CN104437664B - A kind of method preparing alpha-alumina supports - Google Patents
A kind of method preparing alpha-alumina supports Download PDFInfo
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Abstract
The present invention provides a kind of method preparing alpha-aluminium oxide carrier, comprises the steps: that step I, preparation comprise the mixture of following component, a: alumina powder；B: binding agent, described binding agent is Alumina gel, and described Alumina gel can be completely or partially with a false water A12O3With acid reaction formed Alumina gel and replace；C: fluoride-mineralization agent；D: citric acid or the compound containing citrate, its gross weight based on component a～e is 0.01～20.0wt%；E: silicon or silicon-containing compound, its gross weight based on component a～e is 0.0～5.0wt%；F: water；And step II, the mixture obtained in step I is mediated uniformly, is dried after extrusion molding and roasting obtains described alpha-aluminium oxide carrier.The present invention, by using interpolation citric acid or the method containing citrate compound in the feed to prepare alpha-aluminium oxide carrier, can prepare specific surface area increase, the crystal formation alpha-aluminium oxide carrier in interlocking lamellar.
Description
Technical field
The present invention relates to the preparation method of a kind of alpha-alumina supports, it is more particularly related to one is prepared for second
Alkene oxidation produces the method for the alpha-alumina supports of oxirane silver catalyst.
Background technology
Under silver catalyst effect, oxidation of ethylene mainly generates oxirane, occurs side reaction to generate carbon dioxide and water simultaneously,
Wherein activity, selectivity and stability are the main performance index of silver catalyst.Activity refers to that process for ethylene oxide production reaches
Reaction temperature required during certain reaction load；Reaction temperature is the lowest, and the activity of catalyst is the highest.Selectivity refers in reaction
Ethylene changes into the molal quantity of oxirane and the ratio of the overall reaction molal quantity of ethylene.Stability is then expressed as activity and selectivity
Fall off rate, the stability of fall off rate more small catalyst is the best.Use during oxidation of ethylene produces oxirane
High activity, high selectivity and the silver catalyst having good stability can be greatly improved economic benefit, therefore manufacture high activity, height
The silver catalyst of selectivity and good stability is the Main way of silver catalyst research.The performance of silver catalyst is removed and catalyst
Composition and preparation method have outside important relationship, the performance of carrier and the preparation thereof that also use with catalyst have important relationship.
In prior art the preparation method of silver catalyst include porous carrier (such as aluminium oxide) preparation and apply active component with
And auxiliary agent is to the two process on described carrier.In alumina support, add other component improve carrier to improve silver catalyst
Performance be an important research direction, including adding alkaline earth oxide or other salt compounds.
EP0150238(US4428863) in the manufacture process of surface oxidation alumina supporter high-purity, low, a small amount of barium aluminate or silicic acid are used
Barium binding agent, claims to improve crushing strength and the wear resistance of carrier, and the specific surface of prepared carrier is less than 0.3m2/ g,
The activity and selectivity of prepared catalyst all ratios are relatively low.US5384302 claims by pretreatment α-Al2O3Reduce carrier
In Na, K, Ca, Al ion concentration can improve crushing strength and the abrasion resistance properties of carrier.US5739075 passes through
Alumina carrier surface be previously deposited the rare earth metal of amount of auxiliary and another kind of amount of auxiliary slaine (alkaline-earth metal or
VIII transition metal), then carry out calcination processing, the carrier handled well the most at last makes silver catalyst, evaluation result table
Bright, this selectivity of catalyst fall off rate is less than not doing the catalyst sample that pre-deposition processes.
Fluoride, as a kind of mineralizer, has a wide range of applications in the preparation process of alumina support.CN1034678A
By granularity, three water Alpha-aluminas of ratio appropriate mix and a false water Alpha-alumina and carbonaceous material, flux, fluoride,
Binding agent and water mixing, kneaded and formed, alpha-alumina supports is made in drying roasting.The specific surface of this carrier is 0.2～2m2/ g,
Pore radius accounts for total pore volume less than 25% more than the hole of 30 μm；This carrier is through impregnation with silver compound and promoter and is dried activation
After, for oxidation of ethylene epoxy ethane, selectivity is up to 83～84%.CN101007287A is by three water of certain particle size
Alpha-alumina, a false water Alpha-alumina, a certain amount of can after-flame carbonaceous material, flux, fluoride, optional heavy alkaline earth
The compound of metal mixes mutually, adds binding agent and water after mix homogeneously, mediates uniformly, extruded, drying roasting,
Make alpha-alumina supports；The specific surface of described carrier is 0.2～2.0m2/ g, pore volume is 0.35～0.85ml/g, water absorption rate
>=30%, crushing strength 30～120N/ grain.This carrier argent-amine complex, alkali metal compound, alkaline earth metal compound
Solution impregnation, prepares silver catalyst for ethylene epoxidizing epoxy ethane after being dried activation.CN1634652A is in carrier system
In Bei, do not use pore creating material, but directly by three water Alpha-aluminas with certain proportion and a false water aluminium oxide, flux, fluorine
Compound mixes mutually, adds binding agent and water after mix homogeneously, mediates uniformly, extruded, and α-oxygen is made in drying roasting
Change alumina supporter.The carrier specific surface that this invention is made is 0.2～2.0m2/ g, pore volume is 0.35～0.85ml/g, water absorption rate >=30%,
Crushing strength 20～90N/ grain.This carrier argent-amine complex, alkali metal compound and the solution impregnation of alkaline earth metal compound,
Silver catalyst is prepared for ethylene epoxidizing epoxy ethane after being dried activation.
Although above-mentioned patent documentation is respectively adopted in alumina raw material the interpolation method such as alkaline earth metal compound or fluoride
Improve alumina support, the activity and selectivity of catalyst is brought improvement in various degree, but along with middle high selectivity silver
The heavy industrialization application of catalyst, the requirement of alumina support performance is also being improved constantly by this area.
Summary of the invention
In view of the situation of above-mentioned prior art, the present inventor has been carried out extensively at silver catalyst and alumina support field thereof
General deep experimental study, found that by using the method adding citric acid complex in feed particles to prepare oxidation
Alumina supporter, can prepare the alpha-alumina supports that specific surface area increases.
Therefore, the present invention provides a kind of method preparing alpha-alumina supports, comprises the steps: that step I, preparation comprise
The mixture of following component, a: alumina powder；B: binding agent, described binding agent is Alumina gel, and described Alumina gel can be complete
Portion or part are with a false water A12O3With acid reaction formed Alumina gel and replace；C: fluoride-mineralization agent；D: citric acid or
Compound containing citrate, its gross weight based on component a～e is 0.01～20.0wt%；E: silicon or silicon-containing compound,
Its gross weight based on component a～e is 0.0～5.0wt%；F: water；And step II, the mixture obtained in step I is mediated
Uniformly, it is dried after extrusion molding and roasting obtains described alpha-alumina supports.
In the present invention, described Powder Oxidation aluminum can be hydrated alumina, for example, three water α-A12O3And/or the oxidation of β-three water
Aluminum, it is also possible to be non-aqueous aluminium oxide, for example, Alpha-alumina or gama-alumina；But the present invention is more preferably hydrated alumina,
Concrete such as three water α-A12O3And/or β-gibbsite.
In the present invention, in the described mixture of step I, in addition to these several components of above-mentioned a～f, it is also possible to include a small amount of
The material such as alkali metal and/or alkaline-earth metal.
In the present invention, it is preferred that component a gross weight based on component a～e is 4.5～90wt%, component b is based on group
The gross weight of point a～e is 5～95wt%, and component c gross weight based on component a～e is 0.01～3.0wt%, component d based on
The gross weight of component a～e is 0.05～15.0wt%, and component e gross weight based on component a～e is 0.001～2.0wt%.At this
In optimal way, containing a certain amount of element silicon in mixture, so obtained alpha-alumina supports can be in its specific surface area
While increase, support strength is also largely increased.
It is further preferred that component a gross weight based on component a～e is 23～80wt%, component b is based on component a～the gross weight of e
Amount is 18～75wt%, and component c gross weight based on component a～e is 0.1～2.5wt%, and component d is based on component a～e total
Weight is 0.1～10.0wt%, and component e gross weight based on component a～e is 0.01～2.0wt%.Most preferably, component a
Gross weight based on component a～e is 68～80wt%, and component b gross weight based on component a～e is 18～30wt%, component c
Gross weight based on component a～e is 1.2～2.0wt%, and component d gross weight based on component a～e is 0.5～5.0wt%, component
E gross weight based on component a～e is 0.1～1.5wt%.
In the present invention, it is preferred that described acid is aqueous solution of nitric acid, wherein nitric acid is 1:1.25～10 with the volume ratio of water,
Preferably 1:2～4.When preparing the alpha-alumina supports of the present invention, component c fluoride be added to accelerated oxidation aluminum
Transformation of crystal, it is used as mineralizer.In one embodiment of the invention, described fluoride-mineralization agent be selected from fluohydric acid gas,
One or more in aluminium fluoride, ammonium fluoride, Afluon (Asta) and cryolite, preferred fluorinated ammonium.In the present invention, described siliceous
Compound is selected from silicon dioxide, silicate, carborundum, kieselguhr, Anhydrite and silester, preferably silicon dioxide.
In the present invention, described citric acid or the compound containing citrate are selected from citric acid, ammonium citrate, citric acid alkali gold
Belong to salt, alkali earth salt and citric acid rare earth metal salt, optimization citric acid.Citric acid or the chemical combination containing citrate
Thing is a kind of stronger chelating agen, has the strongest coordination ability, and it can form highly stable chelate with metallic aluminium ion,
Therefore advantageous to the specific surface area ratio improving aluminium oxide.
In the present invention, in described step II, sintering temperature is 900～1600 DEG C, preferably 1200～1500 DEG C；Made by roasting
Aluminium oxide is completely converted into α-A1 substantially2O3, such as more than 90% is converted into α-A12O3, obtain α-A12O3Carrier.
Therefore, according to a further aspect in the invention, a kind of alpha-alumina supports prepared as stated above, this load are additionally provided
The specific surface of body is 0.5～3.0m2/ g, water absorption rate is not less than 30%, and the amount of silicon-containing compound is calculated as vehicle weight with element silicon
0.0-1wt%.The crystal formation of the vector product that the present invention obtains is such as in interlocking lamellar.
Finally, the present invention also provides for a kind of described α-Al2O3Carrier is in oxidation of ethylene produces oxirane silver catalyst
Application.
Detailed description of the invention
The present invention combines following embodiment and is described further, but the scope of the present invention is not limited to these embodiments.
Comparative example 1
By 498g tri-water α-A12O3, the false water A1 of 102g2O3With 1.50g BaSO4Put into mix homogeneously in blender, connect
And be poured in kneader.By 10.5g ammonium fluoride at the diluted nitric acid aqueous solution (nitric acid: water=1:3, volume of 0.12 liter
Than) in be completely dissolved after pour in kneader, being kneaded into can the paste of extrusion molding.Finally paste is loaded banded extruder
In, extrusion molding is diameter 8.0mm, the column of long 6.0mm, dries more than 2 hours at 80-120 DEG C so that it is trip
It is reduced to below 10% weight from water content.Dried column is put in natural gas kiln, through 36 hours from room temperature
Being increased to 1360 DEG C, then constant temperature 2 hours, obtain white solid product, and the XRD analysis of this solid being shown, it is
α-A12O3, its related physical performance data is shown in Table 1.
Embodiment 1
By 498g tri-water α-A12O3, the false water A1 of 102g2O3, 8g citric acid put into mix homogeneously in blender, then
It is poured in kneader.By 10.5g ammonium fluoride at the diluted nitric acid aqueous solution (nitric acid: water=1:3, volume ratio) of 0.12 liter
In be completely dissolved after pour in kneader, being kneaded into can the paste of extrusion molding.Finally paste is loaded in banded extruder,
Extrusion molding is diameter 8.0mm, the column of long 6.0mm, dries more than 2 hours at 80-120 DEG C so that it is dissociates and contains
The water yield is reduced to below 10% weight.Dried column is put in natural gas kiln, raised from room temperature through 36 hours
To 1360 DEG C, then constant temperature 2 hours, obtain white solid product, and the XRD analysis of this solid being shown, it is α-A12O3,
Its related physical performance data is shown in Table 1.
Embodiment 2
By 498g tri-water α-A12O3, the false water A1 of 102g2O3, 15g citric acid put into mix homogeneously in blender, then
It is poured in kneader.By 10.5g ammonium fluoride at the diluted nitric acid aqueous solution (nitric acid: water=1:3, volume ratio) of 0.12 liter
In be completely dissolved after pour in kneader, being kneaded into can the paste of extrusion molding.Finally paste is loaded in banded extruder,
Extrusion molding is diameter 8.0mm, the column of long 6.0mm, dries more than 2 hours at 80-120 DEG C so that it is dissociates and contains
The water yield is reduced to below 10% weight.Dried column is put in natural gas kiln, raised from room temperature through 36 hours
To 1360 DEG C, then constant temperature 2 hours, obtain white solid product, and the XRD analysis of this solid being shown, it is α-A12O3,
Its related physical performance data is shown in Table 1.
Embodiment 3
By 498g tri-water α-A12O3, the false water A1 of 102g2O3, 15g citric acid and 1.05g silicon dioxide put into blender
Middle mix homogeneously, is then poured in kneader.By 10.5g ammonium fluoride 0.12 liter diluted nitric acid aqueous solution (nitric acid:
Water=1:3, volume ratio) in be completely dissolved after pour in kneader, being kneaded into can the paste of extrusion molding.Finally by cream
Shape thing loads in banded extruder, and extrusion molding is diameter 8.0mm, the column of long 6.0mm, dries 2 at 80-120 DEG C
More than hour so that it is free water content is reduced to below 10% weight.Dried column is put in natural gas kiln,
Being increased to 1360 DEG C through 36 hours from room temperature, then constant temperature 2 hours, obtain white solid product, the XRD to this solid
Analysis shows that it is α-A12O3, its related physical performance data is shown in Table 1.
Table 1
| Intensity (N/ grain) | Water absorption rate (%) | Specific surface area (m2/ g) | |
| Comparative example 1 | 83 | 47.99 | 0.810 |
| Embodiment 1 | 60 | 48.43 | 0.954 |
| Embodiment 2 | 55 | 51.25 | 1.577 |
| Embodiment 3 | 136 | 48.66 | 1.298 |
As seen from Table 1, compared with comparative example 1, each embodiment uses and adds the oxidation obtained by citric acid in the feed
Alumina supporter is respectively provided with bigger specific surface area, and according to the sign of scanning electron microscope, the crystal formation of above-mentioned alumina support
It is interlocking lamellar.When especially adding a certain amount of element silicon in carrier preparation process, so obtained Alpha-alumina carries
Body also can be largely increased by support strength while its specific surface area increases.
Claims (11)
1. the method preparing alpha-alumina supports, comprises the steps:
Step I, preparation comprises the mixture of following component,
A: alumina powder；
B: binding agent, described binding agent is Alumina gel, and described Alumina gel is completely or partially with a false water A12O3
With acid reaction formed Alumina gel and replace；
C: fluoride-mineralization agent；
D: citric acid or the compound containing citrate, its gross weight based on component a～e is 0.01～20.0wt%；
E: silicon or silicon-containing compound, its gross weight based on component a～e is 0.0～5.0wt%；
F: water；
Step II, mediates the mixture obtained in step I uniformly, is dried after extrusion molding and roasting obtains institute
State alpha-alumina supports；
Described alumina powder is three water α-A12O3And/or β-gibbsite.
Method the most according to claim 1, it is characterised in that: component a is based on component a～the gross weight of e
Being 4.5～90wt%, component b gross weight based on component a～e is 5～95wt%, and component c is based on component a～e
Gross weight be 0.01～3.0wt%, component d gross weight based on component a～e is 0.05～15.0wt%, component e
Gross weight based on component a～e is 0.001～2.0wt%.
Method the most according to claim 2, it is characterised in that: component a is based on component a～the gross weight of e
Being 23～80wt%, component b gross weight based on component a～e is 18～75wt%, and component c is based on component a～e
Gross weight be 0.1～2.5wt%, component d gross weight based on component a～e is 0.1～10.0wt%, component e
Gross weight based on component a～e is 0.01～2.0wt%.
Method the most according to claim 3, it is characterised in that: component a is based on component a～the gross weight of e
Being 68～80wt%, component b gross weight based on component a～e is 18～30wt%, and component c is based on component a～e
Gross weight be 1.2～2.0wt%, component d gross weight based on component a～e is 0.5～5.0wt%, component e base
Gross weight in component a～e is 0.1～1.5wt%.
5. according to the method described in any one in Claims 1 to 4, it is characterised in that: described acid is nitric acid aqueous solution
Solution, wherein nitric acid is 1:1.25～10 with the volume ratio of water.
Method the most according to claim 5, it is characterised in that in described aqueous solution of nitric acid, nitric acid and water
Volume ratio be 1:2～4.
7. according to the method described in any one in Claims 1 to 4, it is characterised in that: described fluoride-mineralization
Agent is one or more in fluohydric acid gas, aluminium fluoride, ammonium fluoride, Afluon (Asta) and cryolite；Described siliceous
Compound is selected from silicon dioxide, silicate, carborundum, kieselguhr, Anhydrite and silester.
Method the most according to claim 7, it is characterised in that described fluoride-mineralization agent is ammonium fluoride；
Described silicon-containing compound is silicon dioxide.
9. according to the method described in any one in Claims 1 to 4, it is characterised in that: described containing citrate
Compound selected from ammonium citrate, alkali metal citrates, alkali earth salt and citric acid rare earth metal
Salt.
10. the alpha-alumina supports prepared according to method described in any one in claim 1～9,
It is characterized in that: specific surface is 0.5～3.0m2/ g, water absorption rate is not less than 30%, and the amount of silicon-containing compound is with silicon unit
Element is calculated as the 0-1wt% of vehicle weight.
α-Al prepared by 11. 1 kinds of methods as described in any one in claim 1～92O3Carrier or right are wanted
Seek the α-Al described in 102O3Carrier application in oxidation of ethylene produces oxirane silver catalyst.
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| CN106311354B (en) * | 2015-07-02 | 2020-07-21 | 中国石油化工股份有限公司 | Method for modifying surface of alumina carrier, carrier obtained thereby and application thereof |
| CN114425373B (en) * | 2020-09-25 | 2023-09-08 | 中国石油化工股份有限公司 | Alpha-alumina carrier, preparation method, silver catalyst and application |
| CN113087106B (en) * | 2021-02-03 | 2022-04-19 | 南京水滴智能环保装备研究院有限公司 | Method for removing silicon from acid liquor |
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| CN103055947A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Preparation method of alumina support |
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| NZ285507A (en) * | 1994-05-13 | 1998-03-25 | Cytec Tech Corp | Catalyst compositions containing a particulate porus support of gamma alumina |
| US6750173B2 (en) * | 2002-04-08 | 2004-06-15 | Scientific Design Company, Inc. | Ethylene oxide catalyst |
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| GB958983A (en) * | 1960-05-10 | 1964-05-27 | Pechiney Prod Chimiques Sa | Catalyst carrier |
| US4206084A (en) * | 1977-08-29 | 1980-06-03 | The Dow Chemical Company | Catalyst for producing maleic anhydride |
| CN1646219A (en) * | 2002-02-25 | 2005-07-27 | 圣戈本陶瓷及塑料股份有限公司 | Catalyst carriers |
| CN1634652A (en) * | 2003-12-31 | 2005-07-06 | 中国石油化工股份有限公司北京燕山分公司研究院 | Silver catalyst carrier for epoxyethane production, preparation method and application thereof |
| CN102441435A (en) * | 2010-09-30 | 2012-05-09 | 中国石油化工股份有限公司 | Method for preparing alumina carrier for silver catalyst, carrier obtained thereby and application thereof |
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