CN106622195A - Alpha- alumina supporter and preparation method thereof and application - Google Patents
Alpha- alumina supporter and preparation method thereof and application Download PDFInfo
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- CN106622195A CN106622195A CN201510711506.8A CN201510711506A CN106622195A CN 106622195 A CN106622195 A CN 106622195A CN 201510711506 A CN201510711506 A CN 201510711506A CN 106622195 A CN106622195 A CN 106622195A
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 23
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
- 239000002210 silicon-based material Substances 0.000 claims abstract description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 3
- 238000010521 absorption reaction Methods 0.000 claims description 22
- 239000004411 aluminium Substances 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 19
- 239000004575 stone Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 229910001679 gibbsite Inorganic materials 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 238000006735 epoxidation reaction Methods 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000499 gel Substances 0.000 claims description 4
- 239000000843 powder Substances 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000002006 petroleum coke Substances 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 239000011260 aqueous acid Substances 0.000 claims description 2
- 238000001354 calcination Methods 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
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- -1 polyethylene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 238000002407 reforming Methods 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 229910052915 alkaline earth metal silicate Inorganic materials 0.000 claims 1
- 239000002585 base Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 230000001131 transforming effect Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 21
- 229910001680 bayerite Inorganic materials 0.000 abstract description 2
- 238000007493 shaping process Methods 0.000 abstract description 2
- 239000007767 bonding agent Substances 0.000 abstract 1
- 238000004898 kneading Methods 0.000 abstract 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 14
- 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 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005453 pelletization Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000001935 peptisation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- WJNDLRMDNMIUGC-UHFFFAOYSA-N ethene;silver Chemical compound [Ag].C=C WJNDLRMDNMIUGC-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005303 weighing 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of a catalyst, and especially relates to a preparation method of an Alpha- alumina supporter. The method includes steps of I), a mixture is prepared from (a), 10-80% of bayerite with granularity of not more than 150 meshes based on total weight of the total mixture; (b), 20-90% of boehmite with granularity of not more than 150 meshes based on the total weight of the total mixture; (c), 0-3.0% of fluoride based on total weight of the total mixture; (d), 0-2.0% of alkaline-earth metal compound based on total weight of total mixture according to alkaline-earth metal element; (e), 0-3.0% of silicon-containing compound based on total weight of total mixture according to silicon element; (f), 10-40% of bonding agent and water based on total weight of total mixture; II), evenly kneading and shaping the mixture acquired in step I); III), drying the product in step II), and then roasting the alumina supporter.
Description
Technical field
The present invention relates to catalyst field, more particularly to a kind of alpha-alumina supports and its preparation method and application.
Background technology
Aluminum oxide is wide at aspects such as chemical industry, environmental protection, vehicle maintenance services as adsorbent, catalyst and catalyst carrier
It is general to use, it is widely applied on chemical industry especially as catalyst carrier.
In environmental protection and chemical industry, the industrial catalyst prepared by alumina support be typically used continuous flowing gas-
Gu in solid, liquid-or gas-liquid-solid heterogeneous system.To meet certain use requirement, alumina support is generally increased by work for ball
Shape, cylinder, trilobes bar shaped, Raschig ring shape, porous honeycomb or gear shape, and require strong with certain machinery
Degree, specific surface area and pore structure.Big specific surface area is conducive to improving the activity of catalyst, and high mechanical strength is for length
Phase uses, and appropriate pore structure is conducive to improving the selectivity of target product in concurrently or sequentially reaction system.
Conventional alumina support includes gama-alumina, η-aluminum oxide and Alpha-alumina, and wherein low specific surface area, surface is more lazy
The alpha-alumina supports of property obtain in the catalyst such as ethylene epoxidizing silver catalyst and steam reformation, selective hydrogenation compared with
Many applications.Alpha-alumina supports preparation method can substantially be divided into three kinds：(1) boehmite is adopted for primary raw material preparation；
(2) it is thin using intending with α-gibbsite (also known as α-gibbsite) and/or surge aluminium stone (Bayerite) as primary raw material
Diaspore or Alumina gel are prepared as adhesive；(3) prepared as primary raw material with the Alpha-alumina for sintering.For modulation carrier and
The performance of catalyst, carrier is generally also possible to add flammable carbonaceous material, mineralizer, shaping assistant etc. that other are helped in preparing
Agent.
In standby alumina support made of stones using α-gibbsite and/or surge aluminium, boehmite or its colloidal sol is generally added to make
For adhesive, otherwise it is difficult to be molded.So, to boehmite, by often requiring that it has higher sour peptization index (
As require higher than 90%).It is generally believed that preparing alumina support by primary raw material of α-gibbsite, especially α-oxygen
When changing aluminium, the addition of boehmite (or Alumina gel) is indispensable；Boehmite crystallite dimension is big (generally higher than
50nm), it is impossible to which peptization (sour peptization index is less than 20%), therefore prior art well has been generally acknowledged that can not be to replace
Boehmite.
Alumina producer extracts aluminum oxide from bauxite, can relatively easily obtain substantial amounts of surge aluminium stone.Different from prior art,
The present invention reports a kind of method that boehmite using surge aluminium stone and low peptization index prepares alumina support, by appropriate
Regulation and control can prepare the alpha-alumina supports with suitable specific surface area and water absorption rate.
The content of the invention
In order to obtain one of the alpha-alumina supports of more excellent performance, present invention one kind is provided different from system of the prior art
The preparation method of standby alpha-alumina supports：
I) total mixture comprising following component is prepared：
Component (a)：The surge aluminium stone of 150 purposes is less than or equal to based on the granularity of the 10-80% of the total mixture gross weight, it is excellent
Granularity of the choosing based on the 10-70% of the total mixture gross weight is less than or equal to the surge aluminium stone of 150 purposes；
Component (b)：The boehmite of 150 mesh is less than or equal to based on the granularity of the 20-90% of the total mixture gross weight,
The granularity for being preferably based on the 30-85% of the total mixture gross weight is less than or equal to the boehmite of 150 mesh；
Component (c)：Fluoride based on the 0-3.0% of the total mixture gross weight；
Component (d)：Alkaline earth metal compound in terms of alkali earth metal, based on the 0-2.0% of the total mixture gross weight；
Component (e)：Silicon-containing compound in terms of element silicon, based on the 0-3.0% of the total mixture gross weight；
Component (f)：The mixture of binding agent and water based on the 10-40% of the total mixture gross weight；
II) by step I) in the total mixture that obtains mediate uniform and be molded；
III) drying steps II) products therefrom, then roasting obtains the alumina support.
The present invention is by the alumina support that prepared using above-mentioned steps except being easy to be molded, with higher intensity and Bi Biao
Also there is higher water absorption rate outside area.
In a specific embodiment, component (a) also includes transition aluminas and/or α-gibbsite.
In a specific embodiment, component (b) also includes boehmite and/or Alumina gel.
In a specific embodiment, the fluoride is metal fluoride and/or ammonium fluoride.
In a specific embodiment, at least one of the alkaline-earth metal in the compound of magnesium, calcium, strontium and barium, excellent
Selected from strontium and/or the compound of barium.
In a specific embodiment, the consumption of the fluoride is the 1.0-3.0% based on the total mixture gross weight.
In a specific embodiment, the consumption of the alkaline earth metal compound, is based on described in terms of alkali earth metal
The 0.1-1.0% of total mixture gross weight.
In a specific embodiment, in terms of element silicon, containing based on the total mixture gross weight in the total mixture
0.02-1.0% silicon-containing compound；The silicon-containing compound includes the dry silica gel of Ludox, particle diameter less than 100nm and alkaline earth
At least one in metal silicate.
In a specific embodiment, binding agent includes at least in acetic acid, hydrochloric acid, nitric acid, sulphur aqueous acid and water
Kind.
In a specific embodiment, also containing the 1-20% carbon containings based on the total mixture gross weight in the total mixture
Material；Preferably, the carbonaceous material includes at least one in petroleum coke, graphite, carbon dust, polyethylene and vaseline.
In a specific embodiment, step II) described in drying carry out at a temperature of 50-120 DEG C, the drying lasts
0.1-24 hours.
In a specific embodiment, the maximum temperature of the roasting is 800-1500 DEG C, and the total time of roasting is 6-80 hours,
Wherein, at the highest temperature the time of constant temperature calcining is 1-10 hours；It is preferred that the maximum temperature of the roasting is 1100-1400 DEG C,
And the total time of roasting is 8-60 hours, wherein, the time of the roasting of the temperature range from 100 DEG C to 500 DEG C is 2-20 hours.
The two of the present invention provide a kind of alpha-alumina supports prepared using as above method, the side pressure of the alpha-alumina supports
Intensity is >=60N/cm, and specific surface area is 1.0-10.0m2/ g, water absorption rate >=35%, silicone content 0-3.0wt%.
The alpha-alumina supports prepared by the present invention have physical property more more preferable than carrier prepared by existing method, therefore, not only expand
The raw material sources of alpha-alumina supports preparation are filled, and more excellent index can also have been obtained during subsequent use.
In a specific embodiment, the side pressure strength of the alpha-alumina supports is >=80N/cm, and specific surface area is 1.0-6.0
m2/ g, water absorption rate >=40%, silicone content 0-2.0wt%.
In a specific embodiment, the side pressure strength of the alpha-alumina supports is >=100N/cm, and specific surface area is 1.4-4.0
m2/ g, water absorption rate >=43%, silicone content 0-1.0wt%.
Known in those skilled in the art, when the specific surface area of alpha-alumina supports is in 5.0m2During/below g, alpha-alumina supports
Principal crystalline phase be Alpha-alumina.Wherein principal crystalline phase refers to crystalline phase of the content in more than 50wt%.For example, principal crystalline phase is alpha-oxidation
The content of aluminium, as Alpha-alumina is in more than 50wt%.Therefore when the specific surface area of alpha-alumina supports of the invention is 5.0
m2During/below g, its principal crystalline phase is Alpha-alumina.
The three of the present invention provide a kind of alpha-alumina supports as above in epoxidation reaction of olefines, catalytic hydrogenation, catalysis
Dehydrogenation and methane vapor conversion and the application in reforming of methane on Ni-Ce.
In the present invention, the specific surface area of carrier is to adopt nitrogen physisorption BET side according to international test standards ISO-9277
What method was determined.The side pressure strength of carrier produces DLII types intelligence detector for strength of particles and determines using Dalian Chemical Research ＆. Design Inst.；
30 support samples are randomly selected, after determining radial direction crushing strength, divided by particle length, is finally averaged and is obtained.This
Term " water absorption rate " used refers to that the carrier saturation of unit mass under room temperature adsorbs the weight percentage (unit of water in bright
It is %).Assay method is：(quality is m to weigh a certain amount of carrier first1), after boiling 1h in boiling water, naturally cool to
Room temperature, carrier takes out and is erected on the moderate wet gauze of water content the attached water unnecessary to remove carrier surface, finally weighs and inhales
Quality m of the carrier after full water2, by formula " water absorption rate=(m2-m1)/m1× 100% " water absorption rate of carrier is calculated.
Specific embodiment
With reference to embodiment, the invention will be further described, but protection scope of the present invention is not limited to following enforcements
Example.
Comparative example 1
Boehmite 150.0g, the ammonium fluoride 8.0g of the surge aluminium stone 420g of 150-250 purposes, 200 mesh excessively are put into blender and are mixed
Close, then proceed in kneader, add 16.5wt% dust technology 120ml, mediate and extrusion molding be external diameter about 8.0mm,
The five hole columns of long 7.2mm, internal diameter 1.6mm, at 80 DEG C 10h is dried, make free water content be reduced to 10wt% with
Under, alumina support green compact are obtained.In being then placed in high-temperature electric resistance furnace, Jing 30h are increased to 1300 DEG C from room temperature, constant temperature 4h,
Obtain alpha-alumina supports.Its crushing strength, water absorption rate and specific surface area are determined, 1 is the results are shown in Table.
Comparative example 2
Preparation method with comparative example 1, added with barium sulfate 2.6g, vaseline 12g, highest sintering temperature when except for the difference that mixing
1350 DEG C, constant temperature 4h obtains alumina support.Its crushing strength, specific surface area and water absorption rate are determined, 1 is the results are shown in Table.
Comparative example 3
By the surge aluminium stone 490.0g of 250-500 purposes, cross the boehmite 100g of 150 mesh, ammonium fluoride 9.0g, barium sulfate 2.8g,
It is put into blender to be well mixed；Then proceed in kneader, add the salpeter solution of 80ml 16wt%, fully mediate；It was found that
Material dissipates, it is difficult to kneaded and formed.
Embodiment 1
Granularity is put into less than or equal to the surge aluminium stone 300g of 150 purposes, boehmite 300g, the ammonium fluoride 8.0g of 200 mesh excessively mixed
Glassware is well mixed；Then proceed in kneader, add the dilute nitric acid solution of 85ml 16wt%, fully mediate；Extrude afterwards
It is shaped to the five hole columns of external diameter about 8.0mm, long 7.2mm, internal diameter 1.6mm；10h is dried at 80 DEG C, makes to dissociate
Water content is reduced to below 10wt%, and alumina support green compact are obtained；In being then placed in high-temperature electric resistance furnace, Jing 30h are from room temperature liter
To 1300 DEG C, constant temperature 4h obtains alpha-alumina supports to height.And its crushing strength, specific surface area and water absorption rate are determined, as a result
It is shown in Table 1.
Embodiment 2
Granularity is less than the surge aluminium stone 400.0g of 150 purposes, crosses boehmite 200g, ammonium fluoride 9.0g, the barium sulfate 2.6 of 200 mesh
G, the powder silica gel 2.0g of 50 nanometers of particle mean size are put into blender and are well mixed；Then proceed in kneader, add 85ml
The salpeter solution of 16wt%, fully mediates；Pelletizing is extruded afterwards is shaped to external diameter about 8.3mm, long 7.5mm, internal diameter 3.6mm
Raschig ring shape particle；12h is dried at 80 DEG C, makes free water content be reduced to below 10wt%, alumina support is obtained
Green compact；In being then placed in high-temperature electric resistance furnace, Jing 30h are increased to 1240 DEG C from room temperature, and constant temperature 4h obtains alpha-alumina supports.
Its crushing strength, water absorption rate and specific surface area are determined, 1 is the results are shown in Table.
Embodiment 3
Preparation method is 1300 DEG C with embodiment 2, except for the difference that highest sintering temperature, and constant temperature 4h obtains alpha-alumina supports.
Its crushing strength, specific surface area and water absorption rate are determined, 1 is the results are shown in Table.
Embodiment 4
Preparation method with embodiment 2, except for the difference that using compression molding, sour addition be 65ml, briquetting pressure 20MPa,
Obtain alpha-alumina supports.Its crushing strength, specific surface area and water absorption rate are determined, 1 is the results are shown in Table.
Embodiment 5
It is slowly added in the case of weighing analytically pure silester 4.2g, strong agitation in the 16wt% salpeter solutions of 95ml,
Persistently stir stand-by after 30min.
Granularity is less than the surge aluminium stone 420.0g of 150 purposes, crosses boehmite 180g, ammonium fluoride 9.0g, the barium sulfate of 200 mesh
1.8g blenders are well mixed；Then proceed in kneader, add above-mentioned salpeter solution, fully mediate；Afterwards extrude pelletizing into
Type is external diameter about 8.3mm, long 7.5mm, the Raschig ring shape particle of internal diameter 3.6mm；12h is dried at 80 DEG C, makes to dissociate
Water content is reduced to below 10wt%, and alumina support green compact are obtained；In being then placed in high-temperature electric resistance furnace, Jing 30h are from room temperature liter
To 1200 DEG C, constant temperature 4h obtains alpha-alumina supports to height.Its crushing strength, water absorption rate and specific surface area are determined, is as a result seen
Table 1.
Embodiment 6
Granularity is less than the surge aluminium stone 200.0g of 150 purposes, crosses boehmite 400g, ammonium fluoride 9.0g, the barium sulfate 3.0 of 200 mesh
G, the powder silica gel 2.5g of 60 nanometers of particle mean size are put into blender and are well mixed；Then proceed in kneader, add 85ml
The salpeter solution of 16wt%, fully mediates；Pelletizing is extruded afterwards is shaped to external diameter about 8.3mm, internal diameter 3.6mm, long 7.5mm
Raschig ring shape particle；12h is dried at 80 DEG C, makes free water content be reduced to below 10wt%, alumina support is obtained
Green compact；In being then placed in high-temperature electric resistance furnace, Jing 30h are increased to 1240 DEG C from room temperature, and constant temperature 4h obtains alpha-alumina supports.
Its crushing strength, water absorption rate and specific surface area are determined, 1 is the results are shown in Table.
Embodiment 7
Granularity is put into into blender less than the boehmite 440g of the surge aluminium stone 160.0g of 150 purposes, 200 mesh excessively to be well mixed；So
After proceed in kneader, add the salpeter solution of 80ml 16wt%, fully mediate；Pelletizing is extruded afterwards is shaped to external diameter about 8.3
Mm, internal diameter 3.6mm, the Raschig ring shape particle of long 7.5mm；12h is dried at 80 DEG C, free water content is reduced to
Below 10wt%, is obtained alumina support green compact；In being then placed in high-temperature electric resistance furnace, Jing 30h are increased to 1210 DEG C from room temperature,
Constant temperature 3h, obtains alpha-alumina supports.Its crushing strength, water absorption rate and specific surface area are determined, 1 is the results are shown in Table.
Embodiment 8
The boehmite 250g that the surge aluminium stone 350.0g of 150-250 purposes will be crossed, crosses 150 mesh, ammonium fluoride 10.0g, barium sulfate 2.2g,
The petroleum coke 42.0g of powder silica gel 1.5g, 150-250 mesh of 60 nanometers of particle mean size is put into blender and is well mixed；Then turn
In entering kneader, the salpeter solution of 80ml 16wt% is added, fully mediated；The pelletizing of extrusion compacting afterwards is shaped to external diameter about 8.3
Mm, internal diameter 3.6mm, the Raschig ring shape particle of long 7.5mm；12h is dried at 80 DEG C, free water content is reduced to
Below 10wt%, is obtained alumina support green compact；In being then placed in high-temperature electric resistance furnace, Jing 30h are increased to 1300 DEG C from room temperature,
Constant temperature 4h, obtains alumina support embodiment 8.Its crushing strength, water absorption rate and specific surface area are determined, 1 is the results are shown in Table.
Embodiment 9
The surge aluminium stone 62.0g of 150-250 purposes, the boehmite 530g for crossing 200 mesh, ammonium fluoride 9.0g, barium sulfate 2.3g are put
Enter blender to be well mixed；Then proceed in kneader, add the salpeter solution of 71ml 16wt%, fully mediate；Squeeze afterwards
Go out the Raschig ring shape particle that pelletizing is shaped to external diameter about 8.3mm, internal diameter 3.6mm, long 7.5mm；12h is dried at 80 DEG C,
Make free water content be reduced to below 10wt%, alumina support green compact are obtained；In being then placed in high-temperature electric resistance furnace, Jing 30h from
Room temperature is increased to 1310 DEG C, and constant temperature 4h obtains alpha-alumina supports.Its crushing strength, water absorption rate and specific surface area are determined,
The results are shown in Table 1.The support strength is higher, but water absorption rate is low, and when carried silver catalyst is prepared, silver content is inclined in catalyst
It is low, it is unfavorable for preparing the high-selectivity catalyst of high silver content.
Table 1
Below as a example by the application by carrier of the present invention in epoxidation of ethylene silver catalyst, the carrier of the present invention is illustrated
Practical application.Actual use includes but is not limited to silver catalyst.The preparation of catalyst
Using with the identical silver catalyst of COMPARATIVE CATALYST EXAMPLE in patent document CN102397795A 1 prepare and evaluation method,
Argentiferous dipping solution is prepared, the alumina support of comparative example 2 of the present invention and embodiment 1 and embodiment 8 is impregnated, at 280 DEG C
Air stream in activate 5min, prepare contrast silver catalyst 1, catalyst 2 and 3, epoxidation of ethylene is micro- counter to be commented
Valency the results are shown in Table 2.
From data in table 2, can prepare that performance is suitable using the carrier of the present invention, or even the second that activity is more excellent
Alkene epoxidation silver catalyst.
Table 2
Claims (12)
1. a kind of method for preparing alpha-alumina supports, methods described comprises the steps：
I) total mixture comprising following component is prepared：
Component (a)：The surge aluminium stone of 150 purposes is less than or equal to based on the granularity of the 10-80% of the total mixture gross weight, it is excellent
Granularity of the choosing based on the 10-70% of the total mixture gross weight is less than or equal to the surge aluminium stone of 150 purposes；
Component (b)：The boehmite of 150 mesh is less than or equal to based on the granularity of the 20-90% of the total mixture gross weight,
The granularity for being preferably based on the 30-85% of the total mixture gross weight is less than or equal to the boehmite of 150 mesh；
Component (c)：Fluoride based on the 0-3.0% of the total mixture gross weight；
Component (d)：Alkaline earth metal compound in terms of alkali earth metal, based on the 0-2.0% of the total mixture gross weight；
Component (e)：Silicon-containing compound in terms of element silicon, based on the 0-3.0% of the total mixture gross weight；
Component (f)：The mixture of binding agent and water based on the 10-40% of the total mixture gross weight；
II) by step I) in the total mixture that obtains mediate uniform and be molded；
III) drying steps II) products therefrom, then roasting obtains the alumina support.
2. method according to claim 1, it is characterised in that component (a) also include transition aluminas and/or α-
Gibbsite；And/or component (b) also includes boehmite and/or Alumina gel.
3. method according to claim 1 and 2, it is characterised in that the alkaline-earth metal is selected from magnesium, calcium, strontium and barium
At least one in compound, preferably is selected from the compound of strontium and/or barium.
4. the method in claim 1-3 described in any one, it is characterised in that the consumption of the fluoride is based on described
The 1.0-3.0% of total mixture gross weight.
5. the method in claim 1-4 described in any one, it is characterised in that the consumption of the alkaline earth metal compound,
It is the 0.1-1.0% based on the total mixture gross weight in terms of alkali earth metal.
6. the method in claim 1-5 described in any one, it is characterised in that in terms of element silicon, in the total mixture
In containing based on the total mixture gross weight 0.02-1.0% silicon-containing compound；The silicon-containing compound include Ludox,
At least one in dry silica gel and alkaline-earth-metal silicate of the particle diameter less than 100nm.
7. the method according to any one in claim 1-6, it is characterised in that binding agent include acetic acid, hydrochloric acid,
At least one in nitric acid, sulphur aqueous acid and water.
8. the method according to any one in claim 1-7, it is characterised in that also contain base in the total mixture
In the 1-20% carbonaceous materials of the total mixture gross weight；Preferably, the carbonaceous material includes petroleum coke, graphite, carbon
At least one in powder, polyethylene and vaseline.
9. the method according to any one in claim 1-8, it is characterised in that step II) described in be dried and exist
Carry out at a temperature of 50-120 DEG C, the drying lasts 0.1-24 hours.
10. the method according to any one in claim 1-9, it is characterised in that the maximum temperature of the roasting is
800-1500 DEG C, the total time of roasting is 6-80 hours, wherein, at the highest temperature the time of constant temperature calcining is 1-10 hours；
It is preferred that the maximum temperature of the roasting be 1100-1400 DEG C, and the total time of roasting be 8-60 hours, wherein, from 100 DEG C to
The time of the roasting of 500 DEG C of temperature range is 2-20 hours.
Alpha-alumina supports prepared by 11. methods according to any one in claim 1-10, it is characterised in that institute
The side pressure strength for stating alpha-alumina supports is >=60N/cm, and specific surface area is 1.0-10.0m2/ g, water absorption rate >=35%, silicone content
0-3.0wt%；It is preferred that the side pressure strength of the alpha-alumina supports is >=80N/cm, specific surface area is 1.0-6.0m2/ g, water suction
Rate >=40%, silicone content 0-2.0wt%；Particularly preferably the side pressure strength of the alpha-alumina supports is >=100N/cm, specific surface
Product is 1.4-4.0m2/ g, water absorption rate >=43%, silicone content 0-1.0wt%.
12. alpha-alumina supports as claimed in claim 11 are in epoxidation reaction of olefines, catalytic hydrogenation, catalytic dehydrogenation, first
Application in alkane steam transforming and methane reforming.
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| CN107413388A (en) * | 2016-05-23 | 2017-12-01 | 中国石油化工股份有限公司 | A kind of alpha-aluminium oxide carrier and preparation method and application |
| CN109201027A (en) * | 2017-07-03 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of alpha-alumina supports and the preparation method and application thereof |
| CN110354910A (en) * | 2018-03-26 | 2019-10-22 | 中国石油化工股份有限公司 | A kind of alpha-alumina supports and the preparation method and application thereof |
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| CN1579617A (en) * | 2003-08-13 | 2005-02-16 | 中国科学院大连化学物理研究所 | Active alumina catalyst, and its preparation method and use |
| CN103241753A (en) * | 2012-02-02 | 2013-08-14 | 中国石油化工股份有限公司 | Alpha-alumina preparation method |
| CN103816940A (en) * | 2012-11-19 | 2014-05-28 | 中国石油化工股份有限公司 | Aluminum oxide carrier and preparation method thereof |
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| CN1579617A (en) * | 2003-08-13 | 2005-02-16 | 中国科学院大连化学物理研究所 | Active alumina catalyst, and its preparation method and use |
| CN103241753A (en) * | 2012-02-02 | 2013-08-14 | 中国石油化工股份有限公司 | Alpha-alumina preparation method |
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| CN107413388A (en) * | 2016-05-23 | 2017-12-01 | 中国石油化工股份有限公司 | A kind of alpha-aluminium oxide carrier and preparation method and application |
| CN107413388B (en) * | 2016-05-23 | 2020-04-07 | 中国石油化工股份有限公司 | α -alumina carrier and preparation method and application thereof |
| CN109201027A (en) * | 2017-07-03 | 2019-01-15 | 中国石油化工股份有限公司 | A kind of alpha-alumina supports and the preparation method and application thereof |
| CN109201027B (en) * | 2017-07-03 | 2021-07-30 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method and application thereof |
| CN110354910A (en) * | 2018-03-26 | 2019-10-22 | 中国石油化工股份有限公司 | A kind of alpha-alumina supports and the preparation method and application thereof |
| CN110354910B (en) * | 2018-03-26 | 2021-12-21 | 中国石油化工股份有限公司 | Alpha-alumina carrier and preparation method and application thereof |
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