CN106140235A - A kind of support type catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof - Google Patents

Abstract

The present invention relates to the catalyst of a kind of support type preparing cis-anhydride by n-butane oxidation, described catalyst comprises active component and carrier, and described active component is (VO)₂P₂O₇, described carrier is TiO₂The SiO of cladding₂Microsphere.Present invention also offers the preparation method of a kind of described catalyst.

Description

A kind of support type catalyst for preparing cis-anhydride by n-butane oxidation and preparation method thereof

Technical field

The present invention relates to catalyst field, more precisely be that a kind of fixed bed carried type n butane oxidation prepares maleic Dicarboxylic anhydride (abbreviation cis-butenedioic anhydride) vpo catalyst and preparation method thereof.

Background technology

Cis-butenedioic anhydride is important Organic Chemicals, be largely used to produce thermosetting resin, unsaturated polyester resin, Pesticide and fine chemical product.The primary raw material of industrial production cis-butenedioic anhydride is benzene and normal butane, due to butane resource Abundant and lower than benzene price, and the strict restriction that environmental administration is to benzene subtraction unit discharge standard, use positive fourth simultaneously It is similar with benzene method equipment therefor that alkane occurs to produce cis-butenedioic anhydride, and normal butane gradually substituted benzene is raw material production cis-butenedioic anhydride.This reaction Maximally efficient most widely used industrial catalyst is vanadium phosphorus oxygen (VPO) series catalysts.

At present, the fixed bed vpo catalyst of industrial applications all uses unsupported catalyst, its activity group It is divided into Vanadyl pyrophosphate.Owing to vpo catalyst itself exists as less in specific surface area, intensity is relatively low, heat transfer The shortcomings such as weak effect.Compared with unsupported catalyst, there is advantages below in loaded catalyst: (1) compares table Area is big, active phase dispersion；(2) mechanical strength of catalyst is improved；(3) heat transfer property of catalyst is strengthened. A lot of materials are used as the carrier of support type vpo catalyst, such as SiO₂、TiO₂、MCM-41、SBA-15、 ZrO₂、Al₂O₃、AlPO₄, SiC etc., but result unsatisfactory, compared with unsupported catalyst The reactivity worth being carried on carrier rear catalyst all decreases.

The silicon substrate carrier of most study includes SiO prepared by pyrolysismethod₂, macro-pore SiO₂、MCM-41、SBA-15 And the MCM-41 containing aluminum, although found that supported catalyst can preferably keep (VO)₂P₂O₇Good Crystal form, but the activity of catalyst is unsatisfactory.The effect being likely due between carrier and catalyst component hinders Active component (VO)₂P₂O₇Form or cause the change of phase composition, and non-selection in these VPO materials Property VOPO₄The V during generally existence increases catalyst of phase⁵⁺/V⁴⁺Ratio, causes the decline of Selectivity of maleic anhydride.Specially Profit CN1935374 provides the method preparing support type vpo catalyst, uses H₃PO₄To ZrO used₂ Carrier carries out surface modification, considerably enhances the catalytic performance of catalyst, but Selectivity of maleic anhydride raises with temperature Decline substantially.Patent CN10357310 is referred to and a kind of uses the TiO after acid treatment₂-ZrO₂Composite oxides The method of carrier, loaded catalyst shows preferable catalytic performance, and this is likely due to answering as carrier Close oxide and compare single ZrO₂For carrier, the bigger crystal grain of specific surface area is less, and suitable VPO component plays Preferably effect, but the preparation technology of composite oxide carrier is complex comparatively speaking.

VPO/TiO₂Catalyst is the most few, due to VPO for the research of selective oxidation of n-butane cis-butenedioic anhydride reaction The reason that method for preparing catalyst is more complicated, the loaded catalyst poor-performing obtained.The most also have Person studies VPO/TiO₂Catalyst, but typically it is applied to other reaction, such as the ammonia of 3-picoline Oxidation reaction, the aspect being applied to normal butane selective oxidation is less.

Summary of the invention

One of the technical problem to be solved be prior art preparing cis-anhydride by n-butane oxidation reaction yield low, The problem of poor selectivity, it is therefore intended that provide a kind of novel support type preparing cis-anhydride by n-butane oxidation VPO to be catalyzed Agent, this catalyst has high activity, high selective feature.It is a further object to provide a kind of system The method of standby support type preparing cis-anhydride by n-butane oxidation vpo catalyst, the method is easy and simple to handle, it is easy to accomplish.

One aspect of the present invention relates to the catalyst of a kind of support type preparing cis-anhydride by n-butane oxidation, comprises activity group Dividing and carrier, described active component is (VO)₂P₂O₇, described carrier is TiO₂The SiO of cladding₂Microsphere.

In a preferred embodiment of the present invention, described loaded catalyst include by weight percentage with Lower component:

～the single dispersing TiO of 60% a.5₂-SiO₂Microsphere supported；Thereon with being loaded in

～the V of 50% b.20₂O₅；

～the P of 50% c.20₂O₅；And

～the metal-oxide of 5% d.0.

In a preferred embodiment of the present invention, described TiO₂-SiO₂Complex microsphere carrier particle size is 200～1000nm, preferably 400～800nm.

In a preferred embodiment of the present invention, described V₂O₅、P₂O₅Derive from vanadium composite phosphorus oxide, And the atomic ratio of described vanadium and phosphorus is between 0.8～2, preferably 1.0～1.4.

In a preferred embodiment of the present invention, described metal-oxide is indium oxide, and indium, vanadium Atomic ratio is 1:100～5:100.

Another aspect of the present invention relates to the preparation method of support type vpo catalyst, comprises the following steps:

1) single dispersing TiO is provided₂-SiO₂Complex microsphere carrier；

2) with vanadic anhydride and phosphoric acid as raw material, with organic alcohols solvent as reducing agent with solvent, heat back Stream reaction, adds afterwards or is added without metal promoter and continue reaction, continue to add polyalcohols chemical combination in reaction system Thing and described single dispersing TiO₂-SiO₂Complex microsphere carrier, mixes the presoma obtained at butane and air Activate under gas atmosphere, obtain described catalyst.

In a preferred embodiment of the present invention, described metal promoter is containing indium compound, preferably indium chloride, At least one in indium acetate or indium nitrate；More preferably indium acetate；Most preferably, according to indium, the atom of vanadium Than be 1/100 to 5/100 add described containing indium compound；Described organic alcohols solvent is isobutanol and benzene first Alcohol；Described polyalcohols compound is preferably Polyethylene Glycol.

In a preferred embodiment of the present invention, described butane and air are preferably volume ratio 1.8/98.2； The air speed of described reaction gas is 1000h^-1；Described roasting, is preferably and is warming up to the heating rate of 2 DEG C/min 380 DEG C of roastings 20 hours, are continuously heating to 430 DEG C of roastings 14 with the heating rate of 3 DEG C/min little subsequently Time.

In a preferred embodiment of the present invention, described TiO₂-SiO₂The preparation method of complex microsphere carrier As follows:

1) at room temperature ammonia is mixed and stirred for alcohols solvent and deionized water, is subsequently added esters of silicon acis, Obtain precipitated liquid, under agitation reaction 4～6 hours；

2) gained is precipitated scrubbed to pH value < after 8, at 80～120 DEG C be dried 8～12 hours；

3) by dried SiO₂Microsphere sample is scattered in alcohols solvent, disperses, and add under ultrasound condition Deionized water, is uniformly mixed；

4) titanate esters is joined in alcohols solvent, after this solution is joined SiO₂In microsphere alcohol dispersion, It is warming up to reflux temperature, under reflux conditions reaction 2～4 hours.

5) gained sample filtering, alcohol are washed, after at 80～120 DEG C be dried 8～12 hours, obtain single dispersing TiO₂-SiO₂Complex microsphere carrier.

In a preferred embodiment of the present invention, described alcohols solvent is preferably dehydrated alcohol；And it is described Titanate esters is butyl titanate or tetraisopropyl titanate, preferably butyl titanate.

Beneficial effects of the present invention:

Using support type vpo catalyst prepared by the present invention, VPO component can be divided on carrier surface equably Cloth, the formation of beneficially VPO active component and the carrying out of surface reaction, thus improve to a certain extent Catalytic performance.Catalyst shows good catalytic effect under higher space velocity.Concrete data refer to embodiment The result be given with table 1.

Accompanying drawing explanation

Fig. 1 support type catalyst for preparing cis-anhydride by n-butane oxidation and the XRD spectra of presoma thereof, wherein (a) table Showing support type vpo catalyst presoma, (b) represents the support type vpo catalyst after activation.

Fig. 2 support type catalyst for preparing cis-anhydride by n-butane oxidation and the SEM picture of presoma thereof, wherein (a) is Single dispersing SiO₂Microsphere, (b) is single dispersing TiO₂-SiO₂Microsphere supported, (c) is support type vpo catalyst Presoma, (d) is the support type vpo catalyst after activation.

Detailed description of the invention

Below in conjunction with embodiment, the present invention is described in detail, but the scope of the present invention is not limited to following enforcement Example.

Embodiment 1

At room temperature, add ammonia (25%) 77mL in the reactor, add dehydrated alcohol 75mL, go from Sub-water 3mL, stirs.It is slowly added dropwise the tetraethyl orthosilicate of 7mL wherein, after dropping, continues React 4 hours.Filter, deionized water wash to pH < 8, be further continued for using absolute ethanol washing sample, at 80 DEG C Lower baking oven is dried 12 hours.SiO by dried 0.3g₂Microsphere sample is scattered in the anhydrous second of 20mL In alcohol, disperse under ultrasound condition, after this dispersion is transferred in another reactor, and add 0.58g Deionized water, be uniformly mixed.The butyl titanate of 0.31g is joined in the dehydrated alcohol of 70mL, Stirring be allowed to fully dissolve, after this solution is slowly added into SiO₂In microsphere alcohols dispersion, it is warming up to back Stream temperature, under reflux conditions reaction 2 hours.By gained sample through filtering, alcohol is washed, after dry at 80 DEG C Dry 12 hours, i.e. obtain monodispersed TiO₂-SiO₂Complex microsphere carrier.

By 2.5g V₂O₅Join in the mixed solution of 70mL isobutanol and 10mL benzyl alcohol and be heated with stirring to Reflux 3 hours, be added thereto to the Polyethylene Glycol that molecular weight is 1500 of 0.8g, the indium acetate of 0.4g, 0.3 The monodispersed TiO of g₂-SiO₂Complex microsphere carrier, continues agitating heating back flow reaction and stops heating after 1 hour, Wait to lower the temperature and backward system is added dropwise to the phosphoric acid 3.8g of 85wt% and heated and stirred keeps 11 hours to backflow, institute Must precipitate through filtering and being dried 20 hours at 120 DEG C after washing.Dried sample tabletting is pulverized, sieve The granule taking required granularity is divided to load reactor, with 2 DEG C/min in the atmosphere of butane/air (1.8/98.2) Heating rate be warming up to 380 DEG C of roastings 20 hours, be continuously heating to the heating rate of 3 DEG C/min subsequently 430 DEG C of roastings 14 hours, obtain single dispersing TiO₂-SiO₂Micro-ball load vpo catalyst, gained catalyst Check and rate through micro fixed-bed reactor, when 430 DEG C, 1.80% butane charging, 2000h^-1Air speed under, Catalyst Conversion reaches 82.0%, and Selectivity of maleic anhydride 67.5%, yield of maleic anhydride is 55.7%.

Comparative example 1

By 2.5g V₂O₅Join in the mixed solution of 70mL isobutanol and 10mL benzyl alcohol and be heated with stirring to Refluxing 3 hours, the indium acetate continuation agitating heating back flow reaction being added thereto to 0.4g stopped adding after 1 hour Heat, the phosphoric acid 3.8g the heated and stirred that are added dropwise to 85wt% in backward system of waiting to lower the temperature keep 9 hours to backflow, It is dried 20 hours at 120 DEG C after gained precipitation filtration washing.Dried sample tabletting is pulverized needed for taking The granule of granularity loads in reactor, with the intensification of 2 DEG C/min in the atmosphere of butane/air (1.8/98.2) Ramp, to 380 DEG C of roastings 20 hours, is continuously heating to 430 DEG C with the heating rate of 3 DEG C/min subsequently Roasting 14 hours, obtains vpo catalyst, and gained catalyst is checked and rated through micro fixed-bed reactor, 430 DEG C time, 1.80% butane charging, 2000h^-1Air speed under, Catalyst Conversion is 75.3%, Selectivity of maleic anhydride 61.4%, yield of maleic anhydride is 46.5%.

Embodiment 2

At room temperature, add ammonia (25%) 10mL in the reactor, add dehydrated alcohol 130mL, go Ionized water 6mL, stirs 30 minutes.It is slowly added dropwise the tetraethyl orthosilicate of 4mL wherein, after dropping, Continue reaction 6 hours.Then filtration washing is to pH < 8, is further continued for using absolute ethanol washing sample, at 80 DEG C Lower baking oven is dried 12 hours.SiO by dried 0.6g₂Microsphere sample is scattered in the anhydrous second of 50mL In alcohol, disperse under ultrasound condition, after this dispersion is transferred in another reactor, and add 1.02g Deionized water, be uniformly mixed.The butyl titanate of 0.97g is joined in the dehydrated alcohol of 80mL, Stirring be allowed to fully dissolve, after this solution is slowly added into SiO₂In microsphere alcohols dispersion, it is warming up to back Stream temperature, under reflux conditions reaction 3 hours.By gained sample through filtering, alcohol is washed, after dry at 80 DEG C Dry 12 hours, i.e. obtain monodispersed TiO₂-SiO₂Complex microsphere carrier.

Subsequent step is with embodiment 1, except adding the Polyethylene Glycol of 0.4g molecular weight 2000, and the indium acetate of 0.3g, The TiO of 0.6g₂-SiO₂Outside microsphere supported.Gained catalyst is checked and rated through micro fixed-bed reactor, at 430 DEG C Time, 1.8% butane charging, 2000h^-1Air speed under, Catalyst Conversion reaches 80.2%, Selectivity of maleic anhydride 66.3%, yield of maleic anhydride is 53.2%.

Embodiment 3

Monodispersed TiO₂-SiO₂Complex microsphere carrier is prepared with embodiment 1.

By 2.5g V₂O₅Join in the mixed solution of 40mL isobutanol and 10mL benzyl alcohol and be heated with stirring to Reflux 3 hours, be added thereto to the Polyethylene Glycol that molecular weight is 6000 of 0.4g, the indium acetate of 0.3g, 0.8 The monodispersed TiO of g₂-SiO₂Microsphere supported, subsequent step is with embodiment 1.Gained catalyst is through miniature fixing Bed reactor examination, when 430 DEG C, 1.8% butane charging, 2000h^-1Air speed under, Catalyst Conversion Reaching 78.4%, Selectivity of maleic anhydride 63.7%, yield of maleic anhydride is 49.9%.

Embodiment 4

At room temperature, add ammonia (25%) 55mL in the reactor, add dehydrated alcohol 75mL, go Ionized water 3mL, stirs.It is slowly added dropwise the tetraethyl orthosilicate of 7mL wherein, after dropping, continues Continuous reaction 4 hours.Filter, wash to pH < 8, be further continued for using absolute ethanol washing sample, dry at 80 DEG C Case is dried 12 hours.SiO by dried 1.5g₂Microsphere sample is scattered in the dehydrated alcohol of 80mL, Under ultrasound condition disperse, after this dispersion is transferred in another reactor, and add 1.52g go from Sub-water, is uniformly mixed.The tetraisopropyl titanate of 1.16g is joined in the dehydrated alcohol of 80mL, stir Mix and be allowed to fully dissolve, after this solution is slowly added into SiO₂In microsphere alcohols dispersion, it is warming up to backflow Temperature, under reflux conditions reaction 4 hours.By gained sample through filter, alcohol wash, after at 80 DEG C be dried 12 hours, i.e. obtain monodispersed TiO₂-SiO₂Complex microsphere carrier.

Subsequent step is with embodiment 1, except adding the Polyethylene Glycol of 0.8g molecular weight 1500, and the indium acetate of 0.2g, The TiO of 1.5g₂-SiO₂Outside microsphere supported.Gained catalyst is checked and rated through micro fixed-bed reactor, at 430 DEG C Time, 1.80% butane charging, 1000h^-1Air speed under, Catalyst Conversion reaches 84.3%, Selectivity of maleic anhydride 53.7%, yield of maleic anhydride is 45.3%.

Embodiment 5

At room temperature, add ammonia (25%) 55mL in the reactor, add dehydrated alcohol 75mL, go from Sub-water 3mL, stirs.It is slowly added dropwise the tetraethyl orthosilicate of 7mL wherein, after dropping, continues React 4 hours.Filter, wash to pH < 8, be further continued for using absolute ethanol washing sample, baking oven at 80 DEG C In be dried 12 hours.SiO by dried 1.5g₂Microsphere sample is scattered in the dehydrated alcohol of 80mL, Under ultrasound condition disperse, after this dispersion is transferred in another reactor, and add 1.52g go from Sub-water, is uniformly mixed.The tetraisopropyl titanate of 1.16g is joined in the dehydrated alcohol of 80mL, stir Mix and be allowed to fully dissolve, after this solution is slowly added into SiO₂In microsphere alcohols dispersion, it is warming up to backflow Temperature, under reflux conditions reaction 4 hours.By gained sample through filter, alcohol wash, after at 80 DEG C be dried 12 hours, i.e. obtain monodispersed TiO₂-SiO₂Complex microsphere carrier.

Subsequent step is with embodiment 1, except the Polyethylene Glycol of interpolation 0.8g molecular weight 1500, the TiO of 1.5g₂-SiO₂ Outside microsphere supported.Gained catalyst is checked and rated through micro fixed-bed reactor, and when 430 DEG C, 1.80% butane enters Material, 1000h^-1Air speed under, Catalyst Conversion reaches 83.9%, Selectivity of maleic anhydride 50.2%, and cis-butenedioic anhydride is received Rate is 42.1%.

Embodiment 6-13

Use the catalyst of embodiment 1, in fixed bed reactors, change reaction temperature, air speed and unstripped gas Composition, its result such as table 1.

Table 1 evaluating catalyst result

* feed gas volume is than the volume ratio for butane Yu air

Claims (10)

1. a catalyst for support type preparing cis-anhydride by n-butane oxidation, comprises active component and carrier, described work Property component is (VO)₂P₂O₇, described carrier is TiO₂The SiO of cladding₂Microsphere.

Catalyst the most according to claim 1, it is characterised in that described loaded catalyst is with weight Percentages includes following components:

～the single dispersing TiO of 60% a.5₂-SiO₂Microsphere supported；Thereon with being loaded in

～the V of 50% b.20₂O₅；

～the P of 50% c.20₂O₅；And

～the metal-oxide of 5% d.0.

Method the most according to claim 1 and 2, it is characterised in that described TiO₂-SiO₂Complex microsphere Carrier particle size is 200～1000nm, preferably 400～800nm.

Catalyst the most according to claim 2, it is characterised in that described V₂O₅、P₂O₅Derive from vanadium Composite phosphorus oxide, and the atomic ratio of described vanadium and phosphorus is between 0.8～2, preferably 1.0～1.4.

5. according to the catalyst described in any one in claim 2-4, it is characterised in that described burning Thing is indium oxide, and the atomic ratio of indium, vanadium is 1:100～5:100.

6. according to the preparation method of the support type vpo catalyst described in any one in claim 1-5, bag Include following steps:

1) single dispersing TiO is provided₂-SiO₂Complex microsphere carrier；

2) with vanadic anhydride and phosphoric acid as raw material, with organic alcohols solvent as reducing agent with solvent, heat back After stream reaction, after adding or being added without metal promoter continuation reaction, in reaction system, add polyalcohols compound And described single dispersing TiO₂-SiO₂Complex microsphere carrier, by the presoma that obtains in butane and air Mixture Activate under atmosphere, obtain described catalyst.

Method the most according to claim 6, it is characterised in that described metal promoter is containing indium compound, Preferably at least one in indium chloride, indium acetate or indium nitrate；More preferably indium acetate；Most preferably, according to Indium, the atomic ratio of vanadium be 1/100 to 5/100 add described containing indium compound；Described organic alcohols solvent is Isobutanol and benzyl alcohol；Described polyalcohols compound is preferably Polyethylene Glycol.

8. according to the method described in claim 6 or 7, it is characterised in that described butane and air are preferably Volume ratio 1.8/98.2；The air speed of described reaction gas is 1000h^-1；Described roasting, is preferably with 2 DEG C/min Heating rate be warming up to 380 DEG C of roastings 20 hours, be continuously heating to the heating rate of 3 DEG C/min subsequently 430 DEG C of roastings 14 hours.

9. according to the method according to any one of claim 6-8, it is characterised in that described TiO₂-SiO₂Multiple Close microsphere supported preparation method as follows:

1) at room temperature ammonia is mixed and stirred for alcohols solvent and deionized water, is subsequently added esters of silicon acis, Obtain precipitated liquid, under agitation reaction 4～6 hours；

2) gained is precipitated scrubbed to pH value < after 8, at 80～120 DEG C be dried 8～12 hours；

3) by dried SiO₂Microsphere sample is scattered in alcohols solvent, disperses, and add under ultrasound condition Enter deionized water, be uniformly mixed；

4) titanate esters is joined in alcohols solvent, after this solution is joined SiO₂In microsphere alcohol dispersion, It is warming up to reflux temperature, under reflux conditions reaction 2～4 hours.

5) gained sample filtering, alcohol are washed, after at 80～120 DEG C be dried 8～12 hours, obtain single dispersing TiO₂-SiO₂Complex microsphere carrier.

10. according to the preparation method according to any one of claim 6-9, it is characterised in that described alcohols is molten Agent is preferably dehydrated alcohol；And described titanate esters is butyl titanate or tetraisopropyl titanate, preferably metatitanic acid Four butyl esters.