CN108339558A - A kind of vanadium-phosphor oxide catalyst and preparation method thereof for preparing cis-anhydride by n-butane oxidation - Google Patents
A kind of vanadium-phosphor oxide catalyst and preparation method thereof for preparing cis-anhydride by n-butane oxidation Download PDFInfo
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- CN108339558A CN108339558A CN201710053664.8A CN201710053664A CN108339558A CN 108339558 A CN108339558 A CN 108339558A CN 201710053664 A CN201710053664 A CN 201710053664A CN 108339558 A CN108339558 A CN 108339558A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
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- 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 provides a kind of vanadium-phosphor oxide catalysts for preparing cis-anhydride by n-butane oxidation, and the processing of vanadium-phosphor oxide catalyst matrix is made by using expanding agent.The mass content of v element is 28% 35% in the catalyst, and the mass content of P elements is 15% 25% in the catalyst.The expanding agent includes 1,1, one or more in 1 trimethylolethane, trimethylolpropane, phthalic anhydride, maleic anhydride, tartaric acid, citric acid and citric acid, the mass ratio of the expanding agent and the vanadium-phosphor oxide catalyst matrix is (5 20):(80‑95).The present invention in the last handling process of catalyst by controlling the addition of expanding agent and controlling the subtractive process of expanding agent, to control and improve the specific surface area and pore structure of processing rear catalyst, and then improve the selectivity of activity and generation cis-butenedioic anhydride of the catalyst in being catalyzed butane selective oxidation reaction.
Description
Technical field
The invention belongs to catalyst synthesis technology fields, are related to a kind of vanadium phosphorus oxygen catalysis for preparing cis-anhydride by n-butane oxidation
Agent and preparation method thereof, the catalyst is suitable for the catalytic reaction process of preparing cis-anhydride by n-butane oxidation, more specifically, of the invention
It is related to providing the catalyst of improved catalytic performance.
Background technology
Maleic anhydride (cis-butenedioic anhydride) is a kind of important Organic Chemicals and fine chemical product, is at present in the world
Be only second to the third-largest acid anhydrides of phthalic anhydride and aceticanhydride, mainly for the production of thermosetting resin, unsaturated polyester resin, for pesticide,
Medicine, coating, ink, lube oil additive, papermaking chemical product, textile chemicals, textile finish, food additives with
And the fields such as surfactant.In addition, using cis-butenedioic anhydride as raw material can also produce 1,4-butanediol (GBL), tetrahydrofuran (THF),
A series of widely used fine chemical products such as maleic acid, fumaric acid and tetrahydrochysene acid anhydrides, exploitation prospect is very wide, mesh
Its preceding application range is also constantly expanding.
Maleic anhydride production technique mainly has benzene catalytic oxidation, normal butane catalytic oxidation, C4 olefin catalytic oxygen by raw material point
Change method and phthalic anhydride by-product method.Early stage maleic anhydride production is but expensive due to benzene using benzene as raw material, and toxicity is also larger, both without
Ji does not meet increasingly harsher environmental requirement yet.In recent years, it is original with inexpensive C-4-fraction (normal butane) in world wide
The technique of material production cis-butenedioic anhydride, becomes the absolute mainstream of maleic anhydride production.Nineteen sixty american petroleum-Texas chemical company
(Petrotex Chemical corp.) establishes the commercial plant of butylene oxidation production cis-butenedioic anhydride.U.S.'s Monsanto in 1974
(Monsento corp.) company realizes the industrial production of preparing cis-anhydride by n-butane oxidation fixed bed process.Another normal butane method production is suitable
Acid anhydride and benzene method equipment therefor are similar, and it is also increasingly bright to turn correction butane oxidation legal system cis-butenedioic anhydride trend for benzene oxidatoin method in China's in recent years
It is aobvious.These factors greatly have stimulated the demand of butane legal system cis-butenedioic anhydride vanadium-phosphor oxide catalyst.
Catalyst for preparing cis-anhydride by n-butane oxidation has V-P-O systems, V-Mo-O systems, Ti-P-O systems and a Mo-P-O systems, and the reaction
Maximally efficient most widely used industrial catalyst is vanadium phosphorus oxygen (VPO) series catalysts.The surface nature of catalyst, the addition of auxiliary agent
And activation method of catalyst etc. all has apparent influence to the performance of catalyst.Although at present using normal butane as the life of raw material
Production route occupies leading position in maleic anhydride production, but catalyst needs to be further increased its activity and selectivity, increases suitable
The yield of acid anhydride.
Invention content
For overcome the deficiencies in the prior art, the present invention provides a kind of vanadium phosphorus oxygens for preparing cis-anhydride by n-butane oxidation to urge
Agent and preparation method thereof, during catalysis of the catalyst prepared using the method for the present invention for preparing cis-anhydride by n-butane oxidation is reacted,
N-butane conversion is high, and Selectivity of maleic anhydride is good.The method of the present invention is simple for process, and cost is relatively low, and is easily achieved.
According to an aspect of the present invention, a kind of vanadium-phosphor oxide catalyst for preparing cis-anhydride by n-butane oxidation is provided, is passed through
Expanding treatment is carried out using expanding agent to vanadium-phosphor oxide catalyst matrix to be made.
According to certain embodiments of the present invention, the mass content of v element is 28%-35% in the catalyst, preferably
For 30%-34%；And/or the mass content of P elements is 15%-25%, preferably 18%-22% in the catalyst.
Vanadium and phosphorus in catalyst of the present invention are mainly with (VO)2P2O7Form exist；Further, described (VO)2P2O7
It is by with liquid phase method obtained presoma VO (HPO in organic solvent4)2·0.5H2After O is activated in particular atmosphere
It obtains.
According to certain embodiments of the present invention, the mass ratio of the expanding agent and the vanadium-phosphor oxide catalyst matrix is
(5-20):(80-95), preferably (8-15):(85-92), more preferably (10-13):(87-90).
In some specific embodiments, the expanding agent includes 1,1,1- trimethylolethane, trimethylolpropane, neighbour
It is one or more in phthalate anhydride, maleic anhydride, tartaric acid, citric acid and citric acid, preferably include 1,1,1- tri-
It is one or more in hydroxymethyl ethane, tartaric acid and maleic anhydride.
The present invention in the last handling process of catalyst by controlling the addition of expanding agent and controlling the removing of expanding agent
Journey to control and improve the specific surface area and pore structure of processing rear catalyst, and then improves catalyst in catalysis butane selection
Property oxidation reaction in activity and generate cis-butenedioic anhydride selectivity.
In the course of the research, inventor has found that the change of specific surface area improves butanes conversion to the activity of catalyst and carries
High Selectivity of maleic anhydride etc. has more important influence, therefore, in one embodiment of the invention, the ratio table of catalyst
Area is 5-80m2/g；Preferably 10-70m2/ g, particularly preferably 10-50m2/g.Within this range, the surface of catalyst is advantageous
It is effectively contacted with catalyst activity position in reactant molecule, while can be conducive to inhibit the further of target product cis-butenedioic anhydride
Peroxidating, so as to play the role of improving catalyst activity and generate Selectivity of maleic anhydride.In the present invention, by molding
Catalyst be added and remove expanding agent and be improved, while under the further promotion of metal promoter, obtained catalyst warp
Fixed bed lab scale reactor is checked and rated, and under the same operating conditions, 0-10% can be improved in the conversion ratio of butane, reaches as high as
9.7%, 0-20% can be improved in the selectivity for generating cis-butenedioic anhydride, reaches as high as 19.3%, 0.2- can be improved in the molar yield of cis-butenedioic anhydride
16%, reach as high as 15.0%.
The molar ratio of the vanadium-phosphor oxide catalyst matrix surface before treatment of v element and P elements is to improving catalyst
Activity and the selectivity etc. that generates cis-butenedioic anhydride there is more important influence.Therefore, one according to the present invention preferred reality
It is 1 that example, the v element and P elements, which are applied, in the molar ratio of the vanadium-phosphor oxide catalyst matrix surface:(0.8-4), preferably 1:
(1.5-3), more preferably 1:(2-3).
In the course of the research, inventor has found that the heap density of catalyst is also an important factor for considering catalyst performance, to urge
The heap density of agent directly reacts the quality of the interior actual catalyst that can be loaded of reaction tube of regular length, with catalyst sample
Product itself are related with sample hole and its sample interstitial volume, while also related with catalyst shape, size and mechanical strength.
Suitable heap density can be reacted with corresponding catalysis and reactor matches, and catalyst is made to give full play to its catalytic performance.Heap is close
Spend it is small, although reaction tube in have smaller pressure drop, the actual mechanical strength of catalyst and activated centre quantity may phases
It should reduce, the surface utilisation of catalyst is smaller；Heap density is excessive, and the number of active center in unit volume increases, it is likely that
Since larger internal mass transfer resistance reduces the surface utilisation of catalyst instead, be unfavorable for the raising of catalyst choice because
This, in a preferred embodiment of the invention, the heap density of the catalyst is 0.6-0.85g/cm3, preferably 0.7-
0.8g/cm3.Within this range, bed pressure drop is suitable, and pressure drop range is 3.5-30kPa (bed height is 0.5~4m), favorably
In catalyst its superperformance is played in holding structure integrality simultaneously.
According to certain embodiments of the present invention, further include assistant metal element in the catalyst, the promoter metal
Element includes one or more in indium, niobium, bismuth, cobalt, zinc and tungsten.
According to a preferred embodiment of the present invention, the molar ratio of the assistant metal element and the v element is (1-
5):(100-1000), preferably (2-3):(150-200).
In the course of the research, inventor has found that, by addition assistant metal element, the performance of catalyst can be significantly improved,
Activity can specifically be significantly improved and generate the selectivity of cis-butenedioic anhydride, to improve the yield of cis-butenedioic anhydride.It is helped when addition niobium element is used as
When agent metallic element, effect is especially apparent.In a specific embodiment, under the same operating conditions, be not added with niobium
Catalyst compare, catalyst is checked and rated through fixed bed lab scale reactor, and the conversion ratio of butane improves 7.6-8.2%, is generated suitable
The selectivity of acid anhydride improves 0.9-1.2%, and the yield of cis-butenedioic anhydride improves 5.7-6.2%.
According to another aspect of the present invention, a kind of system of the vanadium-phosphor oxide catalyst for preparing cis-anhydride by n-butane oxidation is provided
Preparation Method, including：
Vanadium source and phosphorus source are added in liquid medium and react by step A, and vanadium-phosphor oxide catalyst presoma is made；
Step B carries out activation process to the vanadium-phosphor oxide catalyst presoma, vanadium-phosphor oxide catalyst matrix is made；
Step C is handled the vanadium-phosphor oxide catalyst matrix using expanding agent, is made described and is used for n butane oxidation
The vanadium-phosphor oxide catalyst of cis-butenedioic anhydride processed.
The rate of charge of v element and P elements has the selectivity etc. for improving the activity of catalyst and generating cis-butenedioic anhydride
More important influence, therefore, according to certain embodiments of the present invention, vanadium source described in step A and phosphorus source feed intake mole
Than being 1:(0.8-2), preferably 1:(1-1.4), more preferably 1:(1.1-1.2), wherein the vanadium source is in terms of v element, it is described
Phosphorus source is in terms of P elements.
According to a preferred embodiment of the present invention, vanadium source includes one kind in the oxide and vanadate of vanadium
Or a variety of, preferably vanadic anhydride and/or ammonium metavanadate；Phosphorus source includes phosphoric acid or phosphorus pentoxide, preferably 85-
At least one of phosphoric acid, pyrophosphoric acid and polyphosphoric acids of 105wt%.
Assistant metal element is added, the performance of catalyst can be significantly improved, can specifically significantly improve activity and is generated
The selectivity of cis-butenedioic anhydride, to improve the yield of cis-butenedioic anhydride.Therefore, in step, it can be optionally added assistant metal element substance.
In some specific embodiments, the molar ratio of the assistant metal element and the v element is (1-5):(100-1000),
Preferably (2-3):(150-200).
According to a preferred embodiment of the present invention, the assistant metal element includes in indium, niobium, bismuth, cobalt, zinc and tungsten
It is one or more.According to certain embodiments of the present invention, the assistant metal element substance is not particularly limited, is selected
Include the compound of above-mentioned assistant metal element, such as metal salt or the metal oxidation of assistant metal element can be selected
Object.In some specific embodiments, the assistant metal element substance can be carboxylate, the nitric acid of assistant metal element
Salt, phosphate, oxide or chloride, the preferably nitrate or oxide of assistant metal element.
According to certain embodiments of the present invention, step A includes：
Vanadium source is added in liquid medium, is heated to reflux by step A1；
Phosphorus source and polyalkenylalcohols are added into the reaction system of step A1, continues to be heated to reflux by step A2, obtain comprising precipitation
Reaction solution；
Assistant metal element substance is optionally added into the reaction system of step A2 by step A3；
Step A4 carries out solid-liquid separation treatment to the reaction solution comprising precipitation, and obtained precipitation is washed and dry
Processing, obtains vanadium-phosphor oxide catalyst presoma.
According to one embodiment of present invention, the liquid medium in step A1 is not particularly limited, selection is originally
Field common organic solvent, preferably Organic Alcohol or polyalcohols solvent, particularly preferably arbitrary volume than isobutyl
Alcohol and benzyl alcohol mixed solvent.In some specific embodiments, preferably the volume ratio of isobutanol and benzyl alcohol is (100-85):
(0-15)。
According to a preferred embodiment of the present invention, the reaction time of the step A1 is 0-5h, preferably 3-5h.
According to certain embodiments of the present invention, for the method and condition in step A2, there is no particular limitation, such as
It can operate as follows：The reaction system of step A1 is cooled to 25-80 DEG C, phosphorus source and polyalkenylalcohols are added thereto, after
Continuous be heated to reflux is reacted；Preferably, the reaction system of step A1 will be cooled to 25-60 DEG C, thereto be added phosphorus source and
Polyalkenylalcohols continues to be heated to reflux and be reacted.
According to a preferred embodiment of the present invention, the reaction time of the step A2 is 5-24h, preferably 16-20h.
Preparation in accordance with the present invention, for the addition sequence of phosphorus source and polyalkenylalcohols, there is no particular limitation, Ke Yixian
Phosphorus source is added and adds polyalkenylalcohols, polyalkenylalcohols can also first be added and add phosphorus source, can also be added simultaneously.
According to some embodiments of the present invention, for the polyalkenylalcohols, there is no particular limitation, is suitable for the invention poly-
Enol is preferably polyethylene glycol.In some specific embodiments, the molecular weight of the polyethylene glycol is 1500-10000, preferably
Molecular weight is the polyethylene glycol of 1500-6000, and more preferable molecular weight is the polyethylene glycol of 1500-2000.
According to a preferred embodiment of the present invention, it is optionally added or is added without into the reaction system of step A2 and help
Agent metallic element substance.In some specific embodiments, it may be selected the reaction system of step A2 being cooled to 25-80 DEG C, to
Assistant metal element substance is wherein added, continues to be heated to reflux and be reacted, obtains the reaction solution for including precipitation.
Preparation in accordance with the present invention, for the processing of step A4, there is no particular limitation, such as can be to the packet
Reaction solution containing precipitation is filtered or centrifugal treating, is precipitated, then with absolute ethyl alcohol by the washing of precipitate, anhydrous second
The volume ratio of alcohol and precipitation is (310):1, three to five progress can be divided, finally the dry 6-24h at 60-150 DEG C, preferably exists
At 120 DEG C dry 12-24h to get.
According to certain embodiments of the present invention, step B includes：
Then the vanadium-phosphor oxide catalyst presoma and mix lubricant are heated, are mixed by step B1
Material；
Step B2 carries out compression process to the mixed material, obtains briquet；
The briquet is placed in air and/or vapor and/or nitrogen atmosphere and carries out activation process, that is, makes by step B3
Vanadium-phosphor oxide catalyst matrix after must activating.
According to a preferred embodiment of the present invention, the quality of the lubricant and the vanadium-phosphor oxide catalyst presoma it
Than for (0-10):(90-100), preferably (0-5):(95-100), more preferably (3-5):(95-97).It is specific real at some
Apply in example, the lubricant include it is one or more in graphite, starch and stearate, in a preferred embodiment,
The lubricant is graphite.
According to certain embodiments of the present invention, by the vanadium-phosphor oxide catalyst presoma and mix lubricant, then exist
Heat 5-24h at a temperature of 120-275 DEG C, is finally pressed into the effigurate briquet of tool.Preferably implement at some
In example, then the vanadium-phosphor oxide catalyst precursor powder and mix lubricant heat at a temperature of 150-250 DEG C
5-7h is finally pressed into cylindrical billet blocks.
According to a preferred embodiment of the present invention, the density of the briquet is 1.0-1.5g/cm3, preferably 1.1-
1.3g/cm3。
According to certain embodiments of the present invention, the activation process includes：The briquet is placed in air and/or water steams
In gas and/or nitrogen atmosphere, it is warming up to 380-480 DEG C with certain heating rate, then in the item for changing or not changing atmosphere
It is kept under part a period of time, preferred time range is 3-8h；Then the briquet after activation is cold under the protection of inert gas
But be down to room temperature to get.In a preferred embodiment, the briquet is placed in air atmosphere first, with 2.5 DEG C/min
Heating rate be warming up to 375 DEG C, then atmosphere is changed to the mixed atmosphere of 50% vapor, 50% air, air speed is
1500h-1Operating condition, be warming up to 425 DEG C with the heating rate of 4 DEG C/min, with this condition keep 1h after, atmosphere is replaced
For 100% nitrogen, continues to roast 5-6h in this atmosphere, room temperature is then cooled under nitrogen protection, after being activated
Vanadium-phosphor oxide catalyst.
According to certain embodiments of the present invention, the step C includes：
The vanadium-phosphor oxide catalyst matrix is mixed with expanding agent, is then pressed into type, it is thick to obtain catalyst by step C1
Base；
Step C2 carries out removing expanding agent processing to the crude green body, the vanadium for being used for preparing cis-anhydride by n-butane oxidation is made
Phosphor oxide catalyst.
According to a preferred embodiment of the present invention, the vanadium-phosphor oxide catalyst matrix is ground into the powder of 40-100 mesh
Then end is mixed with expanding agent, be pressed into the effigurate catalyst crude green body of tool.Molding method is not particularly limited, can
With using well known to a person skilled in the art methods to be molded said mixture, it is preferable to use the formers such as press machine are to above-mentioned
Mixture is molded, and catalyst and its crude green body after molding can have any shape, and can be circle in some specific embodiments
Cylinder, hollow annular cylinder, sphere, tablet, the scapus or irregular shape that cross section is Y-shaped, preferably cylinder
Body, hollow annular cylinder or cross section are the scapus of Y-shaped.The present invention is not special to the size of the catalyst crude green body
Restriction, in some specific embodiments, a diameter of 4-13mm of the preferably described crude green body is highly 2-8mm；Further preferably
A diameter of 5-8mm of the crude green body is highly 3-6mm.
According to certain embodiments of the present invention, the mass ratio of the expanding agent and the vanadium-phosphor oxide catalyst matrix is
(5-20):(80-95), preferably (8-15):(85-92), more preferably (10-13):(87-90).
In some specific embodiments, the expanding agent includes 1,1,1- trimethylolethane, trimethylolpropane, neighbour
It is one or more in phthalate anhydride, maleic anhydride, tartaric acid, citric acid and citric acid, preferably include 1,1,1- tri-
It is one or more in hydroxymethyl ethane, tartaric acid and maleic anhydride.
The present invention in the last handling process of catalyst by controlling the addition of expanding agent and controlling the removing of expanding agent
Journey to control and improve the specific surface area and pore structure of processing rear catalyst, and then improves catalyst in catalysis butane selection
Property oxidation reaction in activity and generate cis-butenedioic anhydride selectivity.
According to a preferred embodiment of the present invention, the expanding agent in the crude green body is removed by solvent impregnation.Selection
Solvent the expanding agent should be made to be slightly soluble in wherein, be conducive to expanding agent in this way and slowly removed from catalyst structure, to
It avoids the catalyst structure caused by expanding agent fast eliminating quickly to cave in, protects the whole mechanical hardness of catalyst
And wearability.Therefore, it is suitable for the invention solvent and is selected from acetone, ethyl alcohol, anhydrous ether, n-butanol, methyl ethyl ketone, dichloromethane
With it is one or more in ethyl acetate, be preferably selected from one or more in acetone, n-butanol and ethyl acetate.
Preparation in accordance with the present invention, the dosage of expanding agent be also influence one of expanding agent removal effect it is important because
Element, the solvent should submerge crude green body to be dealt with, in some specific embodiments, the volume of the solvent and the crude green body
The ratio between be (1-5):1, preferably (1-3):1.
Preparation in accordance with the present invention, during dipping removes expanding agent, control dip time is to catalyst
Structure and performance are extremely important, if the time is too short, expanding agent removing is bad, and the specific surface area and pore structure of catalyst are bad；
If overlong time, have partial lubrication agent with expanding agent dissolve out and be detached from crude green body, to cause catalyst pore structure into
One step changes, and then influences the whole mechanical hardness and wearability of catalyst, it is therefore necessary to control the time of impregnation.One
In a little specific embodiments, the processing time of the solvent impregnation is 1-24h, preferably 10-24h, more preferably 16-24h.
According to a preferred embodiment of the present invention, the expanding agent in the crude green body, the heat are removed by heat treating process
The treatment temperature of processing is 120-300 DEG C, preferably 150-250 DEG C；Processing time is 12-24h, preferably 20-24h.
The method that the present invention prepares the vanadium-phosphor oxide catalyst for preparing cis-anhydride by n-butane oxidation, by shaping of catalyst mistake
The preformed catalyst that addition expanding agent and the method for removing expanding agent obtain in journey, has expanded the pore structure of catalyst, has increased
The specific surface area of catalyst improves the performance of catalyst.
According to another aspect of the present invention, a kind of method of preparing cis-anhydride by n-butane oxidation is provided, including normal butane is existed
Oxidation reaction is carried out in the presence of the above-mentioned vanadium-phosphor oxide catalyst for preparing cis-anhydride by n-butane oxidation.
The present invention is anti-using the above-mentioned vanadium-phosphor oxide catalyst catalysis butane oxidation cis-butenedioic anhydride for preparing cis-anhydride by n-butane oxidation
It should work well, yield of maleic anhydride is higher.It is 400 DEG C in reaction temperature, space velocities 1500h-1, the item of butane concentration 1.7%
Under part, butanes conversion can reach 81.9%, yield of maleic anhydride 63.8%, selectively 77.9%；And without reaming under similarity condition
The improved vanadium-phosphor oxide catalyst of agent, catalytic performance are that butanes conversion is 83.3%, Selectivity of maleic anhydride 58.6%, and cis-butenedioic anhydride is received
Rate is 48.8%, achieves preferable technique effect.
Description of the drawings
Fig. 1 is the XRD spectra of vanadium-phosphor oxide catalyst presoma (A) and vanadium-phosphor oxide catalyst matrix (B)；
Fig. 2 is the SEM figures of vanadium-phosphor oxide catalyst presoma (A) and vanadium-phosphor oxide catalyst matrix (B)；
Fig. 3 is the aperture of vanadium-phosphor oxide catalyst matrix (A) and the vanadium-phosphor oxide catalyst (B) for preparing cis-anhydride by n-butane oxidation
Distribution map.
Specific implementation mode
Below in conjunction with specific embodiment, the present invention is described in further detail：
Crystalline phase detection is measured using the X-ray diffractometer of Dutch Panaco company in embodiment, and specific surface area uses
The full-automatic specific surface area of ASAP-2020 types and pore-size distribution instrument of Quantachrome companies of the U.S. are measured, the surfaces XPS point
Analysis carries out on Britain's V.G.ESCALAB MK type photoelectron spectrographs.
Embodiment 1
127.2g V are added in 3L round-bottomed flasks2O5, the mixed solution of 1350mL isobutanols and 150mL benzyl alcohols, heating
Stirring was added the polyethylene glycol that the molecular weight of 10.0g is 1500, is added dropwise to the phosphoric acid of 105wt% thereto to reflux 3 hours
150g and heating stirring to reflux are kept for 16 hours, and V/P molar ratios are 1/1.15, and gained precipitation is through centrifuging and with anhydrous second
It is 12 hours dry at 120 DEG C after alcohol washing.Catalyst precursor powder after drying is added and catalyst precursor powder
The graphite that last mass ratio is 3/97, is heated 5 hours in 250 DEG C of air after mixing, after that this powder is pressed into high 3mm is straight
Diameter is the cylindrical structure object of 6mm, this works density is 1.2g/cm3, obtained catalyst precursor works is in air gas
Be warming up to 375 DEG C in atmosphere with the heating rate of 2.5 DEG C/min, after atmosphere is changed to the gaseous mixture of 50% vapor, 50% air
Atmosphere, air speed 1500h-1Operating condition, be warming up to 425 DEG C with the heating rate of 4 DEG C/min, with this condition keep 1 hour
Afterwards, atmosphere is changed to 100% nitrogen, continues roasting 6 hours in this atmosphere, is then cooled to room under nitrogen protection
Temperature, the vanadium-phosphor oxide catalyst after being activated.This catalyst is repeatedly crushed, it is 11/ to be added with catalyst substrates powder mass ratio
The 1 of 89, the sieving of 1,1- trihydroxy ethane are uniformly mixed, and continue the preformed catalyst for being pressed into the scapus that cross section is Y-shaped,
A diameter of 6mm of this preformed catalyst works, a height of 5mm.After it is impregnated 21 hours in acetone (catalyst heap volume/
Solvent volume=1/1.5), obtained catalyst structure object continues drying 24 hours under 60 DEG C of vacuum conditions, is obtained after dry
For the vanadium-phosphor oxide catalyst of preparing cis-anhydride by n-butane oxidation, catalyst bulk density 0.75g/cm3, specific surface area 33.5m2/
G, catalyst external surface P/V (atomic ratio) are 3.1/1, and the mass content of vanadium is 33% in catalyst, and the mass content of phosphorus is
21%.Gained catalyst is checked and rated through 120mL fixed bed lab scale reactors, the charging of 1.7% butane, 1500h-1Air speed under, 400
DEG C when, butanes conversion reaches 81.9%, Selectivity of maleic anhydride 77.9%, yield of maleic anhydride 63.8%；At 410 DEG C, butane turns
Rate reaches 87.3%, Selectivity of maleic anhydride 70.8%, yield of maleic anhydride 61.8%.
Comparative example 1
Do not do that de- expanding agent processing accordingly is outer, other implement step except being not added with 1,1,1- trihydroxy ethane and making expanding agent
Suddenly with embodiment 1.Obtained catalyst bulk density is 0.79g/cm3, specific surface area 22.5m2/ g, catalyst external surface P/V
(atomic ratio) is 2.2/1.Gained catalyst is checked and rated through 120mL fixed bed lab scale reactors, the charging of 1.7% butane, 1500h-1's
Under air speed, at 400 DEG C, butanes conversion reaches 83.3%, Selectivity of maleic anhydride 58.6%, yield of maleic anhydride 48.8%；410
DEG C when, butanes conversion reaches 89.2%, Selectivity of maleic anhydride 56.8%, yield of maleic anhydride 50.7%.
Embodiment 2
127.2g V are added in 3L round-bottomed flasks2O5, the mixed solution of 1250mL isobutanols and 250mL benzyl alcohols, heating
Stirring was added the polyethylene glycol that the molecular weight of 20.0g is 2000, is added dropwise to the phosphoric acid of 105wt% thereto to reflux 3 hours
156g and heating stirring to reflux are kept for 20 hours, and V/P molar ratios are 1/1.20, and gained precipitation is through centrifuging and with anhydrous second
It is 12 hours dry at 120 DEG C after alcohol washing.Catalyst precursor powder after drying is added and catalyst precursor powder
The graphite that last mass ratio is 3/97, is heated 5 hours in 250 DEG C of air after mixing, after that this powder is pressed into high 3mm is straight
Diameter is the cylindrical structure object of 13mm, this works density is 1.22g/cm3, obtained catalyst precursor works is in air
Be warming up to 375 DEG C in atmosphere with the heating rate of 2.5 DEG C/min, after atmosphere is changed to the mixing of 50% vapor, 50% air
Atmosphere, air speed 1500h-1Operating condition, be warming up to 425 DEG C with the heating rate of 4 DEG C/min, keep 1 small with this condition
Atmosphere is changed to 100% nitrogen by Shi Hou, is continued roasting 5 hours in this atmosphere, is then cooled to room under nitrogen protection
Temperature, the vanadium-phosphor oxide catalyst after being activated.This catalyst is repeatedly crushed, it is 5/95 to be added with catalyst substrates powder mass ratio
Tartaric acid sieving be uniformly mixed, and continue to be pressed into hollow cylindrical preformed catalyst, this preformed catalyst works
A diameter of 6mm, a height of 4mm, hollow diameters 3mm.(catalyst heap volume/solvent after it is impregnated 3 hours in n-butanol
Volume=1/1), obtained catalyst structure object continues drying 24 hours under 60 DEG C of vacuum conditions, is obtained after dry for just
The vanadium-phosphor oxide catalyst of butane oxidation cis-butenedioic anhydride, catalyst bulk density 0.74g/cm3, specific surface area 29.0m2/ g, catalysis
Agent outer surface P/V (atomic ratio) is 2.6/1, and the mass content of vanadium is 34% in catalyst, and the mass content of phosphorus is 22%.Gained
Catalyst is checked and rated through 120mL fixed bed lab scale reactors, the charging of 1.8% butane, 1750h-1Air speed under, at 410 DEG C, butane
Conversion ratio reaches 84.7%, Selectivity of maleic anhydride 65.4%, yield of maleic anhydride 55.4%；At 415 DEG C, butanes conversion reaches
86.6%, Selectivity of maleic anhydride 63.9%, yield of maleic anhydride 55.3%.
Comparative example 2
In addition to being not added with tartaric acid and making expanding agent and do not do de- expanding agent processing accordingly, the same embodiment of other implementation steps
2.Obtained catalyst bulk density is 0.76g/cm3, specific surface area 27.2m2/ g, catalyst external surface P/V (atomic ratio) are
2.6/1.Gained catalyst is checked and rated through 120mL fixed bed lab scale reactors, the charging of 1.8% butane, 1750h-1Air speed under,
At 410 DEG C, butanes conversion reaches 86.1%, Selectivity of maleic anhydride 62.8%, yield of maleic anhydride 54.1%；At 415 DEG C, butane
Conversion ratio reaches 87.6%, Selectivity of maleic anhydride 62.4%, yield of maleic anhydride 54.7%.
Embodiment 3
127.2g V are added in 3L round-bottomed flasks2O5, the mixed solution of 1250mL isobutanols and 250mL benzyl alcohols, heating
Stirring was added the polyethylene glycol that the molecular weight of 10.0g is 6000, is added dropwise to the phosphoric acid of 105wt% thereto to reflux 3 hours
130g and heating stirring, which extremely flow back, to be kept for 10 hours, and V/P molar ratios are 1/1, and gained is precipitated through centrifuging and using absolute ethyl alcohol
It is 12 hours dry at 120 DEG C after washing.Catalyst precursor powder after drying is added and catalyst precursor powder
The graphite that mass ratio is 5/95, is heated 5 hours in 250 DEG C of air after mixing, after this powder is pressed into high 3mm diameters
For the cylindrical structure object of 6mm, this works density is 1.12g/cm3, obtained catalyst precursor works is in air gas
Be warming up to 375 DEG C in atmosphere with the heating rate of 2.5 DEG C/min, after atmosphere is changed to the gaseous mixture of 50% vapor, 50% air
Atmosphere, air speed 1500h-1Operating condition, be warming up to 425 DEG C with the heating rate of 4 DEG C/min, with this condition keep 1 hour
Afterwards, atmosphere is changed to 100% nitrogen, continues roasting 5 hours in this atmosphere, is then cooled to room under nitrogen protection
Temperature, the vanadium-phosphor oxide catalyst after being activated.This catalyst is repeatedly crushed, it is 15/ to be added with catalyst substrates powder mass ratio
85 maleic anhydride sieving is uniformly mixed, and continues to be pressed into the preformed catalyst for the scapus that cross section is Y-shaped, this at
A diameter of 6mm of type catalyst structure object, a height of 4mm.(catalyst heap volume/solvent body after it is impregnated 1 hour in acetone
Product=1/1), obtained catalyst structure object continues drying 24 hours under 60 DEG C of vacuum conditions, obtains being used for positive fourth after dry
The vanadium-phosphor oxide catalyst of alkoxide cis-butenedioic anhydride, catalyst bulk density 0.72g/cm3, specific surface area 41.7m2/ g, catalyst
Outer surface P/V (atomic ratio) is 1.8/1, and the mass content of vanadium is 33% in catalyst, and the mass content of phosphorus is 18%.Gained is urged
Agent is checked and rated through 120mL fixed bed lab scale reactors, the charging of 1.8% butane, 1500h-1Air speed under, at 410 DEG C, butane turn
Rate reaches 89.2%, Selectivity of maleic anhydride 60.4%, yield of maleic anhydride 53.9%；At 415 DEG C, butanes conversion reaches
91.3%, Selectivity of maleic anhydride 58.2%, yield of maleic anhydride 53.1%.
Comparative example 3
In addition to being not added with maleic anhydride and making expanding agent and do not do de- expanding agent processing accordingly, other implementation steps are same
Embodiment 3.Obtained catalyst bulk density is 0.73g/cm3, specific surface area 14.5m2/ g, catalyst external surface P/V are (former
Sub- ratio) it is 1.8/1.Gained catalyst is checked and rated through 120mL fixed bed lab scale reactors, the charging of 1.8% butane, 1500h-1Air speed
Under, at 410 DEG C, butanes conversion reaches 88.2%, Selectivity of maleic anhydride 59.7%, yield of maleic anhydride 52.7%；At 415 DEG C
When, butanes conversion reaches 89.9%, Selectivity of maleic anhydride 56.8%, yield of maleic anhydride 51.1%.
By embodiment 1-3 it is found that after addition expanding agent progress expanding treatment compared with the data of comparative example 1-3, butane turns
Rate and generation Selectivity of maleic anhydride improve, and yield of maleic anhydride is also improved.This is because the processing of reaming improves the more of catalyst
Permeability so that the specific surface area of catalyst increases, to have larger contribution to the active surface area at catalysis reaction occurs.Together
When feed gas (hydrocarbon and oxygen) enter the inner surface of catalyst body (piece or grain) efficiently used via duct, and react production
Object promotes reactant in the absorption of catalyst surface and product in catalyst table via diffusion into the surface, effective diffusion of catalyst
The desorption in face, to be conducive to reaction-ure conversion-age and generate the raising of Selectivity of maleic anhydride, the final raising for promoting yield of maleic anhydride.
Embodiment 4
Except the phosphoric acid for the 105wt% that 104.3g is added into reaction system, V/P molar ratios are Qi Tabu outside 1/0.8
Suddenly with embodiment 1.Obtained preformed catalyst heap density is 0.75g/cm3, specific surface area 26.9m2/ g, catalyst appearance
Face P/V (atomic ratio) is 1.5/1, and the mass content of vanadium is 35% in catalyst, and the mass content of phosphorus is 15%.Gained catalyst
It is checked and rated through 120mL fixed bed lab scale reactors, the charging of 1.7% butane, 1500h-1Air speed under, at 400 DEG C, butanes conversion
Reach 76.3%, Selectivity of maleic anhydride 59.8%, yield of maleic anhydride 45.6%.
Embodiment 5
Except the phosphoric acid for the 105wt% that 260.9g is added into reaction system, V/P molar ratios are 1/2, and other steps are same
Embodiment 1.Obtained preformed catalyst heap density is 0.76g/cm3, specific surface area 29.1m2/ g, catalyst external surface P/V
(atomic ratio) is 3.8/1, and the mass content of vanadium is 29% in catalyst, and the mass content of phosphorus is 20%.Gained catalyst passes through
120mL fixed bed lab scale reactors are checked and rated, the charging of 1.7% butane, 1500h-1Air speed under, at 400 DEG C, butanes conversion reaches
To 64.7%, Selectivity of maleic anhydride 79.0%, yield of maleic anhydride 51.1%.
Comparative example 4
Except the phosphoric acid for the 105wt% that 65.2g is added into reaction system, V/P molar ratios are 1/0.5, other steps
With embodiment 1.Obtained preformed catalyst heap density is 0.72g/cm3, specific surface area 22.3m2/ g, catalyst external surface
P/V (atomic ratio) is 0.8/1, and the mass content of vanadium is 48% in catalyst, and the mass content of phosphorus is 12%.Gained catalyst passes through
120mL fixed bed lab scale reactors are checked and rated, the charging of 1.7% butane, 1500h-1Air speed under, at 400 DEG C, butanes conversion reaches
To 63.2%, Selectivity of maleic anhydride 51.6%, yield of maleic anhydride 32.6%.
Comparative example 5
In addition to the phosphoric acid of 105wt% of 391.3g is added into reaction system, V/P molar ratios are 1/3, other steps
With embodiment 1.Obtained preformed catalyst heap density is 0.74g/cm3, specific surface area 28.4m2/ g, catalyst external surface
P/V (atomic ratio) is 4.2/1, and the mass content of vanadium is 30% in catalyst, and the mass content of phosphorus is 26%.Gained catalyst passes through
120mL fixed bed lab scale reactors are checked and rated, the charging of 1.7% butane, 1500h-1Air speed under, at 400 DEG C, butanes conversion reaches
To 60.1%, Selectivity of maleic anhydride 73.7%, yield of maleic anhydride 44.3%.
By embodiment 1,4,5 it is found that V/P molar ratios are in the scope of the invention 1 compared with the data of comparative example 4-5:
In 0.8-2.0, gained catalyst is at 400 DEG C, butanes conversion 64.7-81.9%, yield of maleic anhydride 45.6-63.8%；
And beyond after V/P molar ratio ranges of the present invention, butanes conversion is then 60.1-63.2%, yield of maleic anhydride 32.6-44.3%.
It selects V/P molar ratios in the scope of the invention, is conducive to while forming catalyst activity phase, be formed in catalyst surface
A certain amount of P enrichments.The P of enrichment is typically derived from pyrophosphate and phosphate radical particle formed in catalyst activation process,
The excessive phosphorus in surface can not only prevent the opposite more stable β-VOPO of body4Transformation, while more can effective limiting surface object
The excessive oxidation of kind, is conducive to V in catalyst activity phaseIVThe stabilization at center, for promoting the selectivity of catalyst to have significantly
Effect, therefore the Selectivity of maleic anhydride of catalyst and final yield of maleic anhydride can be significantly improved.
Embodiment 6
Except the 1 of addition, 1,1- trihydroxy ethane and catalyst substrates powder mass ratio are outside 20/80, other steps are the same as implementation
Example 1, the catalyst bulk density after drying are 0.60g/cm3, specific surface area 18.3m2/ g, catalyst external surface P/V (atoms
Than) it is 2.3/1, the mass content of vanadium is 35% in catalyst, and the mass content of phosphorus is 25%.Gained catalyst is solid through 120mL
Fixed bed lab scale reactor is checked and rated, the charging of 1.7% butane, 1500h-1Air speed under, at 400 DEG C, butanes conversion reaches
78.8%, Selectivity of maleic anhydride 68.2%, yield of maleic anhydride 53.7%.
Embodiment 7
Except the 1 of addition, 1,1- trihydroxy ethane and catalyst substrates powder mass ratio are outside 15/85, other steps are the same as implementation
Example 1, the catalyst bulk density after drying are 0.69g/cm3, specific surface area 22.0m2/ g, catalyst external surface P/V (atoms
Than) it is 2.2/1, the mass content of vanadium is 33% in catalyst, and the mass content of phosphorus is 21%.Gained catalyst is solid through 120mL
Fixed bed lab scale reactor is checked and rated, the charging of 1.7% butane, 1500h-1Air speed under, at 400 DEG C, butanes conversion reaches
79.9%, Selectivity of maleic anhydride 68.7%, yield of maleic anhydride 54.9%.
Embodiment 8
Except the 1 of addition, 1,1- trihydroxy ethane and catalyst substrates powder mass ratio are other same embodiments of step outside 8/92
1, the catalyst bulk density after drying is 0.79g/cm3, specific surface area 22.4m2/ g, catalyst external surface P/V (atomic ratio)
It is 2.6/1, the mass content of vanadium is 32% in catalyst, and the mass content of phosphorus is 20%.Gained catalyst is through 120mL fixed beds
Lab scale reactor is checked and rated, the charging of 1.7% butane, 1500h-1Air speed under, at 400 DEG C, butanes conversion reaches 81.4%, suitable
Acid anhydride selectivity 69.2%, yield of maleic anhydride 56.3%.
Embodiment 9
Except the 1 of addition, 1,1- trihydroxy ethane and catalyst substrates powder mass ratio are other same embodiments of step outside 5/95
1, the catalyst bulk density after drying is 0.84g/cm3, specific surface area 15.7m2/ g, catalyst external surface P/V (atomic ratio)
It is 2.2/1, the mass content of vanadium is 31% in catalyst, and the mass content of phosphorus is 20%.Gained catalyst is through 120mL fixed beds
Lab scale reactor is checked and rated, the charging of 1.7% butane, 1500h-1Air speed under, at 400 DEG C, butanes conversion reaches 84.1%, suitable
Acid anhydride selectivity 63.3%, yield of maleic anhydride 53.2%.
Comparative example 6
Except the 1 of addition, 1,1- trihydroxy ethane and catalyst substrates powder mass ratio are outside 25/75, other steps are the same as implementation
Example 1, the catalyst bulk density after drying are 0.56g/cm3, specific surface area 11.5m2/ g, catalyst external surface P/V (atoms
Than) it is 2.2/1, the mass content of vanadium is 35% in catalyst, and the mass content of phosphorus is 24%.Gained catalyst is solid through 120mL
Fixed bed lab scale reactor is checked and rated, the charging of 1.7% butane, 1500h-1Air speed under, at 400 DEG C, butanes conversion reaches
75.7%, Selectivity of maleic anhydride 63.3%, yield of maleic anhydride 47.9%.
Comparative example 7
Except the 1 of addition, 1,1- trihydroxy ethane and catalyst substrates powder mass ratio are other same embodiments of step outside 3/97
1, the catalyst bulk density after drying is 0.86g/cm3, specific surface area 18.1m2/ g, catalyst external surface P/V (atomic ratio)
It is 2.4/1, the mass content of vanadium is 33% in catalyst, and the mass content of phosphorus is 21%.Gained catalyst is through 120mL fixed beds
Lab scale reactor is checked and rated, the charging of 1.7% butane, 1500h-1Air speed under, at 400 DEG C, butanes conversion reaches 86.7%, suitable
Acid anhydride selectivity 59.8%, yield of maleic anhydride 51.8%.
Embodiment 1,6-9 are that addition 1,1,1- trihydroxies ethane carries out expanding treatment as expanding agent and its addition exists
Experimental example in the scope of the invention, comparative example 6-7 are the experiment of the addition of 1,1,1- trihydroxy ethane within the scope of the present invention
Example, comparative example 1 is that the experimental example of expanding agent is not added, by general knowledge known in this field and experimental data comparison it is found that in catalyst
The resistance of interior diffusion can become the rate-limiting factor of reaction in main body, not exist compared to expanding treatment or expanding agent is not carried out
Catalyst in the scope of the invention carries out expanding treatment, the shape inside catalyst granules using the expanding agent in the scope of the invention
At porous duct, is conducive to reaction gas and preferably spreads to contact with the inner surface of catalyst, this not only increases urge
The surface utilisation of agent preferably overcomes the inside diffusional resistance of catalyst simultaneously, so as to improve reactant and product
Diffusion path can significantly improve the Selectivity of maleic anhydride and yield of maleic anhydride of catalyst.
Embodiment 10
127.2g V are added in 3L round-bottomed flasks2O5, the mixed solution of 1350mL isobutanols and 150mL benzyl alcohols, heating
Stirring was to reflux 4 hours, five oxidations two of the molecular weight of addition 15.0g is 6000 thereto polyethylene glycol and 1.85g
Niobium, the molar ratio of assistant metal element and V are 1 in this embodiment：100, it is added dropwise to the phosphatase 11 50g of 105wt% and heats and stir
Mix to reflux and kept for 20 hours, V/P molar ratios are 1/1.15, gained precipitation through centrifugation and after being washed with absolute ethyl alcohol
It is 12 hours dry at 120 DEG C.Catalyst precursor powder after drying is added with catalyst precursor powder quality ratio and is
4/96 graphite heats 5 hours in 250 DEG C of air after mixing, after this powder is pressed into a diameter of 3mm's of high 3mm
Cylindrical structure object, this works density are 1.16g/cm3, obtained catalyst precursor works in air atmosphere with
The heating rate of 2.5 DEG C/min is warming up to 375 DEG C, after atmosphere is changed to the mixed atmosphere of 50% vapor, 50% air, it is empty
Speed is 1500h-1Operating condition, be warming up to 425 DEG C with the heating rate of 4 DEG C/min, with this condition keep 1 hour after, will
Atmosphere is changed to 100% nitrogen, continues roasting 5 hours in this atmosphere, is then cooled to room temperature under nitrogen protection, obtains
Vanadium-phosphor oxide catalyst after activation.This catalyst is repeatedly crushed, the winestone for being 5/95 with catalyst substrates powder mass ratio is added
Acid sieving is uniformly mixed, and continues to be pressed into cylindrical preformed catalyst, a diameter of 5mm of this preformed catalyst works,
A height of 4mm.(catalyst heap volume/solvent volume=1/1), obtained catalyst after it is impregnated 16 hours in ethyl acetate
Works continues drying 24 hours under 60 DEG C of vacuum conditions, and the catalyst bulk density after drying is 0.74g/cm3, specific surface
Product is 25.1m2/ g, catalyst external surface P/V (atomic ratio) are 2.0/1, and the mass content of vanadium is 33% in catalyst, the matter of phosphorus
It is 21% to measure content.Gained catalyst is checked and rated through 120mL fixed bed lab scale reactors, the charging of 1.9% butane, 1750h-1Air speed
Under, at 410 DEG C, butanes conversion reaches 82.6%, Selectivity of maleic anhydride 64.4%, yield of maleic anhydride 53.2%；At 415 DEG C
When, butanes conversion reaches 85.3%, Selectivity of maleic anhydride 62.7%, yield of maleic anhydride 53.5%.
Comparative example 8
In addition to not making except the niobium oxide that 1.85g is not added and corresponding expanding treatment, other steps are the same as embodiment 4.Catalyst
Heap density is 0.75g/cm3, specific surface area 17.2m2/ g, catalyst external surface P/V (atomic ratio) are 2.0/1.Gained is catalyzed
Agent is checked and rated through 120mL fixed bed lab scale reactors, the charging of 1.9% butane, 1750h-1Air speed under, at 410 DEG C, conversion of butane
Rate reaches 72.9%, Selectivity of maleic anhydride 66.3%, yield of maleic anhydride 48.3%；At 415 DEG C, butanes conversion reaches
75.6%, Selectivity of maleic anhydride 64.8%, yield of maleic anhydride 49.0%.
Embodiment 10 and one group of control experiment example that comparative example 8 is the charging of 1.9% butane, embodiment 10 are added tartaric acid and do
Expanding agent processing, and niobium pentaoxide is added using as assistant metal element, compared to comparative example 8, the specific surface of catalyst
Product improves 45.9%, and butanes conversion improves 12.8-13.3%, and yield of maleic anhydride improves 9.2-10.1%.Using niobium as
Metal promoter adds, Nb5+It may replace VO2+In V4+, so as to form V1-xNbxO2P2O7+x。It is coordinated undersaturated cation
Can exist as the L acidic sites of relatively low acid strength, be conducive to the activation of c h bond when initial oxidation of alkanes, show as catalyst
It is catalyzed the raising of butane oxidation reaction butanes conversion.
Embodiment 11
Except the indium acetate that 4.08g is added replaces the niobium pentaoxide of 1.85g, and use is with catalyst substrates powder mass ratio
Catalyst structure is impregnated 10 hours outer (catalyst heaps by 5/95 maleic anhydride as expanding agent in ethyl acetate
Volume/solvent volume=1/1) outside, other steps are with embodiment 10, and the molar ratio of assistant metal element and V are in this embodiment
1：100.Obtained catalyst bulk density is 0.73g/cm3, specific surface area 11.0m2/ g, catalyst external surface P/V (atoms
Than) it is 2.0/1, the mass content of vanadium is 32% in catalyst, and the mass content of phosphorus is 21%.Gained catalyst is solid through 120mL
Fixed bed lab scale reactor is checked and rated, the charging of 1.9% butane, 1750h-1Air speed under, at 410 DEG C, butanes conversion reaches
82.6%, Selectivity of maleic anhydride 64.4%, yield of maleic anhydride 53.2%；At 415 DEG C, butanes conversion reaches 85.3%, cis-butenedioic anhydride
Selectivity 62.7%, yield of maleic anhydride 53.5%.
Embodiment 12
Outside the indium acetate for replacing 4.08g in addition to the indium acetate that 0.51g is added, other steps are the same as embodiment 11, this embodiment
The molar ratio of middle assistant metal element and V are 1：800.Obtained preformed catalyst heap density is 0.76g/cm3, specific surface area
For 21.7m2/ g, catalyst external surface P/V (atomic ratio) are 2.2/1, and the mass content of vanadium is 34% in catalyst, the quality of phosphorus
Content is 20%.Gained catalyst is checked and rated through 120mL fixed bed lab scale reactors, the charging of 1.9% butane, 1750h-1Air speed
Under, at 410 DEG C, butanes conversion reaches 82.4%, Selectivity of maleic anhydride 65.3%, yield of maleic anhydride 53.8%.
Embodiment 13
In addition to the indium acetate that 5.44g is added replaces the indium acetate of 4.08g, other steps are with embodiment 11, in this embodiment
The molar ratio of assistant metal element and V are 2：150.Obtained preformed catalyst heap density is 0.75g/cm3, specific surface area is
10.7m2/ g, catalyst external surface P/V (atomic ratio) are 2.1/1, and the mass content of vanadium is 33% in catalyst, and the quality of phosphorus contains
Amount is 21%.Gained catalyst is checked and rated through 120mL fixed bed lab scale reactors, the charging of 1.9% butane, 1750h-1Air speed under,
At 410 DEG C, butanes conversion reaches 81.8%, Selectivity of maleic anhydride 66.3%, yield of maleic anhydride 54.2%.
Embodiment 14
In addition to the indium acetate that 24.5g is added replaces the indium acetate of 4.08g, other steps are with embodiment 11, in this embodiment
The molar ratio of assistant metal element and V are 6：100.Obtained preformed catalyst heap density is 0.75g/cm3, specific surface area is
10.5m2/ g, catalyst external surface P/V (atomic ratio) are 2.2/1, and the mass content of vanadium is 31% in catalyst, and the quality of phosphorus contains
Amount is 22%.Gained catalyst is checked and rated through 120mL fixed bed lab scale reactors, the charging of 1.9% butane, 1750h-1Air speed under,
At 410 DEG C, butanes conversion reaches 79.4%, Selectivity of maleic anhydride 61.2%, yield of maleic anhydride 48.6%.
Embodiment 15
In addition to the indium acetate that 0.08g is added replaces the indium acetate of 4.08g, other steps are with embodiment 11, in this embodiment
The molar ratio of assistant metal element and V are 1：5140.Obtained preformed catalyst heap density is 0.74g/cm3, specific surface area
For 19.8m2/ g, catalyst external surface P/V (atomic ratio) are 2.2/1, and the mass content of vanadium is 34% in catalyst, the quality of phosphorus
Content is 20%.Gained catalyst is checked and rated through 120mL fixed bed lab scale reactors, the charging of 1.9% butane, 1750h-1Air speed
Under, at 410 DEG C, butanes conversion reaches 76.5%, Selectivity of maleic anhydride 62.5%, yield of maleic anhydride 47.8%.
Embodiment 16
In addition to the indium acetate for being not added with 4.08g, other operations are the same as embodiment 11.Catalyst bulk density is 0.73g/cm3,
Specific surface area is 22.4m2/ g, catalyst external surface P/V (atomic ratio) are 1.9/1, and the mass content of vanadium is 33% in catalyst,
The mass content of phosphorus is 22%.Gained catalyst is checked and rated through 120mL fixed bed lab scale reactors, the charging of 1.9% butane, 1750h-1
Air speed under, at 410 DEG C, butanes conversion reaches 82.8%, Selectivity of maleic anhydride 63.2%, yield of maleic anhydride 52.3%；
At 415 DEG C, butanes conversion reaches 84.7%, Selectivity of maleic anhydride 62.6%, yield of maleic anhydride 53.0%.
Embodiment 11-16 is one group of experimental example of 1.9% butane charging, has data comparison it is found that due to butane inlet amount
It is larger, assistant metal element is added, metal promoter and vanadium are centrally formed suitable ratio, play structural work in the catalyst
With being conducive to improve butanes conversion, Selectivity of maleic anhydride and yield of maleic anhydride；However, the addition of assistant metal element it is excessive or
Very few, butanes conversion, Selectivity of maleic anhydride and yield of maleic anhydride can all decline.Due to each category auxiliary agent electronics itself and atomic property
Difference, required suitable ratio is different after being cooperateed with from vanadium center.Some metal promoters are mutually formed such as with catalyst activity
[(VO)1-x]Mx]2P2O7Solid solution, control the diffusion of oxygen atom, to greatest extent reduce butane non-selective oxidation；Have
Metal promoter inhibits the formation of nonactive phase, promotes VIVThe stabilization at center, while the activity and surface acidity of catalyst are adjusted, it carries
High initial dehydrogenation rate.Therefore the addition of metal promoter has the preferred scope that it is limited.
Embodiment 17
Prepared by catalyst substrates powder and the activation of catalyst stage is the same as embodiment 1.Vanadium-phosphor oxide catalyst after activation is multiple
It is broken, be added to be sieved with the stearic acid that catalyst substrates powder mass ratio is 10/90 and be uniformly mixed, and continue to be pressed into cross section be
The preformed catalyst of the scapus of Y-shaped, a diameter of 6mm of this preformed catalyst works, a height of 5mm.By this catalyst in sky
180 DEG C are risen to the heating rate of 2 DEG C/min in gas, is kept for 6 hours at this temperature, the heating speed with 4 DEG C/min is continued
Degree rises to 190 DEG C, is kept for 6 hours at this temperature, rear to continue to be warming up to 200 DEG C with the heating rate of 2 DEG C/min, warm herein
Continue to be kept for 6 hours under degree, the heating rate for continuing 2 DEG C/min rises to 250 DEG C, is kept for 2 hours at this temperature.What is obtained urges
Agent heap density is 0.74g/cm3, specific surface area 24.0m2/ g, catalyst external surface P/V (atomic ratio) are 2.6/1.Gained
Catalyst is checked and rated through 120mL fixed bed lab scale reactors, the charging of 1.7% butane, 1500h-1Air speed under, at 400 DEG C, butane
Conversion ratio reaches 81.8%, Selectivity of maleic anhydride 75.7%, yield of maleic anhydride 61.9%；At 410 DEG C, butanes conversion reaches
85.3%, Selectivity of maleic anhydride 66.8%, yield of maleic anhydride 57.0%.
Any numerical value mentioned in the present invention, if between any minimum and any of the highest value be there are two
The interval of unit includes then each all values for increasing a unit from minimum to peak.For example, if statement is a kind of
The value of the state-variables such as the amount of component, or temperature, pressure, time is 50-90, in the present specification it means that specific
List 51-89,52-88 ... and the numerical value such as 69-71 and 70-71.For the value of non-integer, can with due regard to
0.1,0.01,0.001 or 0.0001 is a unit.This is only some special examples indicated.In this application, with similar side
The all possible combinations of formula, the numerical value between cited minimum and peak are considered to have disclosed.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (15)
1. a kind of vanadium-phosphor oxide catalyst for preparing cis-anhydride by n-butane oxidation, by using expanding agent to vanadium-phosphor oxide catalyst matrix
Expanding treatment is carried out to be made.
2. catalyst according to claim 1, which is characterized in that the expanding agent and the vanadium-phosphor oxide catalyst matrix
Mass ratio is (5-20):(80-95), preferably (8-15):(85-92), more preferably (10-13):(87-90)；And/or institute
State expanding agent include 1,1,1- trimethylolethanes, trimethylolpropane, phthalic anhydride, maleic anhydride, tartaric acid,
It is one or more in citric acid and citric acid, preferably include 1,1,1- trimethylolethane, tartaric acid and maleic anhydride
In it is one or more.
3. catalyst according to claim 1 or 2, which is characterized in that the mass content of v element is in the catalyst
28%-35%, preferably 30%-34%；And/or the mass content of P elements is 15%-25% in the catalyst, preferably
18%-22%.
4. according to the catalyst described in any one of claim 1-3, which is characterized in that further include auxiliary agent in the catalyst
The molar ratio of metallic element, the assistant metal element and the v element is (1-5):(100-1000), preferably (2-3):
(150-200)；And/or the assistant metal element includes one or more in indium, niobium, bismuth, cobalt, zinc and tungsten.
5. according to the catalyst described in any one of claim 1-4, which is characterized in that the specific surface area of the catalyst is
5-80m2/ g, preferably 10-70m2/ g, more preferably 10-50m2/g；The v element and P elements are in the catalyst surface
Molar ratio be 1:(0.8-4), preferably 1:(1.5-3), more preferably 1:(2-3)；And/or the heap density of the catalyst is
0.6-0.85g/cm3, preferably 0.7-0.8g/cm3。
6. a kind of preparation method of the catalyst as described in any one of claim 1-5, including：
Vanadium source and phosphorus source are added in liquid medium and react by step A, and vanadium-phosphor oxide catalyst presoma is made；
Step B carries out activation process to the vanadium-phosphor oxide catalyst presoma, vanadium-phosphor oxide catalyst matrix is made；
Step C is handled the vanadium-phosphor oxide catalyst matrix using expanding agent, is made described suitable for n butane oxidation system
The vanadium-phosphor oxide catalyst of acid anhydride.
7. preparation method according to claim 6, which is characterized in that mole that vanadium source and phosphorus source feed intake described in step A
Than being 1:(0.8-2), preferably 1:(1-1.4), more preferably 1:(1.1-1.2), wherein the vanadium source is in terms of v element, it is described
Phosphorus source is in terms of P elements；And/or the vanadium source include vanadium oxide and vanadate in it is one or more, preferably five oxidation
Two vanadium and/or ammonium metavanadate；And/or phosphorus source includes phosphoric acid or phosphorus pentoxide, the preferably phosphoric acid of 85-105wt%, coke
At least one of phosphoric acid and polyphosphoric acids.
8. the preparation method described according to claim 6 or 7, which is characterized in that in step, can be optionally added auxiliary agent gold
The molar ratio of category elemental substance, the assistant metal element and the v element is (1-5):(100-1000), preferably (2-
3):(150-200)；And/or the assistant metal element includes one or more in indium, niobium, bismuth, cobalt, zinc and tungsten.
9. according to the preparation method described in any one of claim 6-8, which is characterized in that the step A includes：
Vanadium source is added in liquid medium, is heated to reflux by step A1；
Phosphorus source and polyalkenylalcohols are added into the reaction system of step A1, continues to be heated to reflux by step A2, obtain comprising the anti-of precipitation
Answer liquid；
Assistant metal element substance is optionally added into the reaction system of step A2 by step A3；
Step A4 carries out solid-liquid separation treatment to the reaction solution comprising precipitation, and obtained precipitation is washed and is dried,
Obtain vanadium-phosphor oxide catalyst presoma.
10. according to the preparation method described in any one of claim 6-9, which is characterized in that the step B includes：
Then the vanadium-phosphor oxide catalyst presoma and mix lubricant are heated, obtain mixture by step B1
Material；
Step B2 carries out compression process to the mixed material, obtains briquet；
The briquet is placed in air and/or vapor and/or nitrogen atmosphere and carries out activation process, obtains work by step B3
Vanadium-phosphor oxide catalyst matrix after change.
11. according to the preparation method described in any one of claim 6-10, which is characterized in that the lubricant and the vanadium
The mass ratio of phosphor oxide catalyst presoma is (0-10):(90-100), preferably (0-5):(95-100), more preferably (3-
5):(95-97)；And/or the lubricant includes one or more in graphite, starch and stearate.
12. according to the preparation method described in any one of claim 6-11, which is characterized in that the step C includes：
The vanadium-phosphor oxide catalyst matrix is mixed with expanding agent, is then pressed into type, obtains catalyst crude green body by step C1；
Step C2 carries out removing expanding agent processing to the crude green body, the vanadium phosphorus oxygen for being used for preparing cis-anhydride by n-butane oxidation is made
Catalyst.
13. according to the preparation method described in any one of claim 6-12, which is characterized in that the expanding agent and the vanadium
The mass ratio of phosphor oxide catalyst is (5-20):(80-95), preferably (8-15):(85-92), more preferably (10-13):
(87-90)；And/or the expanding agent includes 1,1,1- trimethylolethanes, trimethylolpropane, phthalic anhydride, suitable fourth
It is one or more in enedioic acid acid anhydride, tartaric acid, citric acid and citric acid, preferably 1,1,1- trimethylolethane, tartaric acid
With it is one or more in maleic anhydride.
14. according to the preparation method described in any one of claim 6-13, which is characterized in that soaked by solvent in step C2
Stain method removes the expanding agent in the crude green body；And/or the ratio between the solvent and the volume of the crude green body are (1-5):1, preferably
(1-3):1；And/or the processing time of the solvent impregnation is 1-24h, preferably 10-24h, more preferably 16-24h；With/
Or the one kind or more of the solvent in acetone, ethyl alcohol, anhydrous ether, n-butanol, methyl ethyl ketone, dichloromethane and ethyl acetate
Kind, it is preferably selected from one or more in acetone, n-butanol and ethyl acetate；And/or the crude green body is removed by heat treating process
In expanding agent；And/or the treatment temperature of the heat treatment is 120-300 DEG C, preferably 150-250 DEG C；Processing time is 12-
For 24 hours, preferably 20-24h.
15. a kind of method of preparing cis-anhydride by n-butane oxidation includes the use by normal butane described in any one of claim 1-5
It is used for just in prepared by any one of the vanadium-phosphor oxide catalyst of preparing cis-anhydride by n-butane oxidation or claim 6-14 the method
Oxidation reaction is carried out in the presence of the vanadium-phosphor oxide catalyst of butane oxidation cis-butenedioic anhydride.
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