CN108101873A - A kind of method that n butane oxidation prepares cis-butenedioic anhydride - Google Patents
A kind of method that n butane oxidation prepares cis-butenedioic anhydride Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- 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
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Abstract
The invention discloses a kind of methods that n butane oxidation prepares cis-butenedioic anhydride.Normal butane is mixed with air, and acquired hybrid reaction gas cocurrent under oxidation reaction condition, is contacted with vanadium-phosphor oxide catalyst and reacted by the vanadium-phosphor oxide catalyst bed of at least two series connection；Wherein, according to the engagement sequence with hybrid reaction gas, the P/V molar ratios of catalyst are less than the P/V molar ratios of catalyst in the bed of upstream in down stream.The method of the present invention can reduce the reaction hot spot of bed, make bed temperature distribution average, effective to inhibit side reaction, improve product selectivity, increase product yield of maleic anhydride.
Description
Technical field
The present invention relates to a kind of method of normal butane cis-butenedioic anhydride, the n butane oxidation that specifically a kind of catalyst grade is matched somebody with somebody
The method for preparing cis-butenedioic anhydride, the reaction process available for the preparing cis-anhydride by n-butane oxidation using fixed-bed process.
Background technology
Maleic anhydride abbreviation cis-butenedioic anhydride also known as maleic anhydride are a kind of important Organic Chemicals, are to be only second to benzene
The big organic acid anhydride in the third place in the world of acid anhydride and aceticanhydride, is widely used in the industries such as petrochemical industry, food processing, medicine, building materials.It is specific
Using including manufacture unsaturated polyester resin, alkyd resin, maleic acid（Maleic acid）, fumaric acid（Fumaric acid）, with
And pesticide, coating, fiberglass, lube oil additive, papermaking chemical product additive, surfactant etc..New method cis-butenedioic anhydride esterification is low
The appearance of pressure hydrogenation production 1,4-butanediol technique, makes fine-chemical intermediate Isosorbide-5-Nitrae-fourth two with high added value
The important source material of alcohol, tetrahydrofuran, γ-fourth lactones, application field are expanded rapidly.
Benzene oxidatoin method, n butane oxidation method are two kinds of main production process of maleic anhydride production, and wherein benzene oxidatoin method is earliest
The technique of application, reactor and catalyst technology are ripe, but since benzene feedstock price is relatively expensive, the environmental pollution of generation
It is relatively serious, therefore its shortcoming is increasingly showed.From Monsanto companies n butane oxidation legal system maleic anhydride process in 1974
Industrialization is realized for the first time, since the technique has the advantages of raw material is inexpensive, and environmental pollution is small, and cis-butenedioic anhydride manufacture is at low cost, at present
Through the main route for becoming global maleic anhydride production.Selective oxidation of n -butane cis-butenedioic anhydride can be divided into fixed bed, fluid bed, Yi Jiyi
The production technologies such as dynamic bed.
At present in the production of preparing cis-anhydride by n-butane oxidation, since the butane raw material availability of fixed-bed process is high, product
Stable quality, it is easy to operate, therefore become the main method of maleic anhydride production, but in the production process in a manner of fixed bed,
Due to oxidation reaction it is strongly exothermic the characteristics of, the reaction heat of main reaction generation cis-butenedioic anhydride is 1236kJ/mol, side reaction generation CO2, CO
Reaction heat is respectively 2656kJ/mol and 1521kJ/mol, is at present to be circulated in using the external world in reactor jacket in industrial production
Melting salt remove reaction heat, but catalyst is local that there are still hot spots, it is difficult to optimal control, and react hot spot presence can pair
Catalyst performance has a negative impact, thus in reaction process hot spot stabilize as reaction process control key, further
Say that the hot spot height of catalyst bed directly affects the stability of the conversion ratio of butane, the yield of cis-butenedioic anhydride and catalyst.
Vanadium-phosphor oxide catalyst is considered as the optimal industrial catalyst of preparing cis-anhydride by n-butane oxidation process, vanadium-phosphor oxide catalyst
The reaction of selective oxidation normal butane is that the major class hydrocarbon selective oxidation carried out by redox (Re-dox) mechanism reacts
Typical Representative, the process of chemical reaction are related to the transfer of 14 electronics, are sloughed and 3 including electronics on 8 hydrogen atoms
The insertion of electronics on oxygen atom, the hot spot of the exploration always vanadium-phosphor oxide catalyst research of reaction mechanism, vanadium-phosphor oxide catalyst
It is a kind of complicated catalyst system, its physical property and structure has much relations with preparation method, and its physical property and structure are to urging
Changing performance has very big influence, and 1985, Hodnett was in CATAL.REV.-SCI.ENG, 27 (3) 373~424 (1985)
In the preparation method of the various presomas of preparing cis-anhydride by n-butane oxidation vanadium-phosphor oxide catalyst is summarized, and as after vanadium
The Classical Bases of phosphor oxide catalyst research.
Hodnett summaries point out, the P/V of catalyst is than activation method of the, addition of auxiliary agent and catalyst etc. to catalysis
The performance of agent has apparent influence.
B.K HODNETT are in Applide Catalysis, 6 (1983) 231~244 to P/V in vanadium-phosphor oxide catalyst
The influence for comparing catalyst property and composition and catalytic performance has carried out detailed research, the results showed that the P/V ratios of catalyst
There is significant impact to the evaluation valence state of vanadium in catalyst, P/V ratios are increased to 1.07 from 0.94, the average valence of vanadium in catalyst
4.04 are dropped to from 4.97.
USP4,632,915 propose a kind of vanadium-phosphor oxide catalyst preparation and activation method, in stirring with reflux cooler
It mixes in reaction kettle, cools down lower addition isobutanol, phosphoric acid（100%）, vanadic anhydride, lithium chloride and iron powder, then be passed through hydrogen chloride gas
Body then when reflux is small more than 2.5 under conditions of 102 DEG C, obtains catalyst precursor, then by drying, roasts, shaping
Afterwards, activation process is first with the heating rate of 3 DEG C/min, under aqueous 1.8% air atmosphere, by the activation temperature of catalyst
Degree rises to 280 DEG C from 230 DEG C, states the normal butane for adding in that molar content is 0.6% in air atmosphere then up, and with 1 DEG C/min
Heating rate continue activation temperature rising to 400 DEG C and keep 1h, be then changed to keep under nitrogen atmosphere 5 it is small when, activation
Terminate.Performance evaluation is carried out to the catalyst after activation, reaction result is：Butanes conversion ＞ 78.1%, cis-butenedioic anhydride molar yield are
54.5%。
USP4,855,459 propose a kind of preparation method of preparing cis-anhydride by n-butane oxidation, be using inert sial ball with
The method of catalyst dilution filling carries out, and filling is diluted by the hot spot generating unit in reaction tube, is reduced instead to reach
Hot(test)-spot temperature is answered, improves Selectivity of maleic anhydride, improves the purpose of yield of maleic anhydride, while the stationary phase of catalyst is extended, but
Its unfavorable factor is the addition of inertia goods and materials, reduces the effective volume of reactor, while also reduces production efficiency.
In the technology of existing fixed bed preparing cis-anhydride by n-butane oxidation, loaded respectively along reaction stream direction in reactor
The catalyst of different activities so that catalytic activity changes from low to high along feedstock direction during Catalyst packing, to realize to oxidation
The control of hot spot is reacted, reaches raising product selectivity, the method for increasing product yield has not been reported so far.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of method for fixed bed process preparing cis-anhydride by n-butane oxidation, with
The hot issue for even eliminating catalyst bed is reduced, extends the service life of catalyst.
The method that a kind of n butane oxidation of the present invention prepares cis-butenedioic anhydride, including herein below：
Normal butane is mixed with air, the vanadium-phosphor oxide catalyst bed that acquired hybrid reaction gas cocurrent passes through at least two series connection
Layer, under oxidation reaction condition, contacts with vanadium-phosphor oxide catalyst and is reacted；According to the engagement sequence with hybrid reaction gas, under
The P/V molar ratios of catalyst in bed are swum less than catalyst d P/V molar ratios in the bed of upstream.
The method according to the invention, wherein in two adjacent vanadium-phosphor oxide catalyst beds, in downstream catalyst bed
P/V molar ratio of the P/V molar ratios of catalyst generally than catalyst in adjacent upstream bed is higher by 0.01~0.15 unit,
It is preferred that 0.02~0.12 unit, most preferably 0.03~0.05 unit.
In the method for the present invention, wherein in each optional vanadium-phosphor oxide catalyst bed, the P/V molar ratios one of catalyst
As for 0.95~1.45, be preferably 0.97~1.25.
In the method for the present invention, the hybrid reaction gas of normal butane and air preferably passes through 3~5 vanadium-phosphor oxide catalyst beds
Layer.When selecting 3 vanadium-phosphor oxide catalyst beds, according to the order contacted with hybrid reaction gas, the catalyst bed of most upstream
The P/V molar ratios of middle catalyst are 1.15~1.25, in Intermediate Catalyst bed the P/V molar ratios of catalyst for 1.15~
1.05, the P/V molar ratios 0.97~1.05 of catalyst in the catalyst bed of most downstream.
In the method for the present invention, v element uses fluorescence quantitative analysis in catalyst, and the measurement of P elements uses colorimetric
Quantitative analysis, the average valence generally use ferrous ammonium sulfate titration of vanadium, such as Qiao Guanghui in vanadium-phosphor oxide catalyst（《Analysis
Laboratory》, the supplementary issue of volume 17, in May, 2008, P222-223）Deng using ferrous ammonium sulfate titration, vpo catalyst is determined
The average valence of vanadium ion.Zeng Ling（《Table mountain Journal of Teachers College》, the 2nd phase of volume 14, in May, 1999, P34-38）And it uses
Ferrous ammonium sulfate titration determines the average valence of vanadium in the research of butane oxidation cis-butenedioic anhydride vpo catalyst.
The vanadium-phosphor oxide catalyst with different P/V molar ratios can be prepared according to the ordinary skill in the art.
In the method for the present invention, recommend to prepare the satisfactory vanadium-phosphor oxide catalyst with different P/V molar ratios using following methods.
The preparation method for the vanadium-phosphor oxide catalyst that the present invention recommends includes herein below：
（1）The presoma of vpo catalyst is prepared using the conventional technical means of the art --- vanadium phosphorus oxide；
（2）By step（1）Gained catalyst precursor is shaped to Raschig ring shape or cylindrical catalyst after drying, roasting
Grain；
（3）By step（2）Rear catalyst is molded to keep under certain temperature, in nitrogen or atmosphere of inert gases or normal butane/
It is activated in empty gaseous mixture atmosphere, obtains the vanadium-phosphor oxide catalyst activated.
Wherein, in step（1）In, the prior art or conventional technical means in this field, such as Chinese patent may be employed
Method disclosed in CN103769181A or United States Patent (USP) USP4,632,915 prepares the precursor of vanadium-phosphor oxide catalyst --- vanadium
Phosphorus oxygenate.The preparation method of the catalyst precursor --- vanadium phosphorus oxide is the common knowledge of this field.
Wherein step（2）In, the molding mode can be extrusion, beat piece or the shaping side of this fields routine such as balling-up
Method.
Wherein step（3）In, described activation can the gaseous mixture of nitrogen/air, the gaseous mixture of vapor/air or
It is carried out under the atmosphere of the one or more combination of the gaseous mixture of normal butane/air.In the present invention, it is preferred to use identical activation item
Part carries out activation process for the prepared catalyst with different P/V molar ratios.
In prepared by the catalyst precursor of the present invention, by the quality for controlling the raw material vanadic anhydride added in and phosphoric acid
Than the catalyst precursor with different P/V molar ratios can be prepared, and the P/V ratios of vanadium-phosphor oxide catalyst precursor are to determine
The key factor of final vpo catalyst performance.This is primarily due to：1st, P/V compares oxidation-reduction quality ability and influences, excessive phosphorus
The movement of Lattice Oxygen is greatly prevented, reduces the oxidability of catalyst.2nd, the influence of catalyst crystalline phases composition can be urged
The phosphorus added in agent near or above（I.e. 1:1）When, 4+The vanadium of valency in air high-temperature calcination when can keep stable, generation is big
(VO) of amount2P2O7Phase, only least a portion of VOPO4It generates, therefore vanadium of the P/V molar ratios than actually affecting catalyst
Average valence.The result is that difference P/V than catalyst possess the average valence of different vanadium, oxidability and product and select
Property.
It, can be according to following grading composition method when selecting three grading catalyst beds in the method for the present invention
Carry out Catalyst packing.On the basis of the volume of whole catalyst, first segment use P/V molar ratios for 1.15~1.25 catalysis
Agent, filling ratio be 20~40%, second segment use P/V molar ratios be 1.15~1.05 catalyst, load ratio be 30~
50%, the 3rd section uses P/V molar ratios to load ratio for 1.05~0.98 catalyst as 20~40%.The specific dress of catalyst
Technology is filled out as the conventional practices in this field.
In the method for the present invention, in hybrid reaction gas obtained by normal butane and air, the volume fraction of normal butane is generally
1.0%~1.8%.The oxidation reaction condition is：Reaction pressure is normal pressure~0.5MPa, and reaction temperature is 380~450 DEG C,
Mixed reaction gas product air speed is 1000~3500 h-1。
Present inventor has been had surprisingly found that when the technique to preparing cis-anhydride by n-butane oxidation is studied using several
The vpo catalyst of the different P/V molar ratios of kind, the active phase (VO) of these catalyst2P2O7Phase, VOPO4The content of phase is different, urges
Agent possesses different vanadium average valences, and catalyst activity is urged there are apparent differentiation using the VPO of different P/V molar ratios
For the grading loading that agent carries out, it can be achieved that the regulation and control of catalyst performance, effective control reaction hot spot improves product yield, and
And this method and the result is that novel and unexpected.
Therefore, compared with prior art, the method for preparing cis-anhydride by n-butane oxidation of the invention has the advantages that：
1st, for n butane oxidation reaction it is strongly exothermic the characteristics of, the present invention according to reaction stream engagement sequence, rubbed using P/V
Your increased mode more gradual than activity from high to low carries out the grading loading of catalyst, carries out preparing cis-anhydride by n-butane oxidation reaction.
In reaction process, high concentration reaction stream contacts the catalyst bed of opposite low activity first, and oxidation reaction will not especially acutely
And it is strongly exothermic, as reaction stream continues to contact higher active catalyst, then since raw material butane concentration is decreased,
The severe degree of reaction is gentle, can so reduce reaction hot spot, makes bed temperature distribution average, effective to inhibit side reaction hair
It is raw, product selectivity is improved, increases product yield of maleic anhydride.
2nd, what is provided in the present invention can be in catalyst precursor in the method for P/V molar ratios in quantitative adjusting catalyst
It in preparation process, is realized by controlling the addition of raw material proportioning i.e. vanadic anhydride and phosphoric acid, method is simple, as a result may be used
It leans on, by the way that P/V molar ratios is controlled to conveniently realize the reactivity of regulation and control catalyst.
3rd, during the production of maleic anhydride industry metaplasia, the service life of vpo catalyst is about 5 years, the catalyst in operation process
The reason for inactivation is the loss of phosphorus in catalyst.The oxidation of normal butane is strong exothermal reaction, is reacted there are hot(test)-spot temperature, and hot spot
Temperature is excessively high to promote the rapidly losing of phosphorus in catalyst.Therefore, hot(test)-spot temperature height is to influence catalyst activity to stablize in reaction
A key factor, reaction hot spot can effectively be reduced using method in the present invention, the use of catalyst can be effectively improved
Service life.
4th, wish that vanadium-phosphor oxide catalyst has preferable activity generally in the art, that is, wish P/V in vanadium-phosphor oxide catalyst
It is mole higher.And in the present invention, by n butane oxidation technique the study found that in fact for different P/V molar ratios
Catalyst, it is less preferable using only effect during a kind of catalyst；However by the catalyst of its difference P/V molar ratio according to one
After fixed order carries out grading, good technique effect can be but obtained.Therefore, the present invention provides a kind of n butane oxidations
New technology route.
Description of the drawings
Fig. 1 is the structure diagram of synthesis reactor used in the present invention.
Fig. 2 is catalyst precursor XRD spectra.Wherein ★-VOHPO4·0.5H2O。
Fig. 3 is the XRD spectra of activated rear gained embodiment 1-4 catalyst prods.
Specific embodiment
The heretofore described vanadium-phosphor oxide catalyst with different P/V molar ratios, can by following recommendation method into
It is prepared by row.
（1）The synthesis of catalyst precursor --- vanadium phosphorus oxide
In the reaction kettle with agitating device and reflux condensate device, isobutanol is added in by charge door, vanadic anhydride and is helped
Agitating device is started in agent, while heats up and keep reaction temperature at 95~120 DEG C, carries out back flow reaction, when maintaining the reflux for reaction
Between 2~12 it is small when, add concentrated phosphoric acid（Concentration 85%~100%）, phosphorus is 0.95~1.35 with vanadium molar ratio, continues to maintain the reflux for
When reaction 4~8 is small, reaction terminates to be discharged by reacting material outlet；After reaction solution is cooled to room temperature, it is filtered；Filter cake is with less
After measuring isobutanol elution three times, when natural air drying 12~24 is small at room temperature by filter cake, it is small that 8~12 are then dried in an oven
When, finally in Muffle furnace at 200~285 DEG C, when roasting 4~8 is small, obtain catalyst precursor-nano V phosphorus of dark brown
Oxide.
（2）The preparation of vanadium-phosphor oxide catalyst
Step（1）Gained vanadium phosphorus oxide is first molded, the shape of obtained vanadium-phosphor oxide catalyst can be tabletting, spherical shape,
The shapes such as extrusion, the object of gained catalyst precursor is mutually VOHPO4·0.5H2O。
（3）The activation process of vanadium-phosphor oxide catalyst
Step（2）Catalyst precarsor after shaping, in nitrogen or atmosphere of inert gases or normal butane/air Mixture atmosphere
Middle carry out activation process is enclosed, obtains the vanadium-phosphor oxide catalyst activated.
Wherein step（3）In, the temperature of the activation is generally 350~450 DEG C, is preferably 375~425 DEG C；During activation
Between generally 5~40 it is small when, be preferably 12~20 it is small when.The volume of nitrogen, inert gas or normal butane/air Mixture atmosphere is empty
Speed is generally 100~2000h-1, it is preferably 500~1000h-1。
In the present invention, it is preferred to use identical activation condition is for the prepared catalyst with different P/V molar ratios
Carry out activation process.Such as, preformed catalyst is inserted in tubular reactor, is 0.6% in normal butane content（v）Normal butane/air
Under atmosphere, normal butane/volume of air air speed 500h is kept-1, activation temperature rises to 400 DEG C by 2 DEG C/min of heating rate from room temperature
Carry out calcination process, and keep at 400 DEG C 40 it is small when, activation process terminate to get to by the present invention in green state
Vanadium-phosphor oxide catalyst.The object of gained catalyst is mutually (VO)2P2O7Phase and least a portion of VOPO4Phase.
Vanadium-phosphor oxide catalyst after overactivation can carry out performance evaluation as follows：By the vanadium of above-mentioned preparation
Phosphor oxide catalyst is fitted into fixed bed reactors, is passed through normal butane air gas mixture, is reacted and generated using gas chromatographic analysis
The composition of object.Evaluation response condition is as follows：380~450 DEG C of reaction temperature, pressure be normal pressure~0.5MPa, normal butane gaseous mixture
Air speed is 1000~3500h-1, concentration of n-butane is 1.0%~1.8%（Percent by volume）, carry out the activity rating examination of catalyst
It tests.
With reference to embodiment, the present invention is described in further detail, and following embodiment is not that the present invention is protected
The limitation of scope, those skilled in the art, which combines description of the invention and full text, can do appropriate extension, these extensions are all
It should be protection scope of the present invention.
Crystalline phase detection is carried out using the D/max-2500X x ray diffractometer xs of RIGAKU companies of Japan in embodiment, specific surface
Product is using the full-automatic specific surface area of AUTOSORB3B types of Quantachrome companies of the U.S. and pore-size distribution instrument.Vanadium in catalyst
Element uses fluorescence quantitative analysis, and the measurement of P elements is analyzed using colorimetric determination, and the average valence of vanadium is adopted in catalyst
Use ferrous ammonium sulfate titration.
Embodiment 1
In the reaction kettle with agitating device and reflux condensate device shown in Fig. 1, isobutanol 442.95kg, five oxidations are added in
Two vanadium 29.53kg, auxiliary agent six water ferric nitrate 0.3kg, auxiliary agent zirconium nitrate 0.5kg open stirring, raise reaction temperature and are maintained at
100 ± 2 DEG C, carry out back flow reaction, maintain the reflux for the time 4 it is small when, add the phosphatase 24 7.50kg of concentration 85%, phosphorus/vanadium mole
Than for 1.27, continue reflux 8 it is small when, reaction terminates.After reaction solution is cooled to room temperature, vacuum filtration, a small amount of isobutanol of filter cake
After elution three times, filter cake is put into enamel tray natural air drying at room temperature, when drying 8 is small in 100 DEG C of baking ovens, finally in Muffle
When roasting 5 is small at 250 DEG C in stove, the catalyst precursor of dark brown is obtained.
Catalyst precursor obtained above is added in into the graphite powder that mass fraction is 4%, after being sufficiently mixed, using rotary
Tablet press machine, it is appropriate to adjust impact dynamics, it is squeezed into Raschig ring shape finished catalyst.
Above-mentioned Raschig ring catalyst 150g is taken to insert in tubular reactor, is 0.6% in normal butane content（v）Normal butane/
Under air atmosphere, normal butane/volume of air air speed 500h is kept-1, 2 DEG C/min of heating rate rises to activation temperature from room temperature
400 DEG C of progress calcination process, and keep at 400 DEG C 40 it is small when, activation process terminate to get to by the present invention in green state
Vanadium-phosphor oxide catalyst.
Gained catalyst detects its crystalline phase as (VO) through XRD2P2O7Phase and β-VOPO4The mixture of phase, specific surface area
21m2/ g, pore volume 0.11cm3/g.Catalyst is through colorimetrically analysing, and phosphorus content 22.92%, catalyst is analyzed through fluorescence method, and vanadium contains
Amount 30.17%, catalyst P/V molar ratios 1.25, the average valence of vanadium is+4.01 in catalyst.
Embodiment 2
In the reaction kettle with agitating device and reflux condensate device shown in Fig. 1, isobutanol 442.95kg, five oxidations are added in
Two vanadium 29.53kg, auxiliary agent six water ferric nitrate 0.3kg, auxiliary agent zirconium nitrate 0.5kg open stirring, raise reaction temperature and are maintained at
100 ± 2 DEG C, carry out back flow reaction, maintain the reflux for the time 4 it is small when, add the phosphatase 24 4.13kg of concentration 85%, phosphorus/vanadium mole
Than for 1.18, continue reflux 8 it is small when, reaction terminates.After reaction solution is cooled to room temperature, vacuum filtration, a small amount of isobutanol of filter cake
After elution three times, reaction terminates.Filter cake is put into enamel tray natural air drying at room temperature, when drying 8 is small in 100 DEG C of baking ovens,
When finally roasting 5 is small at 250 DEG C in Muffle furnace, the catalyst precursor of dark brown is obtained.
Catalyst precursor obtained above is added in into the graphite powder that mass fraction is 4%, after being sufficiently mixed, using rotary
Tablet press machine, it is appropriate to adjust impact dynamics, it is squeezed into Raschig ring shape finished catalyst.
Above-mentioned Raschig ring catalyst 150g is taken to insert in tubular reactor, is 0.6% in normal butane content（v）Normal butane/
Under air atmosphere, normal butane/volume of air air speed 500h is kept-1, 2 DEG C/min of heating rate rises to activation temperature from room temperature
400 DEG C of progress calcination process, and keep at 400 DEG C 40 it is small when, activation process terminate to get to by the present invention in green state
Vanadium-phosphor oxide catalyst.
Gained catalyst detects its crystalline phase as (VO) through XRD2P2O7Phase and β-VOPO4The mixture of phase, specific surface area
27m2/ g, pore volume 0.12cm3/g.Catalyst is through colorimetrically analysing, and phosphorus content 21.12%, catalyst is analyzed through fluorescence method, and vanadium contains
Amount 30.21%, catalyst P/V molar ratios 1.15, the average valence of vanadium is+4.05 in catalyst.
Embodiment 3
In the reaction kettle with agitating device and reflux condensate device shown in Fig. 1, isobutanol 442.95kg, five oxidations are added in
Two vanadium 29.53kg, auxiliary agent six water ferric nitrate 0.3kg, auxiliary agent zirconium nitrate 0.5kg open stirring, raise reaction temperature and are maintained at
100 ± 2 DEG C, carry out back flow reaction, maintain the reflux for the time 4 it is small when, add the phosphoric acid 34.33kg of concentration 100%, phosphorus/vanadium mole
Than for 1.08, continue reflux 8 it is small when, reaction terminates.After reaction solution is cooled to room temperature, vacuum filtration, a small amount of isobutanol of filter cake
After elution three times, reaction terminates.Filter cake is put into enamel tray natural air drying at room temperature, when drying 8 is small in 100 DEG C of baking ovens,
When finally roasting 5 is small at 250 DEG C in Muffle furnace, the catalyst precursor of dark brown is obtained.
Catalyst precursor obtained above is added in into the graphite powder that mass fraction is 4%, after being sufficiently mixed, using rotary
Tablet press machine, it is appropriate to adjust impact dynamics, it is squeezed into Raschig ring shape finished catalyst.
Above-mentioned Raschig ring catalyst 150g is taken to insert in tubular reactor, is 0.6% in normal butane content（v）Normal butane/
Under air atmosphere, normal butane/volume of air air speed 500h is kept-1, 2 DEG C/min of heating rate rises to activation temperature from room temperature
400 DEG C of progress calcination process, and keep at 400 DEG C 40 it is small when, activation process terminate to get to by the present invention in green state
Vanadium-phosphor oxide catalyst.
Gained catalyst detects its crystalline phase as (VO) through XRD2P2O7Phase and β-VOPO4The mixture of phase, specific surface area
35m2/ g, pore volume 0.15cm3/g.Catalyst is through colorimetrically analysing, and phosphorus content 19.32%, catalyst is analyzed through fluorescence method, and vanadium contains
Amount 30.27%, catalyst P/V molar ratios 1.05, the average valence of vanadium is+4.10 in catalyst.
Embodiment 4
In the reaction kettle with agitating device and reflux condensate device shown in Fig. 1, isobutanol 442.95kg, five oxidations are added in
Two vanadium 29.53kg, auxiliary agent six water ferric nitrate 0.3kg, auxiliary agent zirconium nitrate 0.5kg open stirring, raise reaction temperature and are maintained at
100 ± 2 DEG C, carry out back flow reaction, maintain the reflux for the time 4 it is small when, add the phosphoric acid 31.97kg of concentration 100%, phosphorus/vanadium mole
Than for 1.0, continue reflux 8 it is small when, reaction terminates.After reaction solution is cooled to room temperature, vacuum filtration, filter cake is drenched with a small amount of isobutanol
After washing three times, reaction terminates.Filter cake is put into enamel tray natural air drying at room temperature, when drying 8 is small in 100 DEG C of baking ovens, most
When roasting 5 is small at 250 DEG C in Muffle furnace afterwards, the catalyst precursor of dark brown is obtained.
Catalyst precursor obtained above is added in into the graphite powder that mass fraction is 4%, after being sufficiently mixed, using rotary
Tablet press machine, it is appropriate to adjust impact dynamics, it is squeezed into Raschig ring shape finished catalyst.
Above-mentioned Raschig ring catalyst 150g is taken to insert in tubular reactor, is 0.6% in normal butane content（v）Normal butane/
Under air atmosphere, normal butane/volume of air air speed 500h is kept-1, 2 DEG C/min of heating rate rises to activation temperature from room temperature
400 DEG C of progress calcination process, and keep at 400 DEG C 40 it is small when, activation process terminate to get to by the present invention in green state
Vanadium-phosphor oxide catalyst.
Gained catalyst detects its crystalline phase as (VO) through XRD2P2O7Phase and β-VOPO4The mixture of phase, specific surface area
35m2/ g, pore volume 0.15cm3/g.Catalyst is through colorimetrically analysing, and phosphorus content 17.89%, catalyst is analyzed through fluorescence method, and vanadium contains
Amount 30.34%, catalyst P/V molar ratios 0.97, the average valence of vanadium is+4.25 in catalyst.
Embodiment 5
On the small-sized preparing cis-anhydride by n-butane oxidation experimental rig of 200mL fixed beds, reaction tube is that internal diameter is 18mm stainless steel reactions
Pipe, divides three sections of grading loadings from the bottom to top along logistics direction, and catalyst grading distribution scheme is on the basis of the weight of whole catalyst, and the
One section of 1.25 catalyst of P/V molar ratios using embodiment 1, loadings 25%, second segment use the P/V molar ratios of embodiment 3
1.05 catalyst, loadings 50%, the 3rd section of 0.97 catalyst of P/V molar ratios using embodiment 4, loadings 25%,
Inertia magnet ring is filled out in remaining part packing.In 420 DEG C, reaction pressure 0.25MPa of reactor salt temperature, reaction gas is butane volumetric concentration
1.6% normal butane/air Mixture, gas space velocity 1560h-1Reaction condition under carry out the reaction of normal butane cis-butenedioic anhydride.Experiment
As a result it is that n-butane conversion is 82.7%（Mole）, yield of maleic anhydride 70.2%（Mole）.Result of the test and catalyst bed hot spot
1 is shown in Table respectively.
Embodiment 6
On the small-sized preparing cis-anhydride by n-butane oxidation experimental rig of 200mL fixed beds, reaction tube is that internal diameter is 18mm stainless steel reactions
Pipe, divides three sections of grading loadings from the bottom to top along logistics direction, and catalyst grading distribution scheme is on the basis of the weight of whole catalyst, and the
One section of catalyst using the P/V molar ratios 1.15 of embodiment 2, loadings 40%, second segment use P/V moles of embodiment 3
Catalyst than 1.05, loadings 40%, the 3rd section of 0.97 catalyst of P/V molar ratios using embodiment 4, loadings are
20%, rest part filling inertia magnet ring.In 420 DEG C, reaction pressure 0.25MPa of reactor salt temperature, reaction gas is butane body
Normal butane/air Mixture of product concentration 1.6%, gas space velocity 1560h-1Reaction condition under carry out normal butane cis-butenedioic anhydride it is anti-
It should.Result of the test is that n-butane conversion is 84.2%（Mole）, yield of maleic anhydride 67.9%（Mole）.Result of the test and catalyst
Bed hot spot is shown in Table 1 respectively.
Embodiment 7
On the small-sized preparing cis-anhydride by n-butane oxidation experimental rig of 200mL fixed beds, reaction tube is that internal diameter is 18mm stainless steel reactions
Pipe, divides three sections of grading loadings from the bottom to top along logistics direction, and catalyst grading distribution scheme is on the basis of the weight of whole catalyst, and the
One section of catalyst using the P/V molar ratios 1.25 of embodiment 1, loadings 20%, second segment use P/V moles of embodiment 2
Catalyst than 1.15, loadings 50%, the 3rd section of 1.05 catalyst of P/V molar ratios using embodiment 3, loadings are
30%, rest part filling inertia magnet ring.In 420 DEG C, reaction pressure 0.25MPa of reactor salt temperature, reaction gas is butane body
Normal butane/air Mixture of product concentration 1.6%, gas space velocity 1560h-1Reaction condition under carry out normal butane cis-butenedioic anhydride it is anti-
It should.Result of the test is that n-butane conversion is 82.7%（Mole）, yield of maleic anhydride 69.4%（Mole）.Result of the test and catalyst
Bed hot spot is shown in Table 1 respectively.
Comparative example 1
On the small-sized preparing cis-anhydride by n-butane oxidation experimental rig of 200mL fixed beds, reaction tube is that internal diameter is 18mm stainless steel reactions
Pipe, is packed into using USP4, catalyst 100mL prepared by 632,915 methods provided, rest part filling inertia magnet ring.
430 DEG C, reaction pressure 0.25MPa of reaction temperature, reaction gas be butane volumetric concentration 1.8% normal butane/air Mixture, gas
Body air speed is 1560h-1Reaction condition under carry out the reaction of normal butane cis-butenedioic anhydride.Result of the test is that butanes conversion is 78.1%, suitable
Acid anhydride molar yield is 54.5%.Result of the test and catalyst bed hot spot difference table 1.
Comparative example 2
On the small-sized preparing cis-anhydride by n-butane oxidation experimental rig of 200mL fixed beds, reaction tube is that internal diameter is 18mm stainless steel reactions
Pipe, the catalyst of filling P/V molar ratios 0.97, loadings 50mL, rest part filling inertia magnet ring.In reactor salt bath temperature
Degree 420 DEG C, reaction pressure 0.25MPa, reaction gas be butane volumetric concentration 1.6% normal butane/air Mixture, gas space velocity
For 1560h-1Reaction condition under carry out the reaction of normal butane cis-butenedioic anhydride.Result of the test is that n-butane conversion is 98.1%（Mole）,
Yield of maleic anhydride 49.9%（Mole）.Result of the test and catalyst bed hot spot are shown in Table 1 respectively.
Comparative example 3
On the small-sized preparing cis-anhydride by n-butane oxidation experimental rig of 200mL fixed beds, reaction tube is that internal diameter is 18mm stainless steel reactions
Pipe, the catalyst of filling P/V molar ratios 1.25, loadings 50mL, rest part filling inertia magnet ring.In reactor salt bath temperature
Degree 420 DEG C, reaction pressure 0.25MPa, reaction gas be butane volumetric concentration 1.6% normal butane/air Mixture, gas space velocity
For 1560h-1Reaction condition under carry out the reaction of normal butane cis-butenedioic anhydride.Result of the test is that n-butane conversion is 71.4%（Mole）,
Yield of maleic anhydride 50.6%（Mole）.Result of the test and catalyst bed hot spot are shown in Table 1 respectively.
The experimental result of 1 embodiment of table and comparative example
Claims (12)
1. a kind of method that n butane oxidation prepares cis-butenedioic anhydride, including herein below：
Normal butane is mixed with air, the vanadium-phosphor oxide catalyst bed that acquired hybrid reaction gas cocurrent passes through at least two series connection
Layer, under oxidation reaction condition, contacts with vanadium-phosphor oxide catalyst and is reacted；According to the engagement sequence with hybrid reaction gas, under
Swim P/V molar ratio of the P/V molar ratios less than catalyst in the bed of upstream of catalyst in bed.
2. according to the method for claim 1, which is characterized in that in two adjacent vanadium-phosphor oxide catalyst beds, downstream
In catalyst bed the P/V molar ratios of catalyst be higher by 0.01 than the P/V molar ratios of catalyst in adjacent upstream bed~
0.15 unit.
3. according to the method for claim 2, which is characterized in that the P/V molar ratios ratio of catalyst in downstream catalyst bed
The P/V molar ratios of catalyst are higher by 0.02~0.12 unit in adjacent upstream bed.
4. according to the method for claim 3, which is characterized in that the P/V molar ratios ratio of catalyst in downstream catalyst bed
The P/V molar ratios of catalyst are higher by 0.03~0.05 unit in adjacent upstream bed.
5. according to any methods of claim 1-4, which is characterized in that the P/V molar ratios of the vanadium-phosphor oxide catalyst are
0.95~1.45.
6. according to the method for claim 5, which is characterized in that the P/V molar ratios of the vanadium-phosphor oxide catalyst for 0.97~
1.25。
7. according to the method for claim 1, which is characterized in that the number of the vanadium-phosphor oxide catalyst bed is 3~5.
8. according to the method for claim 7, which is characterized in that the number of the vanadium-phosphor oxide catalyst bed is 3.
9. according to the method for claim 8, which is characterized in that when selecting 3 vanadium-phosphor oxide catalyst beds, according to mixing
The order of reaction gas contact is closed, the P/V molar ratios of catalyst are 1.15~1.25 in the catalyst bed of most upstream, intermediate catalyst
The P/V molar ratios of catalyst are 1.15~1.05 in agent bed, the P/V molar ratios 0.97 of catalyst in the catalyst bed of most downstream
~1.05.
10. according to the method for claim 9, which is characterized in that with the stereometer of whole vanadium-phosphor oxide catalysts, most upstream is urged
The filling ratio of agent bed is 20~40%, and the filling ratio of Intermediate Catalyst bed is 30~50%, most downstream catalyst bed
Layer filling ratio is 20~40%.
11. according to the method for claim 1, which is characterized in that in hybrid reaction gas obtained by normal butane and air, normal butane
Volume fraction be 1.0%~1.8%.
12. according to the method for claim 1, which is characterized in that the oxidation reaction condition is：Reaction pressure is normal pressure
~0.5MPa, reaction temperature are 380~450 DEG C, and mixed reaction gas product air speed is 1000~3500 h-1。
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| CN112442001A (en) * | 2019-08-30 | 2021-03-05 | 中国石油化工股份有限公司 | Method for preparing maleic anhydride by oxidizing n-butane |
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