CN108499552A - Alumina support and the preparation method and application thereof - Google Patents
Alumina support and the preparation method and application thereof Download PDFInfo
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- CN108499552A CN108499552A CN201710111589.6A CN201710111589A CN108499552A CN 108499552 A CN108499552 A CN 108499552A CN 201710111589 A CN201710111589 A CN 201710111589A CN 108499552 A CN108499552 A CN 108499552A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 35
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 28
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 28
- 238000000465 moulding Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000002210 silicon-based material Substances 0.000 claims abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 238000010521 absorption reaction Methods 0.000 claims description 23
- 229910001679 gibbsite Inorganic materials 0.000 claims description 21
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 13
- 239000003921 oil Substances 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 7
- 235000012241 calcium silicate Nutrition 0.000 claims description 7
- 239000004575 stone Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 3
- 239000000391 magnesium silicate Substances 0.000 claims description 3
- 235000019792 magnesium silicate Nutrition 0.000 claims description 3
- -1 polyethylene Polymers 0.000 claims description 3
- 229940099259 vaseline Drugs 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910052916 barium silicate Inorganic materials 0.000 claims description 2
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- 229910052917 strontium silicate Inorganic materials 0.000 claims description 2
- QSQXISIULMTHLV-UHFFFAOYSA-N strontium;dioxido(oxo)silane Chemical compound [Sr+2].[O-][Si]([O-])=O QSQXISIULMTHLV-UHFFFAOYSA-N 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000000571 coke Substances 0.000 claims 1
- 238000006735 epoxidation reaction Methods 0.000 claims 1
- 150000002222 fluorine compounds Chemical class 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000002245 particle Substances 0.000 description 17
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 16
- 239000000243 solution Substances 0.000 description 12
- 239000002006 petroleum coke Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001935 peptisation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 150000004673 fluoride salts Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004375 physisorption Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 229910001680 bayerite Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B01J35/612—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention relates to a kind of preparation methods of alpha-aluminium oxide carrier comprising：I the total mixture for including following component) is prepared：Component a, the α gibbsites of the mesh of granularity≤100；The boehmite of 200 mesh of component b, granularity ＜；Component c, fluoride；Component d, alkaline earth metal compound；Component e, silicon-containing compound；Component f, solid carbon-containing material；Component g, liquid organic compound；Component h, binder；II) by step I) in obtained mixture mediate uniformly and be molded regular carrier molding machine using screw rod and be molded；III) by step II) in obtained product be dried, calcination process, the alpha-aluminium oxide carrier is made.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of alpha-alumina supports and the preparation method and application thereof.
Background technology
Aluminium oxide is as adsorbent, catalyst and catalyst carrier in chemical industry, environmental protection, vehicle maintenance service etc.
It is widely used, is widely applied on chemical industry especially as catalyst carrier.
In environmental protection and chemical industry, the industrial catalyst that is prepared by alumina support, which is typically used, continuously to be flowed
In gas-solid, liquid-solid or gas-liquid-solid heterogeneous system.For the requirement for meeting certain, it is ball that alumina support, which is generally increased by work,
Shape, cylinder, trilobes bar shaped, Rasching ring, porous honeycomb or gear shape, and require certain mechanical strength,
Specific surface area and pore structure.Big specific surface area is conducive to improve the activity of catalyst, and high mechanical strength is to make for a long time
With pore structure appropriate is conducive to improve the selectivity of target product in concurrently or sequentially reaction system.
The preparation method of alpha-alumina supports is commonly divided into three kinds：(1) boehmite is used to be prepared for primary raw material；
(2) with α-gibbsite, (also known as α-gibbsite (Gibssite) and/or surge aluminium stone (Bayerite) is adopted for primary raw material
Boehmite or Aluminum sol is used to be prepared as adhesive；(3) it is prepared by primary raw material of the Alpha-alumina of sintering.It is carried for modulation
The performance of body and catalyst, carrier be usually also possible to add in preparing flammable carbonaceous material, mineralizer, shaping assistant etc. other
Auxiliary agent.
From economic considerations, there is larger cost advantage using α-gibbsite.But it is prepared using α-gibbsite
When alumina support, boehmite or its colloidal sol are usually added as adhesive, is otherwise difficult to be molded.To intending thin water aluminium
Stone, by often requiring it with higher sour peptization index (general to require to be higher than 90%).It is generally believed that with α-gibbsite
When preparing alumina support, especially alpha-alumina supports for primary raw material, the addition of boehmite (or Aluminum sol) is not
It can lack.Boehmite crystallite dimension is big (generally higher than 50nm), cannot peptization (sour peptization index is less than 10%) well,
Therefore have been generally acknowledged that cannot be replacing boehmite for the prior art.The experimental study of early period showed using boehmite generation
It is more difficult in carrier extrusion molding as primary raw material for boehmite.It is important as one how formation problems are solved
The technical issues of.
Therefore, presently, there are the problem of be the preparation be badly in need of researching and developing a kind of carrier and be molded easy alpha-alumina supports
Method.
Invention content
The technical problem to be solved by the present invention is to solve the above shortcomings of the prior art and to provide a kind of alpha-alumina supports
Preparation method.The method of the present invention prepares alumina support using the boehmite of cheap α-gibbsite and low peptization index
Method in, regular carrier molding machine is molded by adding liquid organic compound and using screw rod, makes carrier forming process more
It is easy to carry out, and resulting vehicle has preferable physical property, especially has higher side pressure strength and water absorption rate.
For this purpose, first aspect present invention provides a kind of preparation method of alpha-alumina supports comprising following steps：
I the total mixture for including following component) is prepared：
α-three water the aluminium of the mesh of the granularity of component a, the 9.0wt%-70.0wt% based on the total mixture total weight≤100
Stone, the granularity for being preferably based on the 9.4wt%-55.0wt% of the total mixture total weight is α-gibbsite of 120-650 mesh；
The thin water aluminium of 200 purposes of granularity ＜ of component b, the 20.0wt%-90.0wt% based on the total mixture total weight
Stone is preferably based on the boehmite of the mesh of the granularity of the 25.0wt%-80.0wt% of the total mixture total weight≤200；
Component c, the fluoride of the 0.5wt%-3.0wt% based on the total mixture total weight；
Component d, in terms of alkali earth metal, the alkaline-earth metal of the 0-2.0wt% based on the total mixture total weight
Close object；
Component e, in terms of element silicon, the siliceous chemical combination of the 0.02wt%-2.0wt% based on the total mixture total weight
Object；
Component f, the solid carbon-containing material of the 0-20.0wt% based on the total mixture total weight；
Component g, the liquid organic compound of the 1.0wt%-5.0wt% based on component a-f total weights；
Component h, the binder of the 9.0wt%-40.0wt% based on the total mixture total weight；
II) by step I) in obtained total mixture mediate uniformly and regular carrier molding machine molding be molded using screw rod；
III) by step II) in obtained product be dried, calcination process, the alpha-alumina supports are made.
According to the method for the present invention, the component a further includes transition aluminas or surge aluminium stone.In some implementations of the present invention
In example, the content of the component a is the 26.0wt%-43.0wt% based on the total mixture total weight.
According to the method for the present invention, the component b further includes boehmite and/or Aluminum sol.In some realities of the present invention
It applies in example, the content of the component b is the 32.0wt%-66.0wt% based on the total mixture total weight.
According to the method for the present invention, the component c fluorides include metal fluoride and/or ammonium fluoride.The one of the present invention
In a little embodiments, the content of the component c fluorides is the 1.0wt%-3.0wt% based on the total mixture total weight.
In some preferred embodiments of the present invention, the content of the component c fluorides is based on the total mixture total weight
1.0wt%-1.2wt%.
According to the method for the present invention, the component d alkaline earth metal compounds include magnesium, calcium, strontium and barium compound in extremely
Few one kind；It is preferred that the alkaline earth metal compound includes the compound of strontium and/or barium.In some embodiments of the invention, with
The content of alkali earth metal meter, the component d alkaline earth metal compounds is the 0- based on the total mixture total weight
1.0wt%.In some preferred embodiments of the present invention, in terms of alkali earth metal, the component d alkaline earth metal compounds
Content be the 0.1wt%-0.4wt% based on the total mixture total weight.
According to the method for the present invention, the component e silicon-containing compounds include the dry silica gel of Ludox, average grain diameter less than 50nm
At least one of with alkaline-earth-metal silicate；It is preferred that the alkaline-earth-metal silicate include magnesium silicate, calcium silicates, strontium silicate and
At least one of barium silicate.In some embodiments of the invention, in terms of element silicon, the component e silicon-containing compounds contain
Amount is the 0.05wt%-1.0wt% based on the total mixture total weight.In some preferred embodiments of the present invention, with
The content of element silicon meter, the component e silicon-containing compounds is the 0.05wt%- based on the total mixture total weight
0.40wt%.
According to the method for the present invention, the component f solid carbon-containing materials include petroleum coke, graphite, carbon dust, polyethylene and Fan Shi
At least one of woods.In some embodiments of the invention, the content of the component f solid carbon-containing materials is based on described total
The 2.0wt%-20.0wt% of total weight of the mixture.In some preferred embodiments of the present invention, the component f solid carbons
The content of material is the 5.0wt%-9.0wt% based on the total mixture total weight.
According to the method for the present invention, the component g liquid organic compounds include hydro carbons and/or liquid fat substance, excellent
It is white oil to select the liquid organic compound.In some embodiments of the invention, the component g liquid organic compounds contain
Amount is the 1.3wt%-3.0wt% based on component a-f total weights.Heretofore described component g liquid organic compounds are one kind
Shaping assistant.
According to the method for the present invention, the component h binders are the aqueous solution of acid；It is preferred that the acid includes acetic acid, hydrochloric acid, nitre
At least one of acid and sulfuric acid.In some embodiments of the invention, the content of the component h binders is based on described total
The 9.0wt%-15wt% of total weight of the mixture.
According to the method for the present invention, in step I) in addO-on therapy g liquid organic compounds and in step II) in selection use
On the one hand the problem of regular carrier molding machine of screw rod molding is molded, overcomes carrier difficult forming is helped due to the use of molding
Agent, i.e. component g liquid organic compounds；On the other hand, screw rod is molded the pressure of regular carrier molding machine and is directly transmitted by screw rod,
Therefore, extrusion pressure bigger, it is easier to be molded.
In some embodiments of the invention, in step III) in, the temperature of the drying process is 60-100 DEG C, preferably
It is 65-80 DEG C.The time of the drying process is 2-24 hours, preferably 10-18h.
In other embodiments of the present invention, the maximum temperature of the calcination process is 1200-1500 DEG C, preferably
1220-1300℃.The total time of the calcination process is 8-60 hours, preferably 10-55 hours；Wherein, permanent at the highest temperature
The time of temperature roasting is 2-9 hours.
Second aspect of the present invention provides a kind of alpha-alumina supports prepared by method as described in the first aspect of the invention；Institute
State side pressure strength >=60N/cm of alpha-alumina supports, specific surface area 1.0-4.0m2/ g, water absorption rate >=40%, silicone content are
0.05wt%-2.0wt%.There is higher intensity and absorptivity using alumina support prepared by the method for the present invention.
In some preferred embodiments of the present invention, side pressure strength >=80N/cm of the alpha-alumina supports compares table
Area is 1.4-3.0m2/ g, water absorption rate >=45%, silicone content 0.06wt%-1.0wt%.
Third aspect present invention provides a kind of alpha-alumina supports as described in respect of the second aspect of the invention in olefin epoxide
Change the application in reaction, catalytic hydrogenation, catalytic dehydrogenation, methane vapor conversion or methane reforming.
The preparation method of alpha-alumina supports provided by the invention overcomes the problem of carrier difficult forming, and prepares load
The raw materials used inexpensive of body, alpha-alumina supports obtained have higher intensity, specific surface area and water absorption rate.The present invention carries
Alpha-alumina supports prepared by the method for confession have broad application prospects.
Specific implementation mode
To keep the present invention easier to understand, below in conjunction with embodiment, the present invention will be described in detail, these embodiments are only
Serve illustrative, it is not limited to application range of the invention.
The side pressure strength of carrier is measured using Dalian Chemical Research ＆. Design Inst.'s production III type intelligence detector for strength of particles of DL.It surveys
The method of determining is：It randomly selects 30 support samples, measures after radial crushing strength divided by particle length, be finally averaged
It arrives.
The specific surface area of carrier is measured according to international test standards ISO-9277 using nitrogen physisorption BET methods.Example
Such as, Kang Ta companies NOVA2000e type nitrogen physisorption instrument in the U.S. can be used to measure the specific surface area of carrier.
Term used herein " water absorption rate " refers to that the weight percent of the carrier saturation absorption water of unit mass at room temperature contains
It measures (unit is wt%).Assay method is：A certain amount of carrier (quality m is weighed first1), it is naturally cold after boiling 1h in boiling water
But to room temperature, carrier taking-up is erected on the moderate wet gauze of water content to remove the extra attached water of carrier surface, finally claims
Amount is saturated with the quality m of the carrier after water2, by formula " water absorption rate=(m2-m1)/m1× 100% " calculates the water absorption rate of carrier.
Embodiment
Embodiment 1
It is small that α-gibbsite 300g of 150 mesh, the boehmite 300g for crossing 200 mesh, ammonium fluoride 7.0g, average particle size will be crossed
In the calcium silicates 2.3g of 20nm, it is put into blender and is uniformly mixed；Then it is transferred in kneader, technical white oil 16.0g is added, be added
The dilute nitric acid solution of 70mL 15wt% is fully mediated；Then it uses screw rod to be molded regular carrier molding machine and is shaped to outer diameter about
The Raschig ring shape body of 8.0mm, long 7.2mm, internal diameter 3mm；The dry 10h at 65 DEG C, make free water content be reduced to 10wt% with
Under, alumina support green compact are made；It is then placed in high-temperature electric resistance furnace, is increased to 1280 DEG C from room temperature through 30h, constant temperature 3h is obtained
White alpha-alumina supports are named as carrier 1.Its crushing strength, specific surface area and water absorption rate are measured, the results are shown in Table 1.
Embodiment 2
α-gibbsite 300g of 150 mesh will be crossed, cross boehmite 300g, barium sulfate 2.5g, the ammonium fluoride of 200 mesh
8.0g, average particle size are less than magnesium silicate 2.1g, the petroleum coke 65g of 30nm, are put into blender and are uniformly mixed；Then it is transferred to kneader
In, technical white oil 16.0g is added, the dilute nitric acid solution of 75mL 15wt% is added, fully mediates；Then screw rod molding rule are used
Whole carrier molding machine is shaped to the Raschig ring shape body of outer diameter about 8.0mm, long 7.2mm, internal diameter 3mm；Dry 10h, makes at 65 DEG C
Free water content is reduced to 10wt% hereinafter, alumina support green compact are made；It is then placed in high-temperature electric resistance furnace, through 30h from room temperature
1280 DEG C are increased to, constant temperature 3h obtains white alpha-alumina supports, is named as carrier 2.Measure its crushing strength, specific surface area
And water absorption rate, it the results are shown in Table 1.
Embodiment 3
α-gibbsite 350.0g of 150 mesh will be crossed, cross boehmite 250g, ammonium fluoride 9.0g, the barium sulfate of 200 mesh
Powder silica gel 2.0g, the petroleum coke 60g of 2.6g, average particle size less than 20nm are put into blender and are uniformly mixed；Then it is transferred to kneading
In machine, the dilute nitric acid solution of technical white oil 16.0g, 70mL 15wt% is added, fully mediates；Then screw rod is used to be molded regular
Carrier molding machine is shaped to the Raschig ring shape particle of outer diameter about 8.3mm, long 7.5mm, internal diameter 3.0mm；The dry 12h at 80 DEG C,
Free water content is set to be reduced to 10wt% hereinafter, alumina support green compact are made；It is then placed in high-temperature electric resistance furnace, through 30h from room
Temperature is increased to 1240 DEG C, and constant temperature 4h obtains white alpha-alumina supports, is named as carrier 3.Measure its crushing strength, water absorption rate
And specific surface area, it the results are shown in Table 1.
Embodiment 4
α-gibbsite 200.0g of 150 mesh will be crossed, cross boehmite 400g, ammonium fluoride 9.0g, the barium sulfate of 200 mesh
Calcium silicates 2.6g, the petroleum coke 60g of 2.6g, average particle size less than 20nm are put into blender and are uniformly mixed；Then it is transferred to kneader
In, the dilute nitric acid solution of technical white oil 17.0g, 70mL 15wt% is added, fully mediates；Then screw rod is used to be molded regular load
Body forming machine is shaped to the Raschig ring shape particle of outer diameter about 8.3mm, long 7.5mm, internal diameter 3.0mm；Dry 12h, makes at 70 DEG C
Free water content is reduced to 10wt% hereinafter, alumina support green compact are made；It is then placed in high-temperature electric resistance furnace, through 30h from room temperature
1240 DEG C are increased to, constant temperature 4h obtains alpha-alumina supports, is named as carrier 4.It measures its crushing strength, water absorption rate and compares table
Area the results are shown in Table 1.
Embodiment 5
Preparation method is with embodiment 2, the difference is that highest calcination temperature is 1300 DEG C, constant temperature 4h, obtains Alpha-alumina load
Body is named as carrier 5.Its crushing strength, specific surface area and water absorption rate are measured, the results are shown in Table 1.
Embodiment 6
Analytically pure silester 4.5g is weighed, the dust technology of the 15wt% of 70mL is slowly added in the case of intensively stirred
It is persistently for use after stirring 30min in solution.
By α-gibbsite 400.0g that granularity is 200-250 mesh, cross the boehmite 200g of 200 mesh, ammonium fluoride 8.0g,
Barium sulfate 1.8g, petroleum coke 55g are put into blender, are uniformly mixed；Then be transferred in kneader, be added 9.0g technical white oils with
The mixture of 9.0g vaseline is eventually adding above-mentioned dilute nitric acid solution, fully mediates；Then use screw rod be molded regular carrier at
Type machine is shaped to the Raschig ring shape particle of outer diameter about 8.3mm, long 7mm, internal diameter 3.0mm；The dry 12h at 80 DEG C, makes free contain
Water is reduced to 10wt% hereinafter, alumina support green compact are made；It is then placed in high-temperature electric resistance furnace, is increased to from room temperature through 30h
1230 DEG C, constant temperature 4h obtains alpha-alumina supports, is named as carrier 6.Its crushing strength, water absorption rate and specific surface area are measured, is tied
Fruit is shown in Table 1.
Embodiment 7
α-gibbsite 100.0g of 150 mesh, the boehmite 500g for crossing 200 mesh, ammonium fluoride 9.0g, average particle size will be crossed
Powder silica gel 2.0g, petroleum coke 60g less than 20nm are put into blender and are uniformly mixed；Then it is transferred in kneader, industry is added
The dilute nitric acid solution of white oil 17.0g, 70mL 15wt% are fully mediated；Then screw rod is used to be molded regular carrier molding machine molding
For the Raschig ring shape particle of outer diameter about 8.3mm, long 7.5mm, internal diameter 3.0mm；Dry 12h, is made alumina support at 70 DEG C
Green compact；It is then placed in high-temperature electric resistance furnace, 1250 DEG C is increased to from room temperature through 30h, constant temperature 4h obtains alpha-alumina supports, name
For carrier 7.Its crushing strength, water absorption rate and specific surface area are measured, the results are shown in Table 1.
Embodiment 8
By the α of 150-250 mesh-gibbsite 70.0g, boehmite 530g, ammonium fluoride 8.0g, the barium sulfate of 200 mesh excessively
2.1g, average particle size are less than calcium silicates 2.4g, the petroleum coke 40g of 20nm, are put into blender and are uniformly mixed；Then it is transferred to kneader
In, technical white oil 15.0g is added, the dilute nitric acid solution of 65mL 15wt% is added, fully mediates；Then screw rod molding rule are used
Whole carrier molding machine is shaped to the Raschig ring shape particle of outer diameter about 8.3mm, internal diameter 3.6mm, long 7.5mm；It is dry at 80 DEG C
Alumina support green compact are made in 18h；It is then placed in high-temperature electric resistance furnace, is increased to 1220 DEG C from room temperature through 30h, constant temperature 4h is obtained
Alpha-alumina supports are named as carrier 8.Its crushing strength, water absorption rate and specific surface area are measured, the results are shown in Table 1.
Embodiment 9
α-gibbsite the 80.0g, the gamma-alumina 80g for crossing 150 mesh, the boehmite for crossing 200 mesh of 150 mesh will be crossed
Powder silica gel 2.0g, the petroleum coke 58g of 340g, ammonium fluoride 9.0g, average particle size less than 20nm are put into blender and are uniformly mixed；So
After be transferred in kneader, the dilute nitric acid solution of technical white oil 12.0g, 70mL 15wt% is added, fully mediates；Then spiral shell is used
Bar is molded the Raschig ring shape particle that regular carrier molding machine is shaped to outer diameter about 8.3mm, long 7.5mm, internal diameter 3.0mm；At 70 DEG C
Alumina support green compact are made in lower dry 12h；It is then placed in high-temperature electric resistance furnace, is increased to 1300 DEG C from room temperature through 30h, constant temperature
4h obtains alpha-alumina supports, is named as carrier 9.Its crushing strength, water absorption rate and specific surface area are measured, the results are shown in Table 1.
Embodiment 10
α-gibbsite 200.0g of 150 mesh, the boehmite 280g for crossing 200 mesh, boehmite 120g, fluorination will be crossed
Ammonium 9.1g, barium sulfate 2.0g, calcium silicates 2.4g, the petroleum coke 50g for crossing 300 mesh are put into blender and are uniformly mixed；Then it is transferred to and pinches
In conjunction machine, technical white oil 14.0g is added, the dilute nitric acid solution of 80mL 15wt% is added, fully mediates；Then screw rod mould is used
Regular carrier molding machine is pressed to be shaped to the Raschig ring shape particle of outer diameter about 8.3mm, internal diameter 3.0mm, long 7.5mm；It is done at 80 DEG C
Alumina support green compact are made in dry 18h；It is then placed in high-temperature electric resistance furnace, is increased to 1230 DEG C from room temperature through 30h, constant temperature 4h is obtained
To alpha-alumina supports, it is named as carrier 10.Its crushing strength, water absorption rate and specific surface area are measured, the results are shown in Table 1.
Embodiment 11
By the α of 150-250 mesh-gibbsite 75.0g, the boehmite crossed the surge aluminium stone 70g of 150 purposes, cross 200 mesh
455g, ammonium fluoride 8.0g, barium sulfate 2.1g, calcium silicates 2.5g, the petroleum coke 50g for crossing 300 mesh are put into blender and are uniformly mixed；
Then it is transferred in kneader, technical white oil 15.0g is added, the dilute nitric acid solution of 70mL 15wt% is added, fully mediates；Then
The Raschig ring shape particle that regular carrier molding machine is shaped to outer diameter about 8.3mm, internal diameter 3.6mm, long 7.5mm is molded using screw rod；
Dry 18h, is made alumina support green compact at 80 DEG C；It is then placed in high-temperature electric resistance furnace, 1290 is increased to from room temperature through 30h
DEG C, constant temperature 4h obtains alpha-alumina supports and is named as carrier 11.Its crushing strength, water absorption rate and specific surface area are measured, is as a result seen
Table 1.
Comparative example 1
Boehmite 150.0g, the ammonium fluoride 8.2g of α-gibbsite 450g of 120 mesh excessively, 200 mesh excessively are put into mixed
Glassware mixes, and is then transferred in kneader, is added the dust technology 120mL of 15wt%, mediate and extrusion molding be outer diameter about
The five hole columns of 8.0mm, long 7.2mm, internal diameter 1.6mm, the dry 10h at 80 DEG C, make free water content be reduced to 10wt%
Hereinafter, alumina support green compact are made.It is then placed in high-temperature electric resistance furnace, is increased to 1300 DEG C from room temperature through 30h, constant temperature 4h is obtained
To alpha-alumina supports, it is named as carrier 12.Its crushing strength, water absorption rate and specific surface area are measured, the results are shown in Table 1.
Comparative example 2
Preparation method is with comparative example 1, the difference is that added with barium sulfate 2.4g, vaseline 12g, highest calcination temperature when mixing
It it is 1350 DEG C, constant temperature 4h obtains alpha-alumina supports, is named as carrier 13.Measure its crushing strength, specific surface area and water suction
Rate the results are shown in Table 1.
Comparative example 3
Boehmite 102g, the ammonium fluoride 8.0g of the α of 250-500 mesh-gibbsite 486.0g, 150 mesh excessively are put into mixed
Glassware is uniformly mixed；Then it is transferred in kneader, the dilute nitric acid solution of 75mL 15wt% is added, fully mediates, finds material
It dissipates, it is difficult to it is kneaded and formed, regular carrier molding machine molding cannot be molded by screw rod.
Table 1
Compared with comparative example, carrier made from the embodiment of the present invention has higher side pressure strength, higher specific surface area
With higher water absorption rate, and in preparation process carrier be easier be molded.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (11)
1. a kind of preparation method of alpha-alumina supports comprising following steps：
I the total mixture for including following component) is prepared：
α-gibbsite of the mesh of the granularity of component a, the 9.0wt%-70.0wt% based on the total mixture total weight≤100,
The granularity for being preferably based on the 9.4wt%-55.0wt% of the total mixture total weight is α-gibbsite of 120-650 mesh；
The boehmite of 200 mesh of granularity ＜ of component b, the 20.0wt%-90.0wt% based on the total mixture total weight, it is excellent
Select the 25.0wt%-80.0wt% based on the total mixture total weight granularity≤200 mesh boehmite；
Component c, the fluoride of the 0.5wt%-3.0wt% based on the total mixture total weight；
Component d, in terms of alkali earth metal, the alkaline earth metal compound of the 0-2.0wt% based on the total mixture total weight；
Component e, in terms of element silicon, the silicon-containing compound of the 0.02wt%-2.0wt% based on the total mixture total weight；
Component f, the solid carbon-containing material of the 0-20.0wt% based on the total mixture total weight；
Component g, the liquid organic compound of the 1.0wt%-5.0wt% based on component a-f total weights；
Component h, the binder of the 9.0wt%-40.0wt% based on the total mixture total weight；
II) by step I) in obtained total mixture mediate uniformly and regular carrier molding machine molding be molded using screw rod；
III) by step II) in obtained product be dried, calcination process, the alpha-alumina supports are made.
2. according to the method described in claim 1, it is characterized in that, the component a further includes transition aluminas or surge aluminium stone；
The component b further includes boehmite and/or Aluminum sol.
3. method according to claim 1 or 2, which is characterized in that the content of the component c fluorides is based on described total
The 1.0wt%-3.0wt% of total weight of the mixture；It is preferred that the fluoride includes metal fluoride and/or ammonium fluoride.
4. according to the method described in any one of claim 1-3, which is characterized in that in terms of alkali earth metal, described group
It is the 0-1.0wt% based on the total mixture total weight to divide the content of d alkaline earth metal compounds；It is preferred that the alkaline-earth metal
Close at least one of the compound that object includes magnesium, calcium, strontium and barium；The more preferable alkaline earth metal compound include strontium and/or
The compound of barium.
5. according to the method described in any one of claim 1-4, which is characterized in that in terms of element silicon, the component e is siliceous
The content of compound is the 0.05wt%-1.0wt% based on the total mixture total weight；It is preferred that the silicon-containing compound includes
At least one of the dry silica gel of Ludox, average grain diameter less than 50nm and alkaline-earth-metal silicate；It is preferred that the alkaline-earth metal
Silicate includes at least one of magnesium silicate, calcium silicates, strontium silicate and barium silicate.
6. according to the method described in any one of claim 1-5, which is characterized in that the component f solid carbon-containing materials
Content is the 2.0wt%-20.0wt% based on the total mixture total weight；It is preferred that the solid carbon-containing material includes oil
At least one of coke, graphite, carbon dust, polyethylene and vaseline.
7. according to the method described in any one of claim 1-6, which is characterized in that the component g liquid organic compounds
Content be the 1.3wt%-3.0wt% based on component a-f total weights；It is preferred that the liquid organic compound include hydro carbons and/
Or liquid fat substance, the more preferable liquid organic compound are white oil.
8. method according to any one of claims 1-7, which is characterized in that the content of the component h binders is
9.0wt%-15.0wt% based on component a-f total weights；It is preferred that the binder is the aqueous solution of acid；It is preferred that the acid includes
At least one of acetic acid, hydrochloric acid, nitric acid and sulfuric acid.
9. according to the method described in any one of claim 1-8, which is characterized in that in step III) in,
The temperature of the drying process is 60-100 DEG C, preferably 65-80 DEG C；The time of the drying process is 2-24 hours,
Preferably 10-18h；
The maximum temperature of the calcination process is 1200-1500 DEG C, preferably 1220-1300 DEG C；The calcination process it is total when
Between be 8-60 hours, preferably 10-55 hours；Wherein, the time of constant temperature calcining is 2-9 hours at the maximum temperature.
10. a kind of alpha-alumina supports prepared according to any one of claim 1-9 the methods, which is characterized in that institute
State side pressure strength >=60N/cm of alpha-alumina supports, specific surface area 1.0-4.0m2/ g, water absorption rate >=40%, silicone content are
0.05wt%-2.0wt%；It is preferred that side pressure strength >=80N/cm of the alpha-alumina supports, specific surface area 1.4-3.0m2/
G, water absorption rate >=45%, silicone content 0.06wt%-1.0wt%.
11. a kind of alpha-alumina supports according to claim 10 are de- in epoxidation reaction of olefines, catalytic hydrogenation, catalysis
Application in hydrogen, methane vapor conversion or methane reforming.
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| JPH08198621A (en) * | 1995-01-20 | 1996-08-06 | Mizusawa Ind Chem Ltd | Spherical alumina and its production |
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| JPH08198621A (en) * | 1995-01-20 | 1996-08-06 | Mizusawa Ind Chem Ltd | Spherical alumina and its production |
| CN101237926A (en) * | 2005-08-10 | 2008-08-06 | 科学设计有限责任两合公司 | Process for preparation of catalyst carrier and its use in catalyst preperation |
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