methacrylaldehyde and acrylic acid by propylene gas phase catalytic oxidation reaction, the method can suppress the generation of focus in reaction zone or the hot polymerization collection on focus effectively, this catalyst consist of Mo
aw
bbi
cfe
da
eb
fc
gd
he
io
xthe feature of the method is the multiple catalysts that preparation has above-mentioned composition, but (α) kind of possessive volume, (β) temperature of calcining and/or (γ) alkali metal and/or quantity different, and press catalyst activity from unstripped gas entrance to the mode of outlet increase, catalyst is filled into reaction zone successively.Under CN00122609.6 provides the condition existed containing the oxide catalyst of Mo-Bi-Fe compound, methacrylaldehyde and acrylic acid is produced by vapor phase propylene oxide, described packed catalyst is in multitubular reactor of fixed bed, and the method can generate methacrylaldehyde and acrylic acid with high stable yield in long-time.The method is characterized in that and configure in each tubular reactor of two or more reaction zone vertically, each district's filling different catalysts, namely fill out Bi and/or Fe content catalyst from gas access end to gas outlet end and reduce with the ratio of Mo content.CN1672790A provides the acrylic acid catalyst of a kind of catalyzing propone aldehyde gaseous oxidation system, described catalyst comprises molybdenum and vanadium, also comprise at least one volatile catalyst toxic component, its amount is 10 to 100ppb quality through ion chromatography measurement, this catalyst can reduce the temperature of hot spot, and the reduction of the reaction efficiency of suppression thermal degradation.Specific practice is, comprise by making the volatility toxic component of specified quantitative and originally had in highly active catalyst, catalytic activity declines momently, can reduce the temperature of hot spot.CN1165055A is loaded in after on carrier by catalytic active component being divided, and calcine the catalyst of load sharing to suppress the generation of focus, the average grain diameter of catalyst is 4 ~ 16mm, and the average grain diameter of carrier is 3 ~ 12mm, and calcining heat is 500 ~ 600 DEG C.CN1314331A provides a kind of catalyst containing Mo-W-Bi-Fe, this catalyst, by the mode changing the kind of possessive volume calcining heat and/or alkali metal and/or quantity and increase to outlet side from the inlet side of unstripped gas according to catalyst activity, fills reaction zone successively with described multiple types catalyst.Catalyst is at least divided into two-layer in the axial direction of the reaction tube, and this catalyst is the multiple types catalyst with different activities level, can by changing calcining heat and/or the wherein kind of alkali metal and/or quantity and obtain.Hot polymerization collection on the appearance of focus or focus is effectively suppressed.JP200982239A discloses a kind of catalyst of the gas phase oxidation for hydrocarbons such as 3C or 4C, composition Mo (a) Bi (b) Co (c) Ni (d) Fe (e) X (f) Y'(g of this catalyst) Z (h) Q (i) Si (j) O (k) or Mo (12)-V (a') X'(b') Cu (c') Y " (d') Sb (e') Z'(f') Si (g') C (h') O (i').X is selected from sodium, potassium, rubidium, caesium or thallium, and Y' is selected from boron, phosphorus, arsenic or tungsten; Z is selected from magnesium, calcium, zinc, cerium; Y " is selected from magnesium, calcium, barium, zinc or strontium; Z' chosen from Fe, cobalt, nickel, bismuth or aluminium.
All there is a problem in the method that above-mentioned suppression focus produces, the catalyst be filled in reaction tube is diluted from the inlet to the outlet all in a variety of manners, both after having made catalyst runs some cycles, activity decrease also can not change thinner ratio, catalyst also cannot reoffer higher activity, not only load, dismantle, be separated, reclaim catalyst and make troubles, and the reactivity of catalyst can be reduced, especially industrial long-term operation catalyst activity reduction is faster, affects catalyst life.CN101274279 discloses a kind of oxide catalyst, and it is represented by following formula (2): Mo
12bi
afe
ba
cb
dc
ed
fo
x(2) this invention in order to solve to cause due to the appearance of catalyst focus its active or selective due to sintering etc. significantly reduced problem.This invention is such technical solution problem, the catalyst loaded in reactor has specific particle size distribution, space between catalyst granules can by evenly and expand, the appearance of the extra high temperature spot in local (focus) in catalyst layer can be suppressed and do not reduce methacrylaldehyde or acrylic acid output, and methacrylaldehyde or acrylic acid can be obtained long-term and stably.This catalyst particle size relative standard deviation is 0.02-0.20.Because industrial methacrylaldehyde, acrylic acid production loaded catalyst are larger; want that the particle size relative standard deviation ensureing catalyst is 0.02-0.20; the large-scale production of catalyst can be restricted undoubtedly, can because of the irregularity of catalyst size as useless agent process in possible production process.And tons of catalyst, screening particle size relative standard deviation is that the work of 0.02-0.20 is also wasted time and energy very much.
CN201010180103.2 discloses a kind of multilayer composite metal oxide catalyst, and the composition of this O composite metallic oxide catalyst can by formula M o
abi
bni
ccs
dcu
eti
fa
gb
hc
io
jrepresent, wherein: Mo is molybdenum, Bi is bismuth, and Ni is nickel, and Cs is caesium, and Cu is copper, and Ti is titanium, and A is at least one element be selected from arsenic, tellurium, manganese, cerium, niobium, zirconium, rubidium, cadmium and germanium; B is at least one element be selected from cobalt, boron, strontium, tantalum, alkali and alkaline earth metal ions; C is at least one element be selected from vanadium, tin, gallium, zinc, iron, tungsten and antimony; O is oxygen, described O composite metallic oxide catalyst has sandwich construction, reduces successively from internal layer parent to each concentration of element of skin, even if catalyst initial reaction activity is very high, this catalyst effectively can reduce single tube reactor localized heat and gather, and suppresses being emerged of focus.This catalyst mainly controls the focus produced because catalyst initial activity is high.But the selective and yield of object product has much room for improvement.And under the mixed airflow such as propylene, steam long period Scouring Condition, catalyst surface active component has part to run off, and affects catalyst activity and stability.CN201010180184.6 provides a kind of three layers of multi-metal-oxide catalyst and preparation method thereof, this catalyst contains Multimetal oxide as active component, this catalyst is applicable to propylene or corresponding unsaturated aldehyde is produced in selective isobutene oxidation, the organic matter due to unstripped gas middle and high concentration effectively can be suppressed to contact with the catalyst initial stage form higher focus and generate a large amount of accessory substances, improve catalyst choice.This catalyst preparation process is complicated, and three layers of catalyst are easy to come off through long-term operation skin, increases catalyst bed layer resistance, thus causes activity decrease.And the selective and yield of this catalyst object product also has much room for improvement.
CN200980112659.3 discloses and a kind ofly the present invention relates to the coated catalysts comprising following component: (a) carrier, b () comprises molybdenum oxide or forms the ground floor of precursor compound of molybdenum oxide, (c) comprises the second layer of the poly-metal deoxide containing molybdenum and other metal of at least one.The molybdenum oxide of preferred ground floor is MoO
3, the poly-metal deoxide of the second layer is the poly-metal deoxide that general formula I I represents: Mo
12bi
acr
bx
1 cfe
dx
2 ex
3 fo
y.This catalyst is the application type catalyst comprising carrier.Goal of the invention suppresses heterogeneously catalysed partial gas phase oxidation methacrylaldehyde to be acrylic acid coated catalysts inactivation, has the inactivation performance of improvement.This invention is not clearly recorded catalyst and is used for catalyzing propone oxidation acrolein, acrylic acid reactivity worth evaluating data, such as conversion ratio, selective, yield etc.CN200710106391.5 discloses a kind of preparation method of composite oxide catalysts, and wherein this catalyst is the catalyst of the olefin oxidation containing molybdenum and bismuth, and it is characterized in that, its specific area is at 5 ~ 25m
2/ g, its pore volume are in the scope of 0.2 ~ 0.7cc/g, and in the distribution of its fine pore, there is following distribution: the pore volume of fine pore (diameter) shared by the pore of 0.03 ~ 0.1 μm be more than 30% or 30% in total pore volume, be more than 20% or 20% in total pore volume in the pore volume shared by the pore of 0.1 ~ 1 μm, and the pore diameter proportion less than 0.03 μm is less than 10% or 10%, this composite oxide catalysts is represented by following general formula (1): Mo
abi
bco
cni
dfe
ex
fy
gz
hsi
io
j(1) in formula, X is from by magnesium (Mg), calcium (Ca), zinc (Zn), cerium (Ce), the at least a kind of element selected in the group of samarium (Sm) and halogen composition, Y is from by sodium (Na), potassium (K), rubidium (Rb), the at least a kind of element selected in the group that caesium (Cs) and thallium (Tl) form, Z is from by boron (B), phosphorus (P), the at least a kind of element selected in the group that arsenic (As) and tungsten (W) form, in addition, a ~ j represents the atomic ratio of each element, a=12, b=0.5 ~ 7, c=0 ~ 10, d=0 ~ 10, wherein c+d=1 ~ 10, e=0.05 ~ 3, f=0 ~ 2, g=0.04 ~ 2, h=0 ~ 3, i=5 ~ 48, in addition, j is the numerical value of the state of oxidation of the element meeting other.This invention needs pyrolytic silicon dioxide, and catalyst component disperses together with silicon, controls specific surface area of catalyst, pore volume, fine pore distribution, improves conversion ratio and selective etc.The height of beds hot localised points temperature is not mentioned in this invention.High to ingredient requirement, complicated process of preparation, catalytic component is many, and the distribution of specific area, pore volume, fine pore is difficult to effectively control, poor repeatability.
CN101579631 mono-kind for low-carbon alkene vapor phase catalytic oxidation prepare unsaturated aldehyde reaction containing Mo, Bi, Fe, the preparation method of the catalyst of Co composite oxides, this invention causes catalytic component uneven for what exist in prior art because of catalyst precursor different solubility, thus catalyst performance is deteriorated, and catalyst high conversion and high selectivity, the problem that high stability can not get both, the method mainly adds dilution thermal conducting agent when shaping of catalyst, catalyst dilution thermal conducting agent is selected from SiC, elemental silicon powder, the compound of one or more in graphite and carbon fiber.Similar also has CN1647854, CN101850259A.CN101850259A discloses the preparation method that propylene oxidation under a kind of high-speed prepares the catalyst of methacrylaldehyde, and this catalyst is based on Mo-Bi-Fe-Co composite metal oxide, and general formula is; MoaBibFecCodXeYfZgOh, this catalyst has selected the dilution thermal conducting agent with excellent heat conductivity performance to be incorporated in catalyst, and dilution thermal conducting agent is silica flour, solves the rendezvous problem of focus under high-speed, makes catalyst have excellent selective.This invention mainly improves the selective of catalyst by adding dilution thermal conducting agent silica flour in catalyst preparation process.Silica flour is more common in the preparation of methacrylaldehyde acrylic acid catalyst.
JP5293389A discloses a kind of PROPENE IN GAS PHASE OXIDATION and prepares the acrylic acid catalyst of methacrylaldehyde, and the composition of catalyst can have general formula to represent Mo
abi
bfe
ca
dx
ey
fz
gsi
go
i.A is at least one element be selected from cobalt and nickel, X is for being selected from least one element in Mg, Zn, Mn, Ca, Cr, Nb, Ag, Ba, Sn, Ta or Pb, Y is for being selected from P, B, S, Se, Te, Ce, W, Sb or Ti, and Z is selected from Li, Na, K, Rb, Cs or Ti at least one element.Be added with organic polymer in catalyst, this catalyst has loose structure (0.01 ~ 10 micron) and is easy to gas-phase reaction.CN1874984 discloses a kind of method stably using catalyst simultaneously to prepare unsaturated aldehyde and/or unrighted acid with high yield by effectively controlling hot(test)-spot temperature, it is characterized in that: described reactor comprises the reaction zone preparing unsaturated aldehyde, this reaction zone comprises two-layer or multilayer Catalytic Layer, each Catalytic Layer is all filled with the shaped catalyst product as secondary, secondary wherein in each Catalytic Layer is formed by the primary particle with varigrained catalytic active component, and the granularity controlling the primary particle of described catalytic active component reduces to reactor outlet from reactor inlet to make this granularity.This invention is hot issue in order to control catalyst, this invention suppresses focus by controlling the size of catalyst granules, the Catalytic Layer of the primary particle of maximum sized catalytic active component comprises the highest focus of temperature, and the size range of described primary particle is 10 to 150 microns.
In addition, under the high temperature conditions, in catalyst, part active component molybdenum loses from catalyst surface because of distillation.The mixed airflows such as methacrylaldehyde, air (oxygen), nitrogen and steam wash away the loss of active component that also can make in catalyst.For suppressing the loss of molybdenum distillation to cause active decay, CN1121504, by mixing copper component and having the zirconium of specified particle diameter and specific area and/or titanium and/or cerium, can suppress dissipation effect and the over reduction of molybdenum composition; CN1445020 adds the effect that a small amount of tellurium plays stable free molybdenum trioxide and copper molybdate crystal structure, and sublimation and the over reduction of molybdenum suppress to some extent; CN1583261 is with molybdenum, vanadium, copper, tungsten and/or niobium for key component, and the composite oxides formed with other element or its hopcalite form the loss that catalyst suppresses molybdenum.Also have and increase steam consumption and can take away reaction heat, but but steam input greatly often make catalyst member active component solution-off and make activity decrease.
Therefore, need to provide Propylene Selectivity to be oxidized and prepare methacrylaldehyde, acrylic acid catalyst, active component not easily runs off, and water repelling property is good, and improves the selective and yield of object product as far as possible, to obtain larger economic benefit.
Summary of the invention
The object of this invention is to provide the multi-metal-oxide catalyst and preparation method thereof that corresponding unsaturated aldehyde, unsaturated acids are produced in a kind of propylene or selective isobutene oxidation.There is gradient difference from inside to exterior active combination of components substrate concentration in catalyst granules of the present invention, catalyst outer layer each constituent content concentration ratio internal layer maternal concentration is high.Catalyst activity component not easily runs off, and water repelling property is good, and the selective and yield of object product is high.Be specially adapted to Propylene Selectivity oxidation and prepare acrylic acid.
The present invention relates to a kind of multi-metal-oxide catalyst, for low-carbon alkene oxidation reaction, the main composition of this catalyst is by general formula (I) expression below: Mo
abi
bfe
cco
dni
esb
fsi
ga
hb
io
x(I).
Wherein: Mo is molybdenum, Bi is bismuth, and Fe is iron, and Co is cobalt, and Ni is nickel, and Sb is antimony, and Si is silicon, and silicon is the carrier added in catalyst, and A is at least one element be selected from magnesium, strontium, titanium, lanthanum, and B is selected from least one element in calcium, boron, zinc, O is oxygen, a, b, c, d, e, f, g, h, i represent each Elements Atom ratio respectively, and wherein a is a number of 12, and b is a number of 0.5 ~ 6, preferably 1.0 ~ 5, c is a number of 0.5 ~ 5, preferably 1 ~ 4, d is a number of 1 ~ 8, preferably 1 ~ 6, e is a number of 0.5 ~ 6, f is a number of 0.1 ~ 3, g is a number of 0.2 ~ 55, preferably 1 ~ 16, h is a number of 0.05 ~ 4, i is a number of 0.05 ~ 1.5, x is the numerical value determined by the oxygen of each oxide, described multi-metal-oxide catalyst has interior outer double-layer structure, every layer of catalyst mainly forms identical, but silica, one or more molar concentration in aluminium oxide or carborundum is different, outer silica, one or more molar concentration rate internal layer parent in aluminium oxide or carborundum low, in molar content, catalyst outer layer each constituent content concentration ratio internal layer parent is high.
Low-carbon alkene oxidation catalyst of the present invention is double-decker, there is gradient difference from inside to exterior active combination of components substrate concentration in catalyst, is achieved concentration difference mainly through adding the materials such as different amount silica, aluminium oxide, carborundum at ectonexine.In molar content, outer each constituent content is higher by 0.1 ~ 30% than this constituent content of internal layer parent, and preferably 0.1 ~ 15%.
The present invention can add active component lanthanum, and lanthanum and nickel, cobalt, antimony etc. form stable crystal phase structure, as Co
3la
2, Cu
2la, LaNi
5, La
2sb, LaSb etc., the good dispersion of molybdenum, thus suppress part active component molybdenum to lose from catalyst surface because of distillation, active component molybdenum not easily runs off, before and after catalyst reaction, active component molybdenum content is substantially constant, delays active deterioration rate, catalyst activity and good stability.Lanthanum and molybdenum, cobalt ratio are suitable, and in general formula (I), A is lanthanum, and h is a number of 0.05 ~ 2.5, and molybdenum is competed in the add membership and bismuth and cobalt of too much lanthanum, affects catalyst activity.Catalyst mainly forms as shown in general formula (II).
Mo
aBi
bFe
cCo
dNi
eSb
fSi
gLa
hB
iO
x（Ⅱ）
Multi-metal-oxide catalyst of the present invention adopts common preparation method, prepares as adopted following step.
1) by A in the compound containing Mo, Bi, Fe, Co, Ni, Sb and general formula (I)
hb
ithe each elemental constituent compound related to dissolve and mix, form internal layer parent slurries after carrying out co-precipitation, in slurry production process, add one or more in silica, aluminium oxide or carborundum, dry, shaping, roasting obtains catalyst inner layer parent;
2) outer layer catalyst is prepared according to the method for Kaolinite Preparation of Catalyst internal layer parent, control one or more the addition in silica, aluminium oxide or carborundum in outer preparation process, make each concentration of element in outer layer catalyst higher than the concentration of this element of adjacent inner layer;
3) outer layer catalyst of preparation is coated on catalyst inner layer parent successively, after roasting, obtains finished catalyst.
Catalyst inner layer parent of the present invention after shaping and skin all need roasting 3 ~ 10h at 400 ~ 580 DEG C after application, compare not the catalyst of respectively roasting, repeatedly roasting can improve activity and the stability of catalyst.Can be open roasting also can be enclosed roasting, calcination atmosphere can be the inert gases such as helium, nitrogen, argon gas.
Catalyst layer too thick roasting time easily chap, in order to avoid be full of cracks preferably 55 ~ 125 DEG C of oven dry after application, and then roasting.The outer layer catalyst thickness being coated on internal layer parent is 0.1 ~ 2.0mm, preferably 0.2 ~ 1.5mm.
The compound of each component of catalyst of the present invention can use the nitrate, ammonium salt, sulfate, oxide, hydroxide, chloride, acetate etc. of each element, as lanthanum nitrate, magnesium nitrate, antimony oxide, strontium nitrate, titanium dioxide, borax, boric acid, calcium nitrate, zinc nitrate etc.
After catalyst inner layer parent slurries of the present invention are dried, the forming methods such as extrusion molding, granulating and forming, compression molding are usually preferably adopted to be processed into spherical, hollow spheres, ellipticity, cylindric, hollow circuit cylinder etc., preferably hollow circuit cylinder or spherical.
Catalyst of the present invention preferably uses binding agent when applying, and ectonexine catalyst is bondd more firm.Under internal layer parent is in rolling condition, sprays binding agent infiltrates surface, then spray the outer layer catalyst powder prepared, also internal layer parent can be put into the outer layer catalyst slurries prepared and carry out rolling coating.Binding agent is selected from one or more in water, alcohols or ethers.Alcohols is as ethanol, propyl alcohol, butanols; Ethers is as ether and butyl ether.
Each layer surface preferably uneven, rough surface of catalyst of the present invention, is conducive to coating, bonds between layers more firm.
The present invention, in order to improve intensity, the efflorescence degree of catalyst, can to add in glass fibre, graphite, pottery or various whisker one or more in above-mentioned outer layer catalyst.
The present invention has double-decker, and internal layer also can be called internal layer parent.Object product mainly refers to methacrylaldehyde, acrylic acid.
Because catalyst initial reaction activity is very high, so be easy to produce focus or produce heat localization on fixed bed single tube reactor bed, catalyst is easy to sintering, and this is very serious concerning loss suitability for industrialized production methacrylaldehyde acrylic acid.Pass into a certain amount of steam in raw material, because specific heat of water is large, a large amount of reaction heat can be taken away, but steam input greatly often makes catalyst member active component solution-off and makes activity decrease.Therefore catalyst is needed to have good water repelling property.The present invention preferably uses two kinds to have double-deck multi-metal-oxide catalyst, sentencing interior scope to 1/3 or porch to 1/2 in propylene porch uses internal layer concentration higher than the catalyst of outer concentration, as the catalyst of CN201010180103.2, the filling scope of catalyst is not strictly limited, 1/3 of beds can be less than, also can unnecessary 1/3.Because the active component concentration of catalyst external surface is low, so corresponding activity is also low, therefore effectively can suppress being emerged of focus and gathering of heat, reduce the growing amount of accessory substance (as hydrocarbon), improve the selective of object product.Use internal layer concentration lower than the catalyst of outer concentration at residual catalyst bed, density of propylene opposite inlet is lower, and catalyst activity is high, is more conducive to improving the acrylic acid selective and yield of methacrylaldehyde.And catalyst structure is stablized, and active component not easily runs off.Like this, under high-speed reaction condition, two kinds have double-deck catalyst layering filling, reaction bed temperature distribution is more reasonable, (bed temperature declines affects the selective of catalyst and yield to avoid the reaction bed temperature close to the port of export to decline soon, be unfavorable for the steady running of catalyst long period), make catalyst have good water repelling property, improve the selective of object product and yield.
Catalyst activity of the present invention is high, is applicable to Propylene Selectivity oxidation acrolein, acrylic acid.Better be along propylene arrival end to port of export beds porch to the catalyst of the scope filling internal layer concentration between 1/3 or porch to 1/2 place higher than outer concentration, as the catalyst of CN201010180103.2, the filling scope of catalyst is not strictly limited, 1/3 of beds can be less than, also can unnecessary 1/3.Residual catalyst bed loads catalyst of the present invention.
Evaluating catalyst performance index definition is as follows:
Detailed description of the invention
Illustrate that there is double-deck multi-metal-oxide catalyst and preparation method thereof with specific embodiment below, and this catalyst prepares the catalytic performance of methacrylaldehyde in Propylene Selectivity oxidation, but scope of the present invention is not limited to these embodiments.Following examples adopt propylene be propylene content >=99.6%(volume fraction) high concentration propylene.The analytical method of product composition adopts this area universal method.
Embodiment 1:
The preparation of catalyst 1
Step 1: Kaolinite Preparation of Catalyst internal layer parent
(1) preparation of active component slurries (a)
Under agitation, get 169.5 grams of ammonium molybdates and be dissolved in (water temperature more than 65 DEG C) in 1000ml pure water, obtain slurries (1), then get 76.8 grams of cobalt nitrates, 40.4 grams of ferric nitrates, 58.2 grams of nickel nitrates, 3.7 grams of magnesium nitrates are dissolved in (water temperature more than 65 DEG C) in 500ml pure water, fully be uniformly mixed, obtain slurries (2).Get 77.6 grams of bismuth nitrates again, be dissolved under agitation in dust technology, obtain slurries (3).Then, slurries (1) mix with slurries (2), obtain slurries (4), are then added in slurries (4) by slurries (3), then 56 grams of antimony trioxides, obtain active component slurries (a).
(2) preparation of catalyst inner layer parent
57.6 grams of silicon dioxide powders and 3 grams of aluminium oxide are added in active component slurries (a), 80 DEG C of strong stirrings carry out heat drying after coprecipitation reaction for 2 hours, with 160 DEG C of heat treatments 3 hours in nitrogen, then be a granulated into through banded extruder extruding, rolling the ball shape that diameter is 2.5mm, dry rear 550 DEG C of roastings 4 hours for 85 DEG C, obtained catalyst Precursors, this catalyst inner layer parent mainly consists of:
Mo
12Bi
2Fe
1.25Co
3.3Ni
2.5Sb
1.2Si
12Mg
0.25O
x
Step 2: Kaolinite Preparation of Catalyst is outer
(1) preparation of active component slurries (a)
Identical with the preparation of active component slurries (a) in embodiment 1 catalyst inner layer parent.
(2) preparation of catalyst outer layer
Active component slurries (a) and 10.1 grams of silicon dioxide powders and 4 grams of graphite are carried out coprecipitation reaction heat drying after 40 minutes, with 150 DEG C of heat treatments 3 hours in nitrogen, then 500 DEG C of roastings 4 hours, process to obtain catalyst outer layer powder through pulverizing, grinding, sieve, skin mainly consists of:
Mo
12Bi
2Fe
1.25Co
3.3Ni
2.5Sb
1.2Si
3.1Mg
0.25O
x。Outer field constituent content is higher by 0.3% ~ 12.1% than this constituent content of internal layer.
Step 3: Kaolinite Preparation of Catalyst 1
Catalyst inner layer parent step 1 prepared is placed in round bottom container, ethanolic solution is sprayed to catalyst Precursors under container rotation condition, stop operating under the condition of fully wetting catalyst inner layer parent, put it into rapidly another rotate be placed with in the round bottom container of step 2 gained outer layer catalyst powder, apply, coating layer thickness is at 0.5 ~ 1.5mm, and namely gained catalyst 100 DEG C obtains catalyst 1 in 4 hours through 450 DEG C of roastings after drying.
Embodiment 2:
The preparation of catalyst 2
With the preparation process of embodiment 1 catalyst 1 and primary raw material identical, internal layer adds 76.8 grams of silica and 3.1 grams of carborundum.Banded extruder is extruded is the hollow columnar particle of φ 5 × 5mm, and skin adds 5.8 grams of silica and is coated with, and layer thickness, at 0.5 ~ 2.0mm, namely obtains catalyst 2 in 3 hours through 560 DEG C of roastings.Catalyst 2 internal layer parent mainly consists of: Mo
12bi
5fe
4co
5ni
1.5sb
0.8si
16sr
0.1la
0.5b
0.1o
x, skin mainly consists of: Mo
12bi
5fe
4co
5ni
1.5sb
0.8si
1.2sr
0.1la
0.5b
01o
x.Outer field constituent content is higher by 0.11% ~ 13% than this constituent content of internal layer.
Embodiment 3:
With the preparation process of embodiment 1 catalyst 1 and primary raw material identical, internal layer adds 48 grams of silica and 8.5 grams of aluminium oxide, and extruded through banded extruder is the hollow columnar particle of φ 5 × 5mm, and skin adds 3.8 grams of silica.Coating layer thickness, at 0.1 ~ 1.5mm, namely obtains catalyst 3 in 10 hours through 400 DEG C of roastings.Catalyst 3 internal layer parent mainly consists of: Mo
12bi
0.8fe
3co
8ni
4sb
2si
10ti
0.5ca
0.2o
x, skin mainly consists of: Mo
12bi
0.8fe
3co
8ni
4sb
2si
0.8ti
0.5ca
0.2o
x
Comparative example 1:
With the internal layer of catalyst 3 for comparative catalyst 1, make the ball that diameter is 4mm, reaction condition is with the appreciation condition of catalyst 1.
Comparative example 2:
With the skin of catalyst 3 for comparative catalyst 2, make the ball that diameter is 4mm, reaction condition is with the appreciation condition of catalyst 1.
Embodiment 4:
With the preparation process of embodiment 1 catalyst 1 and primary raw material identical, internal layer adds 120 grams of silica, then through banded extruder extruding, rolling is a granulated into the ball shape that diameter is 2mm, skin adds 7.7 grams of silica.Coating layer thickness, at 0.5 ~ 2.0mm, namely obtains catalyst 4 in 6 hours through 480 DEG C of roastings.Catalyst 4 internal layer parent mainly consists of: Mo
12bi
3fe
2.1co
1.3ni
1.1sb
3si
25mg
0.1la
1.0o
x, skin mainly consists of: Mo
12bi
3fe
2.1co
1.3ni
1.1sb
3si
1.6mg
0.1la
1.0o
x
Embodiment 5:
With the preparation process of embodiment 1 catalyst 1 and primary raw material identical, internal layer adds 91.2 grams of silica, then through banded extruder extruding, rolling is a granulated into the ball shape that diameter is 2mm, skin adds 4.8 grams of silica.Coating layer thickness, at 0.5 ~ 2.0mm, namely obtains catalyst 5 in 5 hours through 550 DEG C of roastings.Catalyst 5 internal layer parent mainly consists of: Mo
12bi
1fe
4.8co
5.7ni
5.4sb
1.0si
19sr
0.3o
x, skin mainly consists of:
Mo
12Bi
1Fe
4.8Co
5.7Ni
5.4Sb
1.0Si
1Sr
0.3O
x
Embodiment 6:
Independent loading catalyst 5, reaction condition is with the appreciation condition of catalyst 1.
Comparative example 3:
Independent filling CN21010180103.2 embodiment 5 catalyst, reaction condition is with the appreciation condition of catalyst 1.
Oxidation reaction
Fixed bed single tube reactor internal diameter 25mm, inside establishes thermocouple, along propylene feed orienting response device bed load 15ml CN201010180103. embodiment 5 catalyst (F
1section), the above-mentioned catalyst of 25ml or comparative example catalyst (F
2section), salt bath heating.From above-mentioned reaction tube porch with air speed 900h
-1import the mist of propylene 9 volume %, air 73 volume %, steam 18 volume %.The performance of catalyst as shown in Table 1 and Table 2.React 24 hours and 1000 hours, load beds hot localised points temperature of the present invention not higher than 361 DEG C, adopt two kinds of double-layer catalyst segmentation fillings, compare a kind of catalyst of filling separately, reaction bed temperature distribution is more reasonable, improve object selectivity of product and yield, methacrylaldehyde and acrylic acid total recovery more than 90.6%, when steam intake 18 volume %, through the reaction of 1000 hours, catalyst activity component molybdenum etc. not easily runs off, and catalyst performance stabilised, has good water repelling property.Comparative example 1,2 and 3 poor selectivity, methacrylaldehyde, acrylic acid yield are low.
Table 1 reacts 24 hours post-evaluation results
Table 2 reacts 1000 hours post-evaluation results
Claims (9)
1. a low-carbon alkene oxidation catalyst, is characterized in that catalyst mainly forms as shown in general formula (I): Mo
abi
bfe
cco
dni
esb
fsi
ga
hb
io
x(I), wherein: silicon is the carrier added in catalyst, A is at least one element be selected from magnesium, strontium, titanium, lanthanum, and B is selected from least one element in calcium, boron, zinc, O is oxygen, a, b, c, d, e, f, g, h, i represents each Elements Atom ratio respectively, wherein a is a number of 12, b is a number of 0.5 ~ 6, c is a number of 0.5 ~ 5, d is a number of 1 ~ 8, e is a number of 0.5 ~ 6, f is a number of 0.1 ~ 3, g is a number of 0.2 ~ 55, h is a number of 0.05 ~ 4, i is a number of 0.05 ~ 1.5, x is the numerical value determined by the oxygen of each oxide, described multi-metal-oxide catalyst has interior outer double-layer structure, every layer of catalyst mainly forms identical, but one or more the molar concentration in silica or carborundum is different, one or more molar concentration rate internal layer parent in outer silica or carborundum low, in molar content, catalyst outer layer each active component content concentration ratio internal layer parent is high by 0.1 ~ 30%.
2. catalyst according to claim 1, is characterized in that catalyst outer layer each active component content concentration ratio internal layer parent is high by 0.1 ~ 15%.
3. catalyst according to claim 1, it is characterized in that in general formula (I), A is lanthanum, h is a number of 0.05 ~ 2.5, and catalyst mainly forms as shown in general formula (II), Mo
abi
bfe
cco
dni
esb
fsi
gla
hb
io
x(II).
4. catalyst according to claim 1, is characterized in that b is a number of 1.0 ~ 5.
5. catalyst according to claim 1, is characterized in that c is a number of 1 ~ 4.
6. catalyst according to claim 1, it is characterized in that d is a number of 1 ~ 6, g is a number of 1 ~ 16.
7. the preparation method of catalyst according to any one of claim 1 ~ 6, is characterized in that comprising the steps:
1) by A in the compound containing Mo, Bi, Fe, Co, Ni, Sb and general formula (I)
hb
ieach elemental constituent compound that part relates to dissolves and mixes, and forms internal layer parent slurries, add one or more in silica or carborundum in slurry production process after carrying out co-precipitation, and dry, shaping, roasting obtains catalyst inner layer parent;
2) outer layer catalyst slurries are prepared according to the method for Kaolinite Preparation of Catalyst internal layer parent slurries, control one or more the addition in silica or carborundum in outer preparation process, make each reactive element concentration in outer layer catalyst slurries higher than the concentration of this active element of adjacent inner layer;
3) outer layer catalyst of preparation is coated on catalyst inner layer parent successively, after roasting, obtains finished catalyst.
8. the preparation method of catalyst according to claim 7, it is characterized in that internal layer parent after shaping and skin roasting 3 ~ 10h at 400 ~ 580 DEG C after application, adopt open roasting or enclosed roasting, calcination atmosphere is helium, nitrogen or argon gas.
9. the preparation method of catalyst according to claim 7, is characterized in that the compound of described each component is the one in the nitrate of each element, ammonium salt, sulfate, oxide, hydroxide, chloride or acetate.
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|---|---|---|---|---|
| JP2003170044A (en) * | 2001-12-10 | 2003-06-17 | Asahi Kasei Corp | Catalyst preparation method |
| CN1697694A (en) * | 2003-11-14 | 2005-11-16 | 三菱化学株式会社 | Process for producing composite oxide catalyst |
| CN101579631A (en) * | 2009-06-22 | 2009-11-18 | 上海华谊丙烯酸有限公司 | Method for preparing catalyst applied to low-carbon olefin selective oxidization for undersaturation aldehyde preparation |
| CN101850259A (en) * | 2010-06-01 | 2010-10-06 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst of acrolein through propylene oxidation at high airspeed |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003170044A (en) * | 2001-12-10 | 2003-06-17 | Asahi Kasei Corp | Catalyst preparation method |
| CN1697694A (en) * | 2003-11-14 | 2005-11-16 | 三菱化学株式会社 | Process for producing composite oxide catalyst |
| CN101579631A (en) * | 2009-06-22 | 2009-11-18 | 上海华谊丙烯酸有限公司 | Method for preparing catalyst applied to low-carbon olefin selective oxidization for undersaturation aldehyde preparation |
| CN101850259A (en) * | 2010-06-01 | 2010-10-06 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst of acrolein through propylene oxidation at high airspeed |
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