CN108262075A - A kind of catalyst for hydrotreatment of residual oil carrier and preparation method thereof - Google Patents
A kind of catalyst for hydrotreatment of residual oil carrier and preparation method thereof Download PDFInfo
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- CN108262075A CN108262075A CN201611258776.9A CN201611258776A CN108262075A CN 108262075 A CN108262075 A CN 108262075A CN 201611258776 A CN201611258776 A CN 201611258776A CN 108262075 A CN108262075 A CN 108262075A
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- catalyst
- preparation
- hydrotreatment
- residual oil
- ammonium
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- 239000000243 solution Substances 0.000 claims abstract description 47
- 239000000843 powder Substances 0.000 claims abstract description 25
- 238000004898 kneading Methods 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 22
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 21
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 20
- 238000000465 moulding Methods 0.000 claims abstract description 20
- 239000003292 glue Substances 0.000 claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000012670 alkaline solution Substances 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- 239000000908 ammonium hydroxide Substances 0.000 claims description 18
- 239000011148 porous material Substances 0.000 claims description 17
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 15
- 239000001099 ammonium carbonate Substances 0.000 claims description 14
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- -1 acetum Substances 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- 239000000969 carrier Substances 0.000 abstract description 2
- 230000000630 rising effect Effects 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 24
- 239000003921 oil Substances 0.000 description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910017604 nitric acid Inorganic materials 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 8
- 238000009826 distribution Methods 0.000 description 6
- 241000219782 Sesbania Species 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- UIERETOOQGIECD-UHFFFAOYSA-N Angelic acid Natural products CC=C(C)C(O)=O UIERETOOQGIECD-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- UIERETOOQGIECD-ARJAWSKDSA-N angelic acid Chemical compound C\C=C(\C)C(O)=O UIERETOOQGIECD-ARJAWSKDSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000001935 peptisation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000009827 uniform distribution 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
- 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
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of catalyst for hydrotreatment of residual oil carriers and preparation method thereof, include the following steps：Step 1, acid solution, kneading are added in boehmite dry glue powder；Step 2, alkaline solution, kneading, extruded moulding are added in into step 1 resulting material；Step 3, under conditions of higher than room temperature, the material after step 2 extruded moulding is handled with the alkaline compound solution containing ammonium ion, processing time is 0.5~3 hour；And step 4, step 3 treated material is 1~8 hour dry at 105~140 DEG C, it is then placed in roaster, rising to 600~1050 DEG C with 100~200 DEG C/h of speed roasts 1~8 hour.The carrier of the present invention has the characteristics that hole appearance aperture is big, duct is open.
Description
Technical field
The present invention relates to a kind of catalyst for hydrotreatment of residual oil carriers and preparation method thereof.
Background technology
At present, industrial hydrotreating catalyst mostly the aluminium oxide using aluminium oxide or containing a small amount of auxiliary agent as carrier.It urges
The pore structure of agent carrier has the performance of catalyst important influence.It is generally believed that for heavy oil hydrogenating treatment catalyst,
Especially it is necessary to have open ducts and larger Kong Rong for catalyst for hydrotreatment of residual oil.Duct is open to be conducive in residual oil
The diffusion and reaction of macromolecule hydrocarbon substance, while catalyst aperture can be caused to block to avoid metal impurities or reaction coking；
Big Kong Rong makes catalyst have preferable metal-holding capacity, metal impurities deposition blocking catalyst duct is avoided, so as to cause to urge
The rapid decrease of agent activity.Therefore a hole holds larger and open duct catalyst for hydrotreatment of residual oil, will have good
Reactivity and activity stability.And the preparation of carrier is crucial.
In order to which the hole for improving alumina support holds and obtains open unimpeded duct, at present generally using addition expanding agent
Method, such as US4,448,896 patent introductions add in carbon powder as expanding agent, warp using a kind of boehmite as raw material
Kneading, extrusion, drying and roasting obtain alumina support, as a result so that support strength is poor, pore-size distribution disperse.
In US4,066,574, US4,113,661 and US4 describes a kind of system of alumina support in 341,625 patents
Preparation Method first adds in aqueous solution of nitric acid in Alpha-alumina monohydrate, it is molten fully to add a certain amount of ammonium hydroxide after effect
Liquid, addition are the 0.6~1.2 of nitric acid equivalent.After abundant kneading carrier is obtained through extrusion, drying and roasting.In the carrier,
Aperture holds in the hole of 8.0~15.0nm is at least up to the 70% of total pore volume, and total pore volume is 0.64~0.82mL/g.
US5,177,047 patents improve the above method, reduce the dosage of alkali, be nitric acid equivalent 0.3~
0.5.In resulting vehicle, aperture reaches more than 70% total pore volume, total pore volume 0.62mL/g in the Kong Rong of 7.0~13.0nm.
CN1, equally using first plus oxygen is made in nitric acid peptization, the method that rear plus nitrogen base aqueous solution neutralizes in 154,668 patents
Change alumina supporter.Unlike, alkalinity is per about 0.9~1.1 equivalent of angelic acid in nitrogen base solution.Resulting vehicle aperture is 14.0
The Kong Rong of~22.0nm reaches more than 70% total pore volume, and aperture peak is between 17.0~22.0nm.
In this method, the purpose for adding in ammonia spirit is to neutralize a part of acid solution, to reduce acid to alumina pore knot
The destruction of structure reduces the loss that carrier hole holds.Although the method can play the role of certain reaming, carrier is in drying
Serious with being shunk during roasting, it is limited that hole holds increase；It is excessively high to neutralize alkali addition, causes carrier difficult forming, intensity drop
It is low.
Described in CN1,181,409 it is a kind of first add in alkaline solution after Plus acidic peptizing agent support preparation method.
In the method, the purpose that first adds in alkaline solution is to form a kind of " protective film " in the surfaces externally and internally of aluminum oxide dry glue powder, to subtract
Slow acid and the interaction of aluminium oxide, reduce the loss of Kong Rong.In the carrier, aperture accounts for always in the Kong Rong of 7.0~13.0nm
More than 80% Kong Rong, average pore size is between 9.0~13.0nm.Such method has a disadvantage that：When carrier dry and
It is equally shunk seriously in roasting process, it is limited that hole holds increase；Acid solution is added in after second is that, it is impossible to effectively eliminate excessive hole and
Smaller hole, pore size distribution disperse；Third, support strength is poor, the dosage of acid is necessarily increased to improve intensity, cost increases.
One common drawback of more than support preparation method is that its aperture of prepared carrier is by outer surface to interior in uniform
Distribution, duct is not open enough, and aperture easily occurs in the reaction and blocks, causes the drastically decline of catalyst activity.
Invention content
It is a primary object of the present invention to provide a kind of catalyst for hydrotreatment of residual oil carrier and preparation method thereof, by this hair
Catalyst carrier hole appearance aperture prepared by bright method is big, and duct is open.
To achieve these goals, the present invention provides a kind of preparation methods of catalyst for hydrotreatment of residual oil carrier, should
Preparation method includes the following steps：
Step 1, acid solution, kneading are added in boehmite dry glue powder；
Step 2, alkaline solution, kneading, extruded moulding are added in into step 1 resulting material；
Step 3, under conditions of higher than room temperature, with the alkaline compound solution containing ammonium ion to step 2 extruded moulding after
Material handled, processing time be 0.5~3 hour；And
Step 4, it is step 3 treated material is 1~8 hour dry at 105~140 DEG C, it is then placed in roaster, with
100~200 DEG C/h of speed rises to 600~1050 DEG C and roasts 1~8 hour.
The preparation method of catalyst for hydrotreatment of residual oil carrier of the present invention, wherein, the acid solution is preferably
Salpeter solution, acetum, formic acid solution and hydrochloric acid solution form one or more of group.
The preparation method of catalyst for hydrotreatment of residual oil carrier of the present invention, wherein, the alkaline solution is preferably
Ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, ammonium phosphate, ammonium borate and ammonium acetate solution form one or more of group.
The preparation method of catalyst for hydrotreatment of residual oil carrier of the present invention, wherein, the alkalinity containing ammonium ion
Compound solution is preferably containing NH3The ammonium hydroxide of 5~15wt% or the ammonium carbonate solution of 10~20wt% containing ammonium carbonate, it is described
The dosage of alkaline compound solution containing ammonium ion be step 2 extruded moulding after quality of material 10~30%.
The preparation method of catalyst for hydrotreatment of residual oil carrier of the present invention, wherein, the step 1 adds in acid molten
Before liquid, boehmite dry glue powder is first mixed with extrusion aid.
The preparation method of catalyst for hydrotreatment of residual oil carrier of the present invention, wherein, the step 3 is specially：
Under conditions of room temperature, the material after step 2 extruded moulding is impregnated or sprayed with the alkaline compound solution containing ammonium ion.
The preparation method of catalyst for hydrotreatment of residual oil carrier of the present invention, wherein, the step 1 and step 2
The kneading time is preferably 10~60 minutes.
The preparation method of catalyst for hydrotreatment of residual oil carrier of the present invention, wherein, the roasting condition is preferably
700~850 DEG C are risen to 100~200 DEG C/h of speed, is roasted 1~8 hour.
To achieve these goals, the present invention also provides a kind of preparation method systems of catalyst for hydrotreatment of residual oil carrier
Standby catalyst carrier.
Catalyst carrier prepared by the preparation method of catalyst for hydrotreatment of residual oil carrier of the present invention, wherein, institute
The average pore size for stating catalyst carrier gradually increases from granular center to outer surface.
Compared with the method that existing expansion carrier hole holds, this have the advantage that：
1) carrier pore size distribution is made to tend to concentrate using the preparation process for adding alkali neutralization after first acid adding in kneading process；
2) neutralizing the addition of alkali reduces, and carrier molding is easy, and intensity improves；
3) using neutralisation treatment technique after extruded moulding, making carrier aperture, duct is open, and hole holds bigger in terraced distribution.
Specific embodiment
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, give detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
The present invention a kind of specific preparation process be：It weighs boehmite dry glue powder, adds in acid solution, kneading 10~
50 minutes；Add alkaline solution, kneading 20~60 minutes；The extruded moulding on banded extruder；Under conditions of higher than room temperature, use
Alkali compounds containing ammonium ion handles the material after extruded moulding, and processing time is 0.5~3.0 hour；Then will
Treated, and material is 1~8 hour dry at 105~140 DEG C, is then placed in roaster, with 100~200 DEG C/h of speed
600~1050 DEG C are risen to roast 1~8 hour.During made above, if weighing the thin water aluminium of 500 grams of plans containing butt 75%
Stone dry glue powder, the then acid solution added in are 200~400 grams, and alkaline solution is 100~300 grams.Catalyst carrier shape can be
Cylinder or three (four) leaves grass, drying temperature are 105~140 DEG C, and the time is 1~8 hour.Calcination temperature is 700~850 DEG C, when
Between be 1~8 hour.
Acid solution of the present invention is the aqueous solution of nitric acid, acetic acid, formic acid or hydrochloric acid, and preferably nitric acid or acetic acid is molten
Liquid, preferably acetum；The alkaline solution is ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, ammonium phosphate, ammonium borate, ammonium acetate water
At least one of solution.The alkali compounds containing ammonium ion is ammonium hydroxide or carbonic acid ammonium, preferably ammonium hydroxide.Acid solution
Addition such as can be the acetum of 3~8wt% containing acetic acid can guarantee that the normal molding of aluminium oxide is advisable, and addition is led to
It is often the 3~10% of boehmite dry glue powder quality；Alkaline solution can be containing NH3The ammonium hydroxide of 0.5~3.5wt%, alkalinity
For the addition of solution in terms of alkaline matter, alkaline matter is the 10~150% of the amount of the substance of acid solution middle acid substance.
The alkaline compound solution containing ammonium ion is containing NH3The ammonium hydroxide of 5~15wt% or containing ammonium carbonate 10~
The ammonium carbonate solution of 20wt%.
Before step 1 adds in acid solution, boehmite dry glue powder is first mixed with extrusion aid, and extrusion aid can be sesbania
Powder, starch, polyvinyl alcohol, methylcellulose, preferably field blueness powder, addition for boehmite dry glue powder 2~
8wt%, preferably 3~5wt%.
The shape of catalyst carrier of the present invention can be changed according to different requirements.
The inorganic compound of the elements such as boracic, silicon, phosphorus, titanium, magnesium can be added in support preparation method of the present invention.
Catalyst carrier of the present invention, can be used as catalyst carrier for hydrgenating, especially suitable for residuum hydrogenating and metal-eliminating or residual oil
Hydrodesulfurization catalyst support.
The present invention makes the principle that alumina support duct is open, hole appearance increases and intensity improves be：First add in acid solution
It is made to come into full contact with and act on boehmite dry glue powder, to avoid occurring excessive macropore in shaping carrier, is eliminated simultaneously
A part of aperture forms the aperture that distribution is concentrated；Suitable alkaline solution is added, neutralizes part acid, to reduce acid to oxygen
Change the destruction of aluminium pore structure, increase the Kong Rong of carrier, since the dosage of alkali reduces, support strength improves；With containing after extruded moulding
The alkali compounds of ammonium ion handles wet bar under conditions of higher than room temperature, can make during boehmite after molding occurs again
And reaction, the aperture in the certain depth of carrier surface layer is made to become larger, open " trumpet type " pore passage structure is formed, so as to make carrier
Duct become open.After extruded moulding being happened at due to described this neutralization reaction, molding and machine to carrier
Tool intensity does not have an impact.
The feature further illustrated the present invention below with embodiment and comparative example.
Embodiment 1
Boehmite dry glue powder (contents on dry basis 73.5%) 500g of Yantai Heng Hui Chemical Co., Ltd.s production is weighed, is added
Enter 15 grams of sesbania powder, be uniformly mixed.The acetic acid solution 368g of a concentration of 5wt% is added in afore-mentioned materials, kneading 20min.So
Afterwards containing NH3The ammonium hydroxide 180g of 2.0wt% is added in above-mentioned material, kneading 30min, is squeezed on preceding crowded formula single-screw extruder
Into the cylindrical type of a diameter of 2.0mm.Gained wet bar is soaked in the ammonium hydroxide that solubility is 15wt% 10 minutes.It is handled at 80 DEG C
2 hours.It is 3 hours dry at 120 DEG C, then be placed in roaster, 800 DEG C are risen to 100 DEG C/h of speed, is roasted 3 hours,
Carrier A is obtained, property is shown in Table 1.
Embodiment 2
The boehmite dry glue powder 500g of previous embodiment 1 adds in 15 grams of sesbania powder, is uniformly mixed.A concentration of
The acetic acid solution 368g of 3wt% is added in afore-mentioned materials, kneading 20 minutes.Then containing NH3The ammonium hydroxide 180g of 0.5wt% adds
Enter in above-mentioned material, kneading 40 minutes, the cylindrical type of a diameter of 2.0mm is extruded on preceding crowded formula single-screw extruder.By 30mL
The ammonium hydroxide that solubility is 5wt% is uniformly sprayed onto freshly extruded wet bar.It is handled 0.5 hour at 80 DEG C.The side of embodiment 1 is pressed again
Method is dry, roasting sample, obtains carrier B, property is shown in Table 1.
Embodiment 3
The boehmite dry glue powder 500g of previous embodiment 1 adds in 15 grams of sesbania powder, is uniformly mixed.A concentration of
The acetic acid solution 368g of 8wt% is added in afore-mentioned materials, kneading 20 minutes.Then containing NH3The ammonium hydroxide 180g of 1.5wt% adds
Enter in above-mentioned material, continue kneading 40 minutes, the cylindrical type of diameter 2.0mm is extruded on preceding crowded formula single-screw extruder.By institute
Wet bar is obtained to be soaked in the ammonium carbonate solution that solubility is 10wt% 10 minutes.It is handled 3 hours at 100 DEG C.Embodiment 1 is pressed again
Method is dry, roasting sample, obtain support C, property is shown in Table 1.
Embodiment 4
The boehmite dry glue powder 500g of previous embodiment 1 adds in 15 grams of sesbania powder, is uniformly mixed.A concentration of
The acetic acid solution 368g of 5wt% is added in afore-mentioned materials, kneading 50min.Then containing NH3The ammonium hydroxide 180g of 3.5wt% is added in
In above-mentioned material, kneading 30min is extruded into the cylindrical type of a diameter of 2.0mm on preceding crowded formula single-screw extruder.By 30mL solubility
Ammonium carbonate solution for 20wt% is uniformly sprayed onto freshly extruded wet bar.It is handled 2 hours at 100 DEG C.Embodiment 1 is pressed again
Method is dry, roasting sample, obtain carrier D, property is shown in Table 1.
Comparative example 1
This comparison example be by US4 066,574, US4,113,661, US4,341,625 describe method preparation have aluminium oxide
Carrier.Method described by three patents is essentially identical, only lists a comparative example.
Boehmite 500g same as Example 1 is weighed, adds in 18.4g nitric acid and the mixture of 350g water purifications, is mixed
Close it is uniform, then by 4.6g NH3Add in above-mentioned material with the mixtures of 165g water purifications, then through kneading same as Example 1,
Molding, dry, roasting and etc. obtain carrier E, property is shown in Table 1.
Comparative example 2
This comparison example is that the alumina support of method preparation is described by US5,177,047.
Boehmite dry glue powder 500g same as Example 1 adds in 55g nitric acid and the mixture of 350g water purifications, fills
After dividing mixing, NH is added3The ammonium hydroxide 183g of a concentration of 2.7w% according to the method identical with comparative example 1, obtains carrier F,
Property is shown in Table 1.
Comparative example 3
This comparison example is that the alumina support of method preparation is described by CN1,154,668.
Boehmite dry glue powder 500g same as Example 1 adds in a concentration of 260 grams of 7.6wt% nitric acid, fully mixed
After conjunction, the ammonia spirit 260g of a concentration of 4.5wt% is added, after abundant kneading, according to the method identical with comparative example 1, obtain
To carrier G, its property is shown in Table 1.
Comparative example 4
This comparison example is that the alumina support of method preparation is described by CN1,181,409.
Boehmite dry glue powder 500g same as Example 1 adds in the ammonium hydroxide 100g of a concentration of 4wt%, fully mixed
After pinching, the acetic acid solution 253g of a concentration of 8wt% is added, after abundant kneading, according to the method identical with comparative example 1, obtain
Carrier H, property are shown in Table 1.
1 support of table
H refers to carrier center to the distance of carrier surface in table 1, and 0~5%h refers to carrier surface at away from carrier surface 5%h
Distance, arrive away from the distance at carrier surface 25%h at 5%h~25%h span carrier surfaces 5%h, 25%h~100%h refers to
Away from the distance to carrier center at carrier surface 25%h.In another example：Carrier A carrier surfaces carrier at away from carrier surface 5%h
Average pore size be 13.2nm.
As shown in Table 1, carrier A, B, C and D of the present invention have larger Kong Rong and specific surface, have in terraced distribution
Open pore passage structure, support strength are high；And comparison vehicle E, F, G and H holes hold and specific surface is relatively low, pore passage structure is single, by force
It spends relatively low.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. a kind of preparation method of catalyst for hydrotreatment of residual oil carrier, which is characterized in that the preparation method includes the following steps：
Step 1, acid solution, kneading are added in boehmite dry glue powder；
Step 2, alkaline solution, kneading, extruded moulding are added in into step 1 resulting material
Step 3, under conditions of higher than room temperature, with the alkaline compound solution containing ammonium ion to the object after step 2 extruded moulding
Material is handled, and processing time is 0.5~3 hour；And
Step 4, it is step 3 treated material is 1~8 hour dry at 105~140 DEG C, it is then placed in roaster, with 100
~200 DEG C/h of speed rises to 600~1050 DEG C and roasts 1~8 hour.
2. the preparation method of catalyst for hydrotreatment of residual oil carrier according to claim 1, which is characterized in that the acidity
Solution forms one or more of group by salpeter solution, acetum, formic acid solution and hydrochloric acid solution.
3. the preparation method of catalyst for hydrotreatment of residual oil carrier according to claim 1, which is characterized in that the alkalinity
Solution forms one or more of group by ammonium hydroxide, ammonium carbonate, ammonium hydrogen carbonate, ammonium phosphate, ammonium borate and ammonium acetate solution.
4. the preparation method of catalyst for hydrotreatment of residual oil carrier according to claim 1, which is characterized in that described to contain ammonium
The alkaline compound solution of ion is containing NH3The ammonium hydroxide of 5~15wt% or the ammonium carbonate of 10~20wt% containing ammonium carbonate are water-soluble
Liquid, the dosage of the alkaline compound solution containing ammonium ion for the quality of material after step 2 extruded moulding 10~
30%.
5. the preparation method of catalyst for hydrotreatment of residual oil carrier according to claim 1, which is characterized in that the step
Before 1 adds in acid solution, boehmite dry glue powder is first mixed with extrusion aid.
6. the preparation method of catalyst for hydrotreatment of residual oil carrier according to claim 1, which is characterized in that the step
3 are specially：Under conditions of higher than room temperature, with the alkaline compound solution immersion containing ammonium ion or 2 extruded moulding of spraying step
Material afterwards.
7. the preparation method of catalyst for hydrotreatment of residual oil carrier according to claim 1, which is characterized in that the step
1 and step 2 the kneading time be 10~60 minutes.
8. the preparation method of catalyst for hydrotreatment of residual oil carrier according to claim 1, which is characterized in that the roasting
Condition is to rise to 700~850 DEG C with 100~200 DEG C/h of speed, is roasted 1~8 hour.
9. catalyst prepared by the preparation method of claim 1 to 8 any one of them catalyst for hydrotreatment of residual oil carrier carries
Body.
10. catalyst carrier prepared by the preparation method of catalyst for hydrotreatment of residual oil carrier according to claim 9,
It is characterized in that, the average pore size of the catalyst carrier gradually increases from granular center to outer surface.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114471507A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalytic carrier material, preparation method thereof, catalytic material and application |
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| CN1209355A (en) * | 1997-08-27 | 1999-03-03 | 中国石油化工总公司 | Macroporous alumina supporter and preparation method therefor |
| WO1999019061A1 (en) * | 1997-10-14 | 1999-04-22 | Japan Energy Corporation | Hydrotreating catalyst for heavy oil, carrier for the catalyst, and process for the preparation of the catalyst |
| CN1289645A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing alumina carrier with centralized pores distribution |
| CN1351115A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Demetalating and desulfurizing hydrocatalyst and its preparing process |
| CN102259033A (en) * | 2010-05-24 | 2011-11-30 | 中国石油化工股份有限公司 | Alumina carrier and preparation method thereof as well as hydrogenation catalyst and preparation method thereof |
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| CN1209355A (en) * | 1997-08-27 | 1999-03-03 | 中国石油化工总公司 | Macroporous alumina supporter and preparation method therefor |
| WO1999019061A1 (en) * | 1997-10-14 | 1999-04-22 | Japan Energy Corporation | Hydrotreating catalyst for heavy oil, carrier for the catalyst, and process for the preparation of the catalyst |
| CN1289645A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Process for preparing alumina carrier with centralized pores distribution |
| CN1351115A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Demetalating and desulfurizing hydrocatalyst and its preparing process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114471507A (en) * | 2020-10-27 | 2022-05-13 | 中国石油化工股份有限公司 | Catalytic carrier material, preparation method thereof, catalytic material and application |
| CN114471507B (en) * | 2020-10-27 | 2023-07-28 | 中国石油化工股份有限公司 | Catalytic carrier material and preparation method thereof, catalytic material and application |
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