CN107999107A - A kind of maleic anhydride catalyst and its preparation method and application - Google Patents
A kind of maleic anhydride catalyst and its preparation method and application Download PDFInfo
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- CN107999107A CN107999107A CN201610964062.3A CN201610964062A CN107999107A CN 107999107 A CN107999107 A CN 107999107A CN 201610964062 A CN201610964062 A CN 201610964062A CN 107999107 A CN107999107 A CN 107999107A
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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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- 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 catalyst field, discloses a kind of maleic anhydride catalyst and its preparation method and application.The maleic anhydride catalyst includes the metal composite oxide of carrier and load on the carrier, the metal composite oxide contains V, Mo, the first metal and the second metal, wherein, one or more of first metal in IA, II A, III A, IV A, V A races and group of the lanthanides, one or more of second metal in IA, II A, III A, IV A, V A races and group of the lanthanides, and first metal and second metal differ.Maleic anhydride catalyst provided by the invention can improve conversion ratio and selectivity, improve yield of maleic anhydride.
Description
Technical field
The present invention relates to catalyst field, and in particular, to a kind of maleic anhydride catalyst and its preparation method and application.
Background technology
Maleic anhydride (cis-butenedioic anhydride) is to be only second to aceticanhydride and phthalic anhydride in the world as a kind of important Organic Chemicals
The third-largest anhydride starting material.Cis-butenedioic anhydride mainly for the production of unsaturated polyester resin, alkyd resin, in addition, using cis-butenedioic anhydride as raw material also
It is a series of widely used that 1,4- butanediols, γ-fourth lactones, tetrahydrofuran, maleic acid, fumaric acid and tetrahydrochysene acid anhydrides etc. can be produced
Fine chemical product.In pesticide, medicine, coating, ink, lube oil additive, papermaking chemical product, textile finish, food
The field such as product additive and surfactant has a wide range of applications.Benzene method maleic anhydride accounts for the 40% of whole world production capacity, and Chinese
More than 90% production capacity is benzene method.In cis-butenedioic anhydride preparation process, maleic anhydride catalyst is the key problem in technology of production, and research and development and improvement are urged
Agent performance is current important process.
Sinopec original technology patent is mainly using infusion process production V-Mo-O maleic anhydride catalysts, using rare earth element as helping
Agent, prepares catalyst by preparing the processes such as active component solution, impregnated carrier, stir-frying, drying, passes through lab scale and single column run
Catalyst performance index is evaluated, benzene concentration reaches as high as 55g/m3, conversion ratio reaches 98%, and cis-butenedioic anhydride weight yield is 90%.But
Due to the transformation of the market demand, pursue simply high load capacity cannot meet producer pursue benefit there is an urgent need to urge
The exploitation of catalyst in high yield is developed in the research of agent by being conceived to.Therefore, there is an urgent need to develop new benzene method maleic anhydride catalyst,
The selectivity of catalyst is improved, improves yield of maleic anhydride.
The content of the invention
The object of the present invention is to provide a kind of maleic anhydride catalyst and its preparation method and application, which can carry
High conversion and selectivity, improve yield of maleic anhydride.
The first aspect of the invention is to provide a kind of maleic anhydride catalyst, and the metal composite oxide contains V, Mo,
One metal and the second metal, wherein, the one kind or more of first metal in IA, II A, III A, IV A, V A races and group of the lanthanides
Kind, one or more of second metal in IA, II A, III A, IV A, V A races and group of the lanthanides, and first metal and
Second metal differs.
The second aspect of the invention is to provide a kind of preparation method of maleic anhydride catalyst, and this method includes：
1) prepare containing vanadium-containing compound, molybdate compound, containing the first metallic compound and containing the second metallic compound
The step of aqueous solution；
2) the step of aqueous solution being sprayed onto carrier；
Wherein, one or more of first metal in IA, II A, III A, IV A, V A races and group of the lanthanides, described
One or more of two metals in IA, II A, III A, IV A, V A races and group of the lanthanides, and first metal and second gold medal
Category differs, and the temperature of the carrier is 200-400 DEG C.
The maleic anhydride catalyst that the third aspect of the invention is to provide above-mentioned maleic anhydride catalyst and above-mentioned preparation method obtains
Application in benzene oxidatoin prepares cis-butenedioic anhydride.
High load capacity is pursued simply for the prior art the problem of relatively low yield of maleic anhydride, and the present inventor is for existing
Catalyst component in technology has made intensive studies, and research is found, the reaction for the above-mentioned benzene legal system cis-butenedioic anhydride of the present invention is special
Point, in the catalyst containing the first metallic element and the second metallic element, can be greatly improved during benzene method prepares cis-butenedioic anhydride
Benzene conversion ratio, catalyst choice and yield of maleic anhydride, so as to complete the present invention.Maleic anhydride catalyst provided by the invention is full
On the premise of sufficient process units burden requirement, ensure benzene conversion ratio >=98%, cis-butenedioic anhydride weight yield >=95%, has good profit
With value and economic value.
For maleic anhydride catalyst benzene conversion ratio provided by the invention more than 98%, reaction end gas can be without catalyst combustion
Processing is directly discharged, meanwhile, maleic anhydride catalyst preparation method simple and fast of the invention, is catalyzed using cis-butenedioic anhydride provided by the invention
Agent carries out maleic anhydride production, and the soak time of catalyst is short, cost-effective easy to use.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of maleic anhydride catalyst, which includes carrier and load answering on the carrier
Metal oxide is closed, the metal composite oxide contains V, Mo, the first metal and the second metal, wherein, first metal
One or more in IA, II A, III A, IV A, V A races and group of the lanthanides, second metal be selected from IA, II A, III A, IV A,
One or more in V A races and group of the lanthanides, and first metal and second metal differ.
According to the present invention, in order to further improve benzene conversion ratio during benzene method prepares cis-butenedioic anhydride, catalyst choice
And yield of maleic anhydride, one or more of preferably described first metallic element in group of the lanthanides, second metallic element are selected from IA
One or more in race and V A races.It is highly preferred that one or more of first metal in neodymium, dysprosium and praseodymium, described
Second metal is selected from caesium and/or bismuth.
In the present invention, in order to improve benzene conversion ratio, catalyst choice and the yield of maleic anhydride of catalyst, it is preferable that institute
State in metal composite oxide, the V in terms of vanadic anhydride with molybdenum oxide (MoO3) meter Mo, with most the first metal oxygen of high state
First metal of compound meter and using the bimetallic molar ratio that most the second metal oxide of high state is counted as 1：0.01-1：0.001-
0.08：0.0001-0.05；It is highly preferred that V in terms of vanadic anhydride with the Mo in terms of molybdenum oxide, with most the first metal of high state
First metal of oxide meter and using the bimetallic molar ratio that most the second metal oxide of high state is counted as 1：0.05-0.9：
0.005-0.07：0.005-0.05.
In addition, in the metal composite oxide, the first metal preferably in terms of most the first metal oxide of high state and with
The most bimetallic molar ratio of the second metal oxide of high state meter is 1：0.01-1, more preferably 1：0.05-0.9.
, according to the invention it is preferred to the metal composite oxide also contains P.In addition, aoxidized as P in the composition metal
Content in thing can be determined according to the content of the V in the metal composite oxide.Preferably, the composition metal oxidation
In thing, the molar ratio of the V counted using vanadic anhydride and the P counted using phosphorus pentoxide is 1：0.001-0.1；More preferably 1：
0.01-0.1。
, according to the invention it is preferred to the metal composite oxide also contains Ni.In addition, as Ni in the composition metal oxygen
Content in compound can be determined according to the content of the V in the metal composite oxide.Preferably, the composition metal oxygen
In compound, the molar ratio of the V counted using vanadic anhydride and the Ni counted using nickel protoxide is 1：0.001-0.1；More preferably 1：
0.001-0.08。
, according to the invention it is preferred to the metal composite oxide also contains Na.As Na in the metal composite oxide
In content can be determined according to the content of the V in the metal composite oxide.Preferably, the metal composite oxide
In, the molar ratio of the V counted using vanadic anhydride and the Na counted using sodium oxide molybdena is 1：0.01-0.2；More preferably 1：0.05-0.2.
A preferred embodiment according to the present invention, the metal composite oxide contain V, Mo, P, Ni, Na,
One metal and the second metal.And in the metal composite oxide, V in terms of the vanadic anhydride and Mo in terms of molybdenum oxide,
P in terms of phosphorus pentoxide, the Ni in terms of nickel protoxide, the Na in terms of sodium oxide molybdena, in terms of most the first metal oxide of high state
First metal and using the bimetallic molar ratio that most the second metal oxide of high state is counted as 1：0.01-1：0.001-0.1：
0.001-0.1：0.01-0.2：0.001-0.08：0.0001-0.05.It is highly preferred that in terms of most the first metal oxide of high state
First metal and using the bimetallic molar ratio that most the second metal oxide of high state is counted as 1：0.01-1；More preferably 1：
0.05-0.8。
In the present invention, there is no particular limitation for the carrier, can use the conventional use of various loads of catalyst field
Body, such as Carboround, silica supports or alumina carrier etc..The process of cis-butenedioic anhydride is prepared for benzene method, it is described
Carrier is preferably Carboround, alumina carrier.
For example, the carrier can be using carborundum as carrier framework, low pressure china clay is binding agent, and methylcellulose is interim
Binding agent and pore creating material.Other components, such as Ludox (the preferably acidity without Na can also further be contained in the carrier
Ludox), polypropylene etc..Preferably, the carrier is with silicon carbide powder, low pressure china clay, methylcellulose or cornstarch
The carrier obtained for raw material through overmolding and roasting.In order to ensure the performance of resulting vehicle, in the carrier, the granularity of carborundum
For 20-200 mesh, the granularity of low pressure china clay is 60-300 mesh, and methylcellulose viscosity is 17-555 centipoises, and polypropylene granularity is
10-150 mesh.The weight ratio of each raw material can be carborundum：Low pressure china clay：Methylcellulose：Polypropylene：Ludox=1：0.1-
0.4：0.04-0.2：0.06-0.3：0.1-0.4, is preferably 1：0.15-0.35：0.06-0.1：0.1-0.2：0.17-0.35.Institute
Stating the preparation method of carrier can be：By said ratio carry out material mixing, add water to mediate, place 8-24 it is small when after, by into
Type, drying and roasting are made.The drying condition can include：Drying time is 3-4h, and drying temperature is 110-120 DEG C, institute
Stating roasting condition can include：Roasting time is 48-144h, and calcination temperature is 1200-1400 DEG C.The shape and ruler of the carrier
Very little there is no particular limitation, such as can be spherical, ring-type etc., specifically can suitably choose as needed.
In order to ensure benzene conversion ratio, catalyst choice and the yield of maleic anhydride of the maleic anhydride catalyst, in the case of preferable,
The specific surface area of the carrier is 0.1-20m2/ g, aperture 10-200nm.
Present invention also offers a kind of preparation method of maleic anhydride catalyst, this method includes：
1) prepare containing vanadium-containing compound, molybdate compound, containing the first metallic compound and containing the second metallic compound
The step of aqueous solution；
2) the step of aqueous solution being sprayed onto carrier；
Wherein, one or more of first metal in IA, II A, III A, IV A, V A races and group of the lanthanides, described
One or more of two metals in IA, II A, III A, IV A, V A races and group of the lanthanides, and first metal and second gold medal
Category differs, and the temperature of the carrier is 200-400 DEG C.
Preferably, first metallic compound that contains is the first metal oxide, and second metallic compound that contains is the
Two metal oxides.It is highly preferred that one or more of first metal in group of the lanthanides, described to contain the second metallic compound
One or more in IA races and V A races.It is further preferred that the one kind of first metal in neodymium, dysprosium and praseodymium
Or it is a variety of, second metal is selected from caesium and/or bismuth.
It is particularly preferred that as it is described containing the first metallic compound be one kind in neodymia, dysprosia and praseodymium oxide or
It is a variety of, it is cesium oxide and/or bismuth oxide as second metallic compound that contains.
According to the present invention, can be one kind in vanadate, metavanadate and vanadate as the vanadium-containing compound
Or it is a variety of, it is specifically as follows sodium salt, ammonium salt, sylvite etc..Preferably, the vanadium-containing compound is selected from ammonium metavanadate, sodium metavanadate
It is preferably ammonium metavanadate with the one or more in vanadic anhydride.
According to the present invention, can be the one or more in molybdate and/or molybdenum oxide as the molybdate compound；It is excellent
Selection of land, more preferably one or more of the molybdate compound in ammonium molybdate, sodium molybdate and molybdenum oxide, ammonium molybdate.
According to the present invention, in order to improve benzene conversion ratio, catalyst choice and the yield of maleic anhydride of gained catalyst, preferably
Ground, vanadium-containing compound in terms of vanadic anhydride with the molybdate compound in terms of molybdenum oxide, with most the first metal oxide of high state
Meter contains the first metallic compound and the molar ratio containing the second metallic compound counted using most the second metal oxide of high state as 1：
0.01-1：0.001-0.08：0.0001-0.05.It is highly preferred that vanadium-containing compound in terms of vanadic anhydride with terms of molybdenum oxide
Molybdate compound, in terms of most the first metal oxide of high state containing the first metallic compound and with most the second metal of high state aoxidize
The molar ratio containing the second metallic compound of thing meter is 1：0.05-0.9：0.005-0.07：0.005-0.05.
According to the present invention, in the aqueous solution, metallizing containing first preferably in terms of most the first metal oxide of high state
Compound and the molar ratio containing the second metallic compound counted using most the second metal oxide of high state is 1：0.01-1, more preferably 1：
0.05-0.8。
According to the present invention, the aqueous solution also contains phosphorus-containing compound.As the phosphorus-containing compound, can have to be phosphorous
Machine compound or inorganic phosphor-contained compound, are preferably phosphorous inorganic salts, such as can be selected from ammonium dihydrogen phosphate and/or tricresyl phosphate
Sodium.In addition, the dosage as phosphorus-containing compound in the aqueous solution can be determined according to vanadium-containing compound.Preferably, in institute
State in aqueous solution, the molar ratio of the vanadium-containing compound counted using vanadic anhydride and the phosphorus-containing compound counted using phosphorus pentoxide is 1：
0.001-0.1, more preferably 1：0.01-0.1.
According to the present invention, the aqueous solution also contains nickel compound containing.Can be nickeliferous as the nickel compound containing
Inorganic salts, are preferably the one or more in nickel nitrate, nickel chloride and nickel sulfate.In addition, as nickeliferousization in the aqueous solution
The dosage of compound can be determined according to vanadium-containing compound.Preferably, in the aqueous solution, vanadium is contained in terms of vanadic anhydride
Compound and the molar ratio for the nickel compound containing counted using nickel protoxide is 1：0.001-0.1, more preferably 1：0.001-0.08.
According to the present invention, the aqueous solution also contains compounds containing sodium.As the compounds containing sodium, phosphoric acid can be selected from
One or more in trisodium, sodium dihydrogen phosphate, sodium nitrate and sodium chloride, are preferably tertiary sodium phosphate.In addition, as described water-soluble
The dosage of compounds containing sodium can be determined according to vanadium-containing compound in liquid.Preferably, in the aqueous solution, with five oxidations two
The molar ratio of the vanadium-containing compound of vanadium meter and the compounds containing sodium counted using sodium oxide molybdena is 1：0.01-0.2, more preferably 1：0.05-
0.2。
In the preferred embodiment of the present invention, the phosphorus-containing compound and the compounds containing sodium are phosphoric acid
Trisodium, at this time, as long as the dosage of tertiary sodium phosphate meets the dosage of phosphorus-containing compound in the aqueous solution and compounds containing sodium i.e.
Can.
There is no particular limitation for the preparation method of the aqueous solution, ensures whole compound uniform dissolutions.To be terrible
To the aqueous solution of uniform dissolution, it can also contain certain dissolution aids in the aqueous solution, not have as the dissolution aids
It is special to limit, as long as the uniform aqueous solution of solvent can be finally obtained.It for example can be grass as the dissolution aids
One or more in acid, hydrochloric acid and sulfuric acid.In addition, the dosage as dissolution aids, so as to finally obtaining what is be uniformly dissolved
Subject to aqueous solution.
In addition, do not required particularly for the addition sequence of each compound, can be specifically chosen according to its property.It is preferred that
Ground, can be first miscible with water by dissolution aids, then adds vanadium-containing compound and is dissolved, and is subsequently added into prepared in advance contain
Molybdenum compound aqueous solution is mixed, and is added containing the first metallic compound and is mixed to get institute containing the second metallic compound
Stating aqueous solution, (also referred to as activearm liquid separation, has fully dissolved containing the first metallic compound and containing the second metal compound in order to obtain
The activearm liquid separation of thing, can also add dissolution aids in aqueous, such as can be acid, be preferably oxalic acid or hydrochloric acid).Separately
Outside, before adding containing the first metallic compound and being mixed containing the second metallic compound, can also first add in aqueous
Enter the one or more in phosphorus-containing compound, nickel compound containing and compounds containing sodium, then add containing the first metallic compound
With carry out being mixed to get the aqueous solution containing the second metallic compound.
Temperature when above-mentioned each compound adds is preferably 15-40 DEG C.
It is understood that above-mentioned maleic anhydride catalyst preparation method can be used for preparing what the first aspect of the present invention provided
Maleic anhydride catalyst, the carrier used in the maleic anhydride catalyst preparation method is identical with the carrier in above-mentioned maleic anhydride catalyst, herein
Repeat no more.
In order to ensure catalyst uniform load on carrier, the sprinkling process of the activearm liquid separation should be as far as possible uniform,
The instruments such as spray gun can be used to carry out, and further can rotate carrier, ensure that its each face uniformly receives the activearm
Liquid separation.
The maleic anhydride catalyst obtained present invention also offers above-mentioned maleic anhydride catalyst and above-mentioned preparation method is in benzene oxidatoin system
Application in standby cis-butenedioic anhydride.
In the present invention, maleic anhydride catalyst provided by the invention needs to be activated before use, and activation method can be：
First blowing air simultaneously heats up (such as can be 200-400 DEG C, be preferably 250-350 DEG C), and then passing to Low Concentration of Benzene, (benzene concentration is
2-10g/m3), then used after induction (such as can be that 400-450 DEG C of salt bath induces 24h).
The maleic anhydride catalyst of the present invention can be used for fixed bed reactors, its performance can use solid single tube simulator into
Row characterization.In 345-360 DEG C of salt temperature, air speed 2000-2200h-1, benzene concentration 45-60g/m3Experimental condition under, the present invention
Maleic anhydride catalyst benzene conversion ratio be more than 98%, cis-butenedioic anhydride weight yield be more than 95%.The above results show the present invention's
Maleic anhydride catalyst has good activity and selectivity, can meet process specifications, can be benzene method maleic anhydride prepare it is cost-effective,
Suitable for industrialized production.
The present invention will be described in detail by way of examples below.
In following embodiments, load factor=(weight of weight-empty vectors of obtained maleic anhydride catalyst)/obtained suitable
The weight % of the weight of acid anhydride catalyst × 100, catalyst choice=cis-butenedioic anhydride molar yield/benzene conversion ratio × 100%.
Preparation example 1
This preparation example is used to illustrate prepared by carrier.
By silicon carbide powder (200g, 60 mesh), low pressure china clay (50g, 100 mesh), (16.6g, viscosity are methylcellulose
17-23 centipoises), polypropylene (33.4g, 20-40 mesh) after mixing, add 50mL Ludox (trade mark 90-IV) and 50mL
The mixed solution of distilled water, is fully mediated by plastics kneader again after being sufficiently mixed, and is stood curing 12h, is extruded with extruder
The cylinder ring of 6*3*5,110 DEG C of drying 4h, 1300 DEG C of kiln fuse 72h, and kiln discharge after cooling, that is, obtain empty vectors.
Embodiment 1
The present embodiment is used for the preparation method for illustrating maleic anhydride catalyst.
Activearm liquid separation is prepared first, and its preparation method is as follows：First 450.2g oxalic acid is dissolved in 60 DEG C of hot water, is cooled to
271.2g ammonium metavanadates (NH is added at 30 DEG C4VO3) (purity more than 99.9%), stir to dissolve, then add ammonium molybdate
((NH4)2Mo4O13·2H2O aqueous solution (containing ammonium molybdate 173.9g)), then it is separately added into tertiary sodium phosphate (Na3PO4·12H2O)
35.07g, nickel nitrate (Ni (NO3)2.6H2O) 5.63g, contains the first metallic compound by component as shown in Table 1 and additive amount
With fully dissolved with oxalic acid containing the second metallic compound after add in above-mentioned aqueous solution, be sufficiently stirred more than 30min, be made blackish green
Color activearm liquid separation.
Then this solution is uniformly sprayed at by the rotating 25kg for heating (300 DEG C of heating-up temperature) by spray gun
Empty vectors made from embodiment 1) on, natural cooling, that is, the cis-butenedioic anhydride that supported on carriers, which is made, metal composite oxide is catalyzed
Agent C1.In metal composite oxide in obtained maleic anhydride catalyst C1, V in terms of vanadic anhydride with terms of molybdenum oxide
Mo, the P in terms of phosphorus pentoxide, the Ni in terms of nickel protoxide, the Na in terms of sodium oxide molybdena, with neodymia (Nd2O3) meter Nd and with
Cesium oxide (Cs2O) molar ratio of the Cs of meter is 1：0.9：0.04：0.02：0.12：0.03：0.01.Load factor is as shown in table 1.
Embodiment 2
According to embodiment 1 method carry out, unlike, containing the first metallic compound and containing the second metallic compound according to
It is added shown in table 1, obtained supported on carriers has the maleic anhydride catalyst C2 of metal composite oxide.In obtained cis-butenedioic anhydride catalysis
In metal composite oxide in agent C2, V in terms of the vanadic anhydride and Mo in terms of molybdenum oxide, the P in terms of phosphorus pentoxide,
Ni in terms of nickel protoxide, the Na in terms of sodium oxide molybdena, with dysprosia (Dy2O3) meter Dy and with cesium oxide (Cs2O) the Cs of meter
Molar ratio is 1：0.9：0.04：0.02：0.12：0.03：0.01.Load factor is as shown in table 1.
Embodiment 3
According to embodiment 1 method carry out, unlike, containing the first metallic compound and containing the second metallic compound according to
It is added shown in table 1, obtained supported on carriers has the maleic anhydride catalyst C3 of metal composite oxide.In obtained cis-butenedioic anhydride catalysis
In metal composite oxide in agent C3, V in terms of the vanadic anhydride and Mo in terms of molybdenum oxide, the P in terms of phosphorus pentoxide,
Ni in terms of nickel protoxide, the Na in terms of sodium oxide molybdena, with praseodymium oxide (PrO2) meter Pr and with bismuth oxide (Bi2O3) meter Bi
Molar ratio is 1：0.9：0.04：0.02：0.12：0.06：0.008.Load factor is as shown in table 1.
Comparative example 1
Carried out according to the method for embodiment 1, unlike, it is added without containing the first metallic compound and containing the second metal compound
Thing, is made contrast maleic anhydride catalyst C4, its load factor is 14.30 weight %.
Table 1
Test case
This test case is illustrating the evaluation method of maleic anhydride catalyst.
Activation is first passed through before carrying out evaluating catalyst experiment, activation method is using first blowing air to logical low concentration after 300 DEG C
Benzene (concentration 10g/m3) activation method, activate after under 420 DEG C of salt baths induce 24h formally measured again.
Measure is carried out using single tube evaluation test.Evaluating apparatus uses loaded catalyst to evaluate dress for the single tube of 1.8L
Put, single tube reactor in φ 32mm × 3.5mm, built-in Thermal couple casing pipe φ=6 × 1mm, long 3800mm, single tube is placed in fused salt and adds
In the U-shaped casing of heat.Raw air is preheated to be mixed into reactor, is trapped through catalyst reaction generation gas with ice-water bath, then
Titrated with standard alkali solution, calculate yield of maleic anhydride.Reaction condition is air speed 2000h-1, benzene concentration 50g/m3, salt temperature 350
℃。
With gas-chromatography (Rayleigh analytical instrument company, model SD-3400 are divided in north) measure reactor inlet and outlet benzene concentration
Change and tail gas in CO and CO2Content, it is as shown in table 2 by the measurement result being calculated.
Table 2
In addition, repetitive test and die-away test are carried out to above-mentioned maleic anhydride catalyst C1, the results showed that the catalyst performance
Can be good, repeatability is stablized, and resists frequent driving and parking ability strong.
By the contrast of above-described embodiment and comparative example, maleic anhydride catalyst of the invention is than contrast maleic anhydride catalyst C4
Benzene conversion ratio, yield of maleic anhydride and catalyst choice with higher.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (17)
1. a kind of maleic anhydride catalyst, which includes the metal composite oxide of carrier and load on the carrier,
It is characterized in that, the metal composite oxide contains V, Mo, the first metal and the second metal, wherein, the first metal choosing
One or more from IA, II A, III A, IV A, V A races and group of the lanthanides, second metal are selected from IA, II A, III A, IV A, V A
One or more in race and group of the lanthanides, and first metal and second metal differ.
2. maleic anhydride catalyst according to claim 1, wherein, the one kind or more of first metallic element in group of the lanthanides
Kind, one or more of second metallic element in IA races and V A races；
Preferably, one or more of first metal in neodymium, dysprosium and praseodymium, second metal are selected from caesium and/or bismuth.
3. maleic anhydride catalyst according to claim 1, wherein, in the metal composite oxide, in terms of vanadic anhydride
V and the Mo in terms of molybdenum oxide, the first metal in terms of most the first metal oxide of high state and aoxidized with most the second metal of high state
The bimetallic molar ratio of thing meter is 1：0.01-1：0.001-0.08：0.0001-0.05；
Preferably, the V in terms of vanadic anhydride and the Mo in terms of molybdenum oxide, the first gold medal in terms of most the first metal oxide of high state
Belong to and using the bimetallic molar ratio that most the second metal oxide of high state is counted as 1：0.05-0.9：0.005-0.07：0.005-
0.05。
4. maleic anhydride catalyst according to claim 3, wherein, the first metal in terms of most the first metal oxide of high state and
Using the bimetallic molar ratio that most the second metal oxide of high state is counted as 1：0.01-1.
5. according to the maleic anhydride catalyst described in any one in claim 1-4, wherein, the metal composite oxide also contains
P；
Preferably, in the metal composite oxide, the molar ratio of V and the P in terms of phosphorus pentoxide in terms of vanadic anhydride
For 1：0.001-0.1.
6. according to the maleic anhydride catalyst described in any one in claim 1-4, wherein, the metal composite oxide also contains
Ni；
Preferably, in the metal composite oxide, the molar ratio of V and the Ni in terms of nickel protoxide in terms of vanadic anhydride are
1：0.001-0.1.
7. according to the maleic anhydride catalyst described in any one in claim 1-4, wherein, the metal composite oxide also contains
Na；
Preferably, in the metal composite oxide, the molar ratio of the V counted using vanadic anhydride and the Na counted using sodium oxide molybdena is 1：
0.01-0.2。
8. maleic anhydride catalyst according to claim 1, wherein, the carrier for Carboround alumina carrier or
Silica supports；
Preferably, the specific surface area of the carrier is 0.1-20m2/ g, aperture 10-200nm.
9. a kind of preparation method of maleic anhydride catalyst, it is characterised in that this method includes：
1) prepare containing vanadium-containing compound, molybdate compound, containing the first metallic compound and containing the water-soluble of the second metallic compound
The step of liquid；
2) the step of aqueous solution being sprayed onto carrier；
Wherein, one or more of first metal in IA, II A, III A, IV A, V A races and group of the lanthanides, second gold medal
Belong to the one or more in IA, II A, III A, IV A, V A races and group of the lanthanides, and first metal and second metal are not
It is identical；The temperature of the carrier is 200-400 DEG C.
10. preparation method according to claim 9, wherein, first metallic compound that contains is the first metal oxide,
Second metallic compound that contains is the second metal oxide；
Preferably, one or more of first metal in group of the lanthanides, second metal is in IA races and V A races
It is one or more；
Preferably, one or more of first metal in neodymium, dysprosium and praseodymium, second metal are selected from caesium and/or bismuth；
Preferably, first metallic compound that contains is the one or more in neodymia, dysprosia and praseodymium oxide, described to contain the
Two metallic compounds are cesium oxide and/or bismuth oxide.
11. preparation method according to claim 9, wherein, the vanadium-containing compound be selected from ammonium metavanadate, sodium metavanadate,
One or more in vanadyl oxalate and vanadic anhydride, the molybdate compound is in ammonium molybdate, sodium molybdate and molybdenum oxide
One or more.
12. preparation method according to claim 9, wherein, vanadium-containing compound in terms of vanadic anhydride with molybdenum oxide
The molybdate compound of meter, contain the first metallic compound and with most the second metal oxygen of high state in terms of most the first metal oxide of high state
The molar ratio containing the second metallic compound of compound meter is 1：0.01-1：0.001-0.08：0.0001-0.05；
Preferably, the vanadium-containing compound in terms of vanadic anhydride with terms of molybdenum oxide molybdate compound, with most the first gold medal of high state
Belong to the rubbing containing the second metallic compound containing the first metallic compound and in terms of most the second metal oxide of high state of oxide meter
You are than being 1：0.05-0.9：0.005-0.07：0.005-0.05.
Preferably, in the aqueous solution, the first metallic compound is contained and in terms of most the first metal oxide of high state with highest
The molar ratio containing the second metallic compound of state the second metal oxide meter is 1：0.05-0.9.
13. the preparation method according to claim 9 or 12, wherein, the aqueous solution also contains phosphorus-containing compound；
Preferably, the molar ratio of the vanadium-containing compound counted using vanadic anhydride and the phosphorus-containing compound counted using phosphorus pentoxide is 1：
0.001-0.1；
Preferably, the phosphorus-containing compound is ammonium dihydrogen phosphate and/or tertiary sodium phosphate.
14. the preparation method according to claim 9 or 12, wherein, the aqueous solution also contains nickel compound containing；
Preferably, the molar ratio of the vanadium-containing compound counted using vanadic anhydride and the nickel compound containing counted using nickel protoxide is 1：
0.001-0.1；
Preferably, the nickel compound containing is the one or more in nickel chloride, nickel sulfate and nickel nitrate.
15. the preparation method according to claim 9 or 12, wherein, the aqueous solution also contains compounds containing sodium；
Preferably, the molar ratio of the vanadium-containing compound counted using vanadic anhydride and the compounds containing sodium counted using sodium oxide molybdena is 1：
0.01-0.2；
Preferably, the compounds containing sodium is the one or more in tertiary sodium phosphate, sodium dihydrogen phosphate, sodium nitrate and sodium chloride.
16. according to the preparation method described in any one in claim 9-15, wherein, the carrier is Carboround, two
Silica support or alumina carrier；
Preferably, the specific surface area of the carrier is 0.1-20m2/ g, aperture 10-200nm.
17. the system in the maleic anhydride catalyst or claim 9-16 in claim 1-8 described in any one described in any one
Application of the maleic anhydride catalyst made from Preparation Method in benzene oxidatoin prepares cis-butenedioic anhydride.
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| US4097501A (en) * | 1976-05-19 | 1978-06-27 | The Standard Oil Company | Use of coated catalysts in the preparation of maleic anhydride |
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