CN107866246A - Hydro carbons selective oxidation catalyst and preparation method thereof - Google Patents
Hydro carbons selective oxidation catalyst and preparation method thereof Download PDFInfo
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- CN107866246A CN107866246A CN201610846450.1A CN201610846450A CN107866246A CN 107866246 A CN107866246 A CN 107866246A CN 201610846450 A CN201610846450 A CN 201610846450A CN 107866246 A CN107866246 A CN 107866246A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
- B01J27/198—Vanadium
- B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
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Abstract
The present invention relates to a kind of hydro carbons selective oxidation catalyst and preparation method thereof.Problem can be remarkably decreased by solving supported V PO catalyst epistasis present in prior art.By using following steps：1) by selected catalyst carrier mineral acid treatment；2) obtained carrier in a certain amount of addition step 1 containing vanadium solution is carried out impregnating to obtain precursor A；3) heated after mixing precursor A, organic solvent, phosphoric acid and promoter elements compound and keep 2 48h, after filtration washing is dried, 1 20h is calcined at a temperature of no more than 300 DEG C and obtains catalyst precursor B；4) precursor B is carried out at 350 500 DEG C in the atmosphere of special composition being calcined supported catalyst is made in the technical scheme of final catalyst, there is preferable Load Balanced and higher active selectable, the Selective Oxidation available for low-carbon hydro carbons.
Description
Technical field
The present invention relates to a kind of hydro carbons selective oxidation catalyst and preparation method thereof, the catalyst prepared with methods described,
Available for hydro carbons Selective Oxidation, maleic anhydride is produced especially suitable for low-carbon alkanes selective oxidation.
Technical background
The vapor phase catalytic oxidation of low-carbon hydro carbons is a kind of important catalytic reaction.Organic acid anhydride chemical combination is prepared available for catalysis
A variety of oxidation products such as thing.One of wherein typical product is maleic anhydride (cis-butenedioic anhydride).
Vanadium series catalyst is one of main catalyst system of lower carbon number hydrocarbons gas-like phase Selective Oxidation.By years of researches
It is to produce the maximally efficient caltalyst of cis-butenedioic anhydride to catalyzed gas hydro carbons especially normal butane so far to think vpo catalyst
System.The hypophosphite monohydrate hydrogen-oxygen vanadium (VOHPO of presoma half is made in industrialized vpo catalyst generally use aqueous phase or organic phase method4·
0.5H2O), gained presoma obtains final catalyst by shaping and calcination activation.
The barium oxide such as vanadic anhydride (V of Aqueous phase vpo catalyst presoma generally use pentavalent2O5) in water and HCl
Obtained by being reacted in the presence of in the environment of, and current vpo catalyst presoma is mainly prepared using organic phase method, and it is made
The backflow in organic solvent (predominantly alcohols) of the barium oxide and phosphoric acid of standby process generally use pentavalent obtains presoma, this
During the variable condition of vanadium be reduced to tetravalence barium oxide V by organic alcohols for pentavalent barium oxide2O4, gained tetravalence vanadium oxygen
Compound obtains VOHPO with phosphoric acid back flow reaction4·0.5H2O.Work is had been achieved with as the vpo catalyst obtained by above-mentioned preparation method
Industry, but there are still some shortcomings for the performance of vpo catalyst.Wear no resistance, be catalyzed as the intensity of vpo catalyst in itself is weaker
Agent specific surface area is smaller etc., by VPO it is supported be an approach solving the above problems, as CN1935374 proposes one kind
ZrO2Supported V PO method, Li etc. are in " n-Butane oxidation over VPO catalysts supported on
A kind of SBA-15 supported Vs PO side is proposed in SBA-15 " (Journal of Catalysis, 2006,238,232-241)
Method；Y.H.Taufiq-Yap etc. is in " n-Butane Oxidation over γ-Al2O3Supported Vanadium
Phosphate Catalysts " (Journal of Natural Gas Chemistry, 2007,16,266-272) are attempted
Al2O3Supported V PO method etc..But the mode that most of supported method generally uses add carrier VPO precursor solutions is real
Existing dip loading, because VPO precursor solutions prepared by organic method are usually suspended liquid status, its uniformity loaded would generally
By a definite limitation, the performance of supported catalyst have impact on.Therefore, solve the uniform well loaded of vpo catalyst, and ensure to bear
The active selectable that catalyst can be maintained after load is the developing direction of supported V PO catalyst.
The content of the invention
To be solved by this invention is the problem of supported V PO catalyst epistasis can be remarkably decreased present in prior art,
A kind of preparation method of the loaded vanadium-phosphor catalyst for hydro carbons Selective Oxidation is provided, this method passes through first by carrier in vanadium
Dip loading in the homogeneous phase solution of compound, then by heating response and leading in autoclave with phosphorus-containing compound and reduction solvent
Cross subsequent treatment and improved loaded vanadium-phosphor catalyst is made.The loaded vanadium-phosphor catalyst made from this method, load are more uniformly distributed,
Catalytic performance is preferable.
In order to solve the above technical problems, catalyst of the present invention, is included following with total catalyst weight percentages
Component：
A) 35~55% carrier compound；
B) 40%~60% active catalytic components；The active component is based on elemental mole ratios with consisting of formula：
VPaXbYcZdOe, in formula, X is selected from least one of transition metal element；Y is in alkali metal or alkaline-earth metal
At least one element；Z is selected from least one of IVA or VA races element；
Wherein a=0.9~1.4；B=0.001~0.3；C=0~0.2；D=0~0.1；E is each element in satisfaction composition
Oxygen element mol ratio needed for chemical valence.
In above-mentioned technical proposal, X is selected from least one of transition metal element, preferably using Mo, Zn, Nb, Co, Zr member
One or more in element.
In above-mentioned technical proposal, Y is selected from least one of alkali metal or alkaline-earth metal element, preferably using Li or Na.
In above-mentioned technical proposal, Z is selected from least one of IVA or VA races element, preferably using Si or Bi.
In above-mentioned technical proposal, preferable scheme is that X is selected from Mo and Zn；Y is selected from Na；Z is selected from Bi.
Method for preparing catalyst of the present invention, the technical scheme of use comprise the following steps：
1) selected catalyst carrier is mixed with inorganic acid, filters and dry after heating stirring reaction 2-24h；
2) a certain amount of vfanadium compound is dissolved by heating in oxalic acid solution, after the completion of reaction to be dissolved, adds institute in step 1
Obtained carrier is impregnated, and the carrier after dipping, which is dried and is calcined 1-24h at 500-600 DEG C, obtains precursor A；
3) airtight heating 2-48h in autoclave, institute are added after mixing precursor A, organic solvent, phosphoric acid and co-catalyst
Product is obtained after filter washing is dried, 1-20h is calcined at a temperature of no more than 300 DEG C and obtains catalyst precursor B；
4) precursor B is carried out at 350-500 DEG C in the atmosphere of special composition being calcined to obtain final catalyst.
In above-mentioned technical proposal, the catalyst carrier described in step 1), to be not readily dissolved in the porous oxidation of acids used
Thing, can include the carriers such as inorganic oxide, composite oxides, molecular sieve, and the characteristic feature of selected carrier should be included preferably
Physical strength and larger specific surface area.Oxide carrier specific surface area should be greater than 50m2/g.Preferably, the oxide carries
Body is composite oxide carrier.In above-mentioned technical proposal, preferably, the complex element containing Ti and Zr in complex carrier.
In above-mentioned technical proposal, the inorganic acid described in step 1) can be hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid etc..At this
In preparation method, preferably using phosphoric acid.
In above-mentioned technical proposal, the vfanadium compound described in step 2), the tetravalence or pentavalent compound of vanadium are referred mainly to, is selected
Vfanadium compound and coordinative solvent preferably form homogeneous phase solution, so as to realize the uniform load of vfanadium compound, in this preparations just
In method, preferably using ammonium metavanadate.
In above-mentioned technical proposal, the organic solvent described in step 3), mainly include primary alconol class, secondary alcohol class, polyalcohols,
The one or more of organic amine, organic acid compound, preferable technical scheme are to use primary alcohols solvent；Preferred skill
Art scheme is that described organic solvent is using isobutanol and the single or mixed system of phenmethylol.
In above-mentioned technical proposal, the co-catalyst described in step 3), it should be in claim 1 in active component composition
X, the compound of Y, Z element.Described element compound, can be the inorganic salts or organic salt of these elements, preferably solvable
In the corresponding salt compounds of used organic solvent.Before being contacted with the precursor A in above-mentioned technical proposal, described is optional
Element should be sufficiently mixed with the organic solvent described in step 3), phosphorus-containing compound.
In above-mentioned technical proposal, the phosphoric acid described in its step 3), vanadium unit cellulose content in its phosphorus element-containing and precursor A
Molar ratio should control in 0.9-1.3.
Above-mentioned technical scheme, it is technically characterized in that the reduction for carrying out supported catalyst in step 3) using autoclave is anti-
Should.Realize that reduction reaction generates presoma by temperature control, the desorption of dipping layer is reduced by autoclave environment, so as to be lifted
Catalyst performance.It is 100-200 DEG C, preferably 120-160 DEG C that autoclave, which controls temperature range,.
In above-mentioned technical proposal, the process for being thermally treated resulting in active catalyst under special atmosphere in step 4) is described
Special atmosphere be lighter hydrocarbons/air mixed gas, or the mixed gas of air/inert/water vapour, or empty
The mixed gas of gas/inert gas/oxycarbide/water vapour, activation temperature are 350~500 DEG C.Preferred technical scheme
For described heat treatment activation process, activation temperature is 380~450 DEG C.Described lighter hydrocarbons, low-carbon alkanes are referred mainly to, preferably just
Butane；Described inert gas, can be nitrogen, helium or argon gas；Described oxycarbide, mainly carbon dioxide.
Using technical scheme, aoxidized by using by the catalyst carrier of acid treatment uniform load vanadium first
Thing, then heating response reduces and adds a variety of co-catalysts in autoclave, finally in special atmosphere calcination activation preparation
Method, prepared supported V PO catalyst, there is preferable Load Balanced and higher active selectable, available for low-carbon
The Selective Oxidation of hydro carbons, cis-butenedioic anhydride is produced especially suitable for selective oxidation of n -butane.
The present invention, but content not thereby limiting the invention are further illustrated with example below.
Embodiment
【Embodiment 1】
The zirconium oxychloride of 0.025mol titanium tetrachloride and 0.075mol is dissolved in deionized water under condition of ice bath, is made into
Concentration is 0.5M solution.Resulting solution is instilled under stirring condition in 25wt% ammonia spirit and detect the pH in solution
Value, stops being added dropwise and stirring when pH value reaches about 9, at room temperature it is still aging overnight after filter, and be washed with deionized water
Wash to silver nitrate solution detection without Cl ions, 20h is dried at 120 DEG C.It is about by dried composite oxides addition concentration
In 1M phosphoric acid solution and 80 DEG C of stirring holding 10h are warming up to, after gained acid treatment composite oxides are by filtration washing, in baking
120 DEG C of dryings in case, it is placed in Muffle furnace the roasting 6h under the conditions of 500 DEG C and obtains composite oxide carrier.
0.6mol oxalic acid is added in 500ml deionized waters and dissolved, adds 0.2mol ammonium metavanadates, heated solution thereto
And stirring and dissolving, carrier 20g is added in vanadium solution upon dissolution and impregnates 20h, in 120 DEG C of dry 20h after filtering, and in horse
Not 550 DEG C of roasting 6h obtain catalyst precursor A in stove.
By with vanadium molar amount precursor A 0.3mol and mixed 400ml isobutanols, 100ml phenmethylols, 95%wt
Phosphoric acid (phosphorus and vanadium stoichiometric mole ratio are about 1.05), 0.003mol phosphomolybdic acids, 0.01mol zinc acetylacetonates, 0.0005mol oxalic acid
Sodium and 0.001mol bismuth acetates are together added in autoclave, and heating autoclave is to 140 DEG C of reaction 10h, cooled and filtered and with different
Butanol washs, and gained filter cake dries 20h at 110 DEG C, and 260 DEG C of roasting 6h, obtain precursor B in air atmosphere.By precursor B
Then 425 DEG C of roastings are warming up in the atmosphere of the vapor of the carbon dioxide of the nitrogen of the air of volume ratio 20%/20%/10%/50%
3h, finally 425 DEG C of roasting 3h obtain active catalyst in the steam atmosphere of the carbon dioxide of 40% nitrogen/10%/50%.Gained is urged
Agent is fed in 1.5vol% butane, 1600hr-1Air speed, checked and rated in fixed bed reactors at 390 DEG C, measure butanes conversion
For 84.7%, yield of maleic anhydride 58.2%.
【Comparative example 1】
By vanadic anhydride 0.3mol and mixed 400ml isobutanols, 100ml phenmethylols, 95%wt phosphoric acid (phosphorus with
Vanadium stoichiometric mole ratio be about 1.05), 0.003mol phosphomolybdic acids, 0.01mol zinc acetylacetonates, 0.0005mol sodium oxalates and
0.001mol bismuth acetates are together added in autoclave, and heating autoclave to 140 DEG C of reaction 10h, cooled and filtered simultaneously uses isobutanol
Washing, gained filter cake dry 20h at 110 DEG C, and 260 DEG C of roasting 6h, obtain precursor B in air atmosphere.Precursor B is subsequent
425 DEG C of roasting 3h are warming up in the atmosphere of the vapor of the carbon dioxide of the nitrogen of the air of volume ratio 20%/20%/10%/50%, most
425 DEG C of roasting 3h obtain active catalyst in the steam atmosphere of the carbon dioxide of 40% nitrogen/10%/50% afterwards.Gained catalyst
Fed in 1.5vol% butane, 1600hr-1Air speed, checked and rated in fixed bed reactors at 390 DEG C, measuring butanes conversion is
82.9%, yield of maleic anhydride 54.3%.
【Embodiment 2】
The zirconium oxychloride of 0.025mol titanium tetrachloride and 0.075mol is dissolved in deionized water under condition of ice bath, is made into
Concentration is 0.5M solution.Resulting solution is instilled under stirring condition in 25wt% ammonia spirit and detect the pH in solution
Value, stops being added dropwise and stirring when pH value reaches about 9, at room temperature it is still aging overnight after filter, and be washed with deionized water
Wash to silver nitrate solution detection without Cl ions, 20h is dried at 120 DEG C.It is about by dried composite oxides addition concentration
In 1M phosphoric acid solution and 80 DEG C of stirring holding 10h are warming up to, after gained acid treatment composite oxides are by filtration washing, in baking
120 DEG C of dryings in case, it is placed in Muffle furnace the roasting 6h under the conditions of 500 DEG C and obtains composite oxide carrier.
0.6mol oxalic acid is added in 500ml deionized waters and dissolved, adds 0.2mol ammonium metavanadates, heated solution thereto
And stirring and dissolving, carrier 20g is added in vanadium solution upon dissolution and impregnates 20h, in 120 DEG C of dry 20h after filtering, and in horse
Not 550 DEG C of roasting 6h obtain catalyst precursor A in stove.
By with vanadium molar amount precursor A 0.3mol and mixed 400ml isobutanols, 100ml phenmethylols, 95%wt
Phosphoric acid (phosphorus and vanadium stoichiometric mole ratio are about 1.05), 0.003mol phosphomolybdic acids, 0.01mol zinc acetylacetonates together add autoclave
In, heating autoclave to 140 DEG C of reaction 10h, cooled and filtered is simultaneously washed with isobutanol, and gained filter cake is dried at 110 DEG C
20h, 260 DEG C of roasting 6h, obtain precursor B in air atmosphere.By precursor B then the nitrogen of the air of volume ratio 20%/20%/
425 DEG C of roasting 3h are warming up in the atmosphere of the vapor of 10% carbon dioxide/50%, finally the carbon dioxide of 40% nitrogen/10%/
425 DEG C of roasting 3h obtain active catalyst in 50% steam atmosphere.Gained catalyst is fed in 1.5vol% butane, 1600hr-1
Air speed, checked and rated in fixed bed reactors at 390 DEG C, measure butanes conversion as 83.1%, yield of maleic anhydride 57.0%.
【Embodiment 3】
By 20g ZrO2Add in the phosphoric acid solution that concentration is about 1M and be warming up to 80 DEG C of stirrings and keep 8h, gained acid treatment
ZrO2After filtration washing, in 120 DEG C of dryings in baking oven, it is placed in Muffle furnace the roasting 6h under the conditions of 500 DEG C and is aoxidized
Thing carrier.
0.6mol oxalic acid is added in 500ml deionized waters and dissolved, adds 0.2mol ammonium metavanadates, heated solution thereto
And stirring and dissolving, carrier 20g is added in vanadium solution upon dissolution and impregnates 20h, in 120 DEG C of dry 20h after filtering, and in horse
Not 550 DEG C of roasting 6h obtain catalyst precursor A in stove.
By with vanadium molar amount precursor A 0.3mol and mixed 400ml isobutanols, 100ml phenmethylols, 95%wt
Phosphoric acid (phosphorus and vanadium stoichiometric mole ratio are about 1.05), 0.003mol phosphomolybdic acids, 0.01mol zinc acetylacetonates, 0.0005mol oxalic acid
Sodium and 0.001mol bismuth acetates are together added in autoclave, and heating autoclave is to 140 DEG C of reaction 10h, cooled and filtered and with different
Butanol washs, and gained filter cake dries 20h at 110 DEG C, and 260 DEG C of roasting 6h, obtain precursor B in air atmosphere.By precursor B
Then 425 DEG C of roastings are warming up in the atmosphere of the vapor of the carbon dioxide of the nitrogen of the air of volume ratio 20%/20%/10%/50%
3h, finally 425 DEG C of roasting 3h obtain active catalyst in the steam atmosphere of the carbon dioxide of 40% nitrogen/10%/50%.Gained is urged
Agent is fed in 1.5vol% butane, 1600hr-1Air speed, checked and rated in fixed bed reactors at 390 DEG C, measure butanes conversion
For 82.5%, yield of maleic anhydride 55.3%.
【Embodiment 4】
The zirconium oxychloride of 0.025mol titanium tetrachloride and 0.075mol is dissolved in deionized water under condition of ice bath, is made into
Concentration is 0.5M solution.Resulting solution is instilled under stirring condition in 25wt% ammonia spirit and detect the pH in solution
Value, stops being added dropwise and stirring when pH value reaches about 9, at room temperature it is still aging overnight after filter, and be washed with deionized water
Wash to silver nitrate solution detection without Cl ions, 20h is dried at 120 DEG C.It is about by dried composite oxides addition concentration
In 1M phosphoric acid solution and 80 DEG C of stirring holding 10h are warming up to, after gained acid treatment composite oxides are by filtration washing, in baking
120 DEG C of dryings in case, it is placed in Muffle furnace the roasting 6h under the conditions of 500 DEG C and obtains composite oxide carrier.
0.6mol oxalic acid is added in 500ml deionized waters and dissolved, adds 0.2mol ammonium metavanadates, heated solution thereto
And stirring and dissolving, carrier 20g is added in vanadium solution upon dissolution and impregnates 20h, in 120 DEG C of dry 20h after filtering, and in horse
Not 550 DEG C of roasting 6h obtain catalyst precursor A in stove.
By with vanadium molar amount precursor A 0.3mol and mixed 400ml isobutanols, 100ml phenmethylols, 95%wt
Phosphoric acid (phosphorus and vanadium stoichiometric mole ratio are about 0.9), 0.003mol phosphomolybdic acids, 0.01mol zinc acetylacetonates, 0.0005mol oxalic acid
Sodium and 0.001mol bismuth acetates are together added in autoclave, and heating autoclave is to 140 DEG C of reaction 10h, cooled and filtered and with different
Butanol washs, and gained filter cake dries 20h at 110 DEG C, and 260 DEG C of roasting 6h, obtain precursor B in air atmosphere.By precursor B
Then 425 DEG C of roastings are warming up in the atmosphere of the vapor of the carbon dioxide of the nitrogen of the air of volume ratio 20%/20%/10%/50%
3h, finally 425 DEG C of roasting 3h obtain active catalyst in the steam atmosphere of the carbon dioxide of 40% nitrogen/10%/50%.Gained is urged
Agent is fed in 1.5vol% butane, 1600hr-1Air speed, checked and rated in fixed bed reactors at 390 DEG C, measure butanes conversion
For 89.6%, yield of maleic anhydride 54.7%.
【Embodiment 5】
The zirconium oxychloride of 0.025mol titanium tetrachloride and 0.075mol is dissolved in deionized water under condition of ice bath, is made into
Concentration is 0.5M solution.Resulting solution is instilled under stirring condition in 25wt% ammonia spirit and detect the pH in solution
Value, stops being added dropwise and stirring when pH value reaches about 9, at room temperature it is still aging overnight after filter, and be washed with deionized water
Wash to silver nitrate solution detection without Cl ions, 20h is dried at 120 DEG C.It is about by dried composite oxides addition concentration
In 1M phosphoric acid solution and 80 DEG C of stirring holding 10h are warming up to, after gained acid treatment composite oxides are by filtration washing, in baking
120 DEG C of dryings in case,
It is placed in Muffle furnace the roasting 6h under the conditions of 500 DEG C and obtains composite oxide carrier.
0.6mol oxalic acid is added in 500ml deionized waters and dissolved, adds 0.2mol ammonium metavanadates, heated solution thereto
And stirring and dissolving, carrier 20g is added in vanadium solution upon dissolution and impregnates 20h, in 120 DEG C of dry 20h after filtering, and in horse
Not 550 DEG C of roasting 6h obtain catalyst precursor A in stove.
By with vanadium molar amount precursor A 0.3mol and mixed 400ml isobutanols, 100ml phenmethylols, 95%wt
Phosphoric acid (phosphorus and vanadium stoichiometric mole ratio are about 1.05), 0.003mol phosphomolybdic acids, 0.01mol zinc acetylacetonates, 0.0005mol oxalic acid
Sodium and 0.001mol bismuth acetates are together added in autoclave, and heating autoclave is to 120 DEG C of reaction 10h, cooled and filtered and with different
Butanol washs, and gained filter cake dries 20h at 110 DEG C, and 260 DEG C of roasting 6h, obtain precursor B in air atmosphere.By precursor B
Then 425 DEG C of roastings are warming up in the atmosphere of the vapor of the carbon dioxide of the nitrogen of the air of volume ratio 20%/20%/10%/50%
3h, finally 425 DEG C of roasting 3h obtain active catalyst in the steam atmosphere of the carbon dioxide of 40% nitrogen/10%/50%.Gained is urged
Agent is fed in 1.5vol% butane, 1600hr-1Air speed, checked and rated in fixed bed reactors at 390 DEG C, measure butanes conversion
For 83.5%, yield of maleic anhydride 56.1%.
【Embodiment 6】
The zirconium oxychloride of 0.025mol titanium tetrachloride and 0.075mol is dissolved in deionized water under condition of ice bath, is made into
Concentration is 0.5M solution.Resulting solution is instilled under stirring condition in 25wt% ammonia spirit and detect the pH in solution
Value, stops being added dropwise and stirring when pH value reaches about 9, at room temperature it is still aging overnight after filter, and be washed with deionized water
Wash to silver nitrate solution detection without Cl ions, 20h is dried at 120 DEG C.It is about by dried composite oxides addition concentration
In 1M phosphoric acid solution and 80 DEG C of stirring holding 10h are warming up to, after gained acid treatment composite oxides are by filtration washing, in baking
120 DEG C of dryings in case, it is placed in Muffle furnace the roasting 6h under the conditions of 500 DEG C and obtains composite oxide carrier.
0.6mol oxalic acid is added in 500ml deionized waters and dissolved, adds 0.2mol ammonium metavanadates, heated solution thereto
And stirring and dissolving, carrier 20g is added in vanadium solution upon dissolution and impregnates 20h, in 120 DEG C of dry 20h after filtering, and in horse
Not 550 DEG C of roasting 6h obtain catalyst precursor A in stove.
By with vanadium molar amount precursor A 0.3mol and mixed 500ml isobutanols, 95%wt phosphoric acid (phosphorus and vanadium
Stoichiometric mole ratio be about 1.05), 0.003mol phosphomolybdic acids, 0.01mol zinc acetylacetonates, 0.0005mol sodium oxalates and
0.001mol bismuth acetates are together added in autoclave, and heating autoclave to 140 DEG C of reaction 10h, cooled and filtered simultaneously uses isobutanol
Washing, gained filter cake dry 20h at 110 DEG C, and 260 DEG C of roasting 6h, obtain precursor B in air atmosphere.Precursor B is subsequent
425 DEG C of roasting 3h are warming up in the atmosphere of the vapor of the carbon dioxide of the nitrogen of the air of volume ratio 20%/20%/10%/50%, most
425 DEG C of roasting 3h obtain active catalyst in the steam atmosphere of the carbon dioxide of 40% nitrogen/10%/50% afterwards.Gained catalyst
Fed in 1.5vol% butane, 1600hr-1Air speed, checked and rated in fixed bed reactors at 390 DEG C, measuring butanes conversion is
84.1%, yield of maleic anhydride 57.2%.
Claims (9)
1. a kind of hydro carbons selective oxidation catalyst, it is characterised in that include following components with total catalyst weight percentages：
A) 35~55% carrier compound；
B) 40%~60% active catalytic components；The active component is based on elemental mole ratios with consisting of formula：
VPaXbYcZdOe
In formula, X is selected from least one of transition metal element；
Y is selected from least one of alkali metal or alkaline-earth metal element；
Z is selected from least one of IVA or VA races element；
Wherein a=0.9~1.4；
B=0.001~0.3；
C=0~0.2；
D=0~0.1；
E is to meet the oxygen element mol ratio in composition needed for each element chemical valence.
2. a kind of preparation method of hydro carbons selective oxidation catalyst as described in claim 1, comprises the following steps：
1) selected catalyst carrier is mixed with inorganic acid, filters and dry after heating stirring reaction 2-24h；
2) vfanadium compound of metering is dissolved by heating in oxalic acid solution, after the completion of reaction to be dissolved, adds obtained load in step 1
Body is impregnated, and the carrier after dipping, which is dried and is calcined 1-24h at 500-600 DEG C, obtains precursor A；
3) airtight heating 2-48h in autoclave, gained production are added after mixing precursor A, organic solvent, phosphoric acid and co-catalyst
Thing is after filter washing is dried, and roasting 1-20h obtains catalyst precursor B at a temperature of no more than 300 DEG C；
4) precursor B is carried out at 350-500 DEG C in the atmosphere of special composition being calcined to obtain final catalyst.
3. hydro carbons selective oxidation method for preparing catalyst as claimed in claim 2, it is characterised in that the catalysis described in step 1
Agent carrier, to be not readily dissolved in the porous oxide of acids used, in inorganic oxide, composite oxides and molecular sieve extremely
Few one kind, the specific surface area of the carrier are more than 50m2/g。
4. hydro carbons selective oxidation method for preparing catalyst as claimed in claim 2, it is characterised in that the nothing described in step 1
Machine acid is selected from least one of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid.
5. hydro carbons selective oxidation method for preparing catalyst as claimed in claim 2, it is characterised in that the vanadium described in step 2
Compound, tetravalence or pentavalent compound selected from vanadium.
6. hydro carbons selective oxidation method for preparing catalyst as claimed in claim 2, the organic solvent described in its step 3, choosing
From primary alconol class, secondary alcohol class, polyalcohols, organic amine, organic acid compound one or more.
7. hydro carbons selective oxidation method for preparing catalyst as claimed in claim 2, phosphoric acid and presoma described in its step 3
A, its it is phosphorous with the ratio of v element be 0.9-1.3.
8. hydro carbons selective oxidation method for preparing catalyst as claimed in claim 2, the autoclave described in its step 3, it adds
Thermal response temperature range is 100-200 DEG C.
9. hydro carbons selective oxidation method for preparing catalyst as claimed in claim 2, it is characterised in that the spy described in step 4
Surely composition atmosphere refers to the mixed atmosphere of lighter hydrocarbons/air, or the mixed atmosphere of air/inert/water vapour, or empty
The mixed atmosphere of gas/inert gas/oxycarbide/water vapour；Described lighter hydrocarbons refer mainly to C1~C5 low-carbon alkanes；Described is lazy
Property gas, selected from nitrogen, helium or argon gas.
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| JP2002348107A (en) * | 2001-05-30 | 2002-12-04 | Tonen Chem Corp | Intercalation complex and method for producing the same |
| CN103537310A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Catalyst and method for preparing maleic anhydride by normal butane oxidization |
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| JP2002348107A (en) * | 2001-05-30 | 2002-12-04 | Tonen Chem Corp | Intercalation complex and method for producing the same |
| CN103537310A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Catalyst and method for preparing maleic anhydride by normal butane oxidization |
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