CN108927146A - A kind of inferior heavy oil hydrogenation catalyst and preparation method thereof - Google Patents
A kind of inferior heavy oil hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN108927146A CN108927146A CN201710367714.XA CN201710367714A CN108927146A CN 108927146 A CN108927146 A CN 108927146A CN 201710367714 A CN201710367714 A CN 201710367714A CN 108927146 A CN108927146 A CN 108927146A
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- heavy oil
- oil hydrogenation
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- charcoal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 239000000295 fuel oil Substances 0.000 title claims abstract description 57
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000003610 charcoal Substances 0.000 claims abstract description 50
- 239000008187 granular material Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000005554 pickling Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000008246 gaseous mixture Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 238000006477 desulfuration reaction Methods 0.000 abstract description 9
- 230000023556 desulfurization Effects 0.000 abstract description 9
- 239000000725 suspension Substances 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002002 slurry Substances 0.000 abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 41
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 16
- 239000003921 oil Substances 0.000 description 13
- 238000002803 maceration Methods 0.000 description 9
- 239000010970 precious metal Substances 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 235000013162 Cocos nucifera Nutrition 0.000 description 5
- 244000060011 Cocos nucifera Species 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000001802 infusion Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/31—Density
-
- 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
- B01J35/617—500-1000 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
- B01J35/633—Pore volume less than 0.5 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G35/00—Reforming naphtha
- C10G35/04—Catalytic reforming
- C10G35/06—Catalytic reforming characterised by the catalyst used
- C10G35/085—Catalytic reforming characterised by the catalyst used containing platinum group metals or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of inferior heavy oil hydrogenation catalyst and preparation method thereof, which includes the following steps, S1：Powdered active carbon and binder are mixed into ball particle charcoal；S2：Pickling and charing process successively are carried out to spheric granules charcoal, the spheric granules charcoal that obtains that treated；S3：By treated, spheric granules charcoal is immersed in solution containing Pt, obtains catalyst precursor；S4：Catalyst precursor is activated and roasted simultaneously under reactive gaseous agent atmosphere, the catalyst is finally made.In the catalyst, the content of Pt is 0.1wt%~2wt%；Heap density is 0.4~0.6g/mL, for can be very good to be suspended in heavy oil in the reactors such as ebullated bed, suspension bed, slurry bed system, bulk bed, inferior heavy oil hydrogenation process is carried out, desulfurization nitrogen, demetalization, the significant effect for taking off carbon residue, are significantly better than that traditional inferior heavy oil hydrogenation process.
Description
Technical field
The invention belongs to technical field of petrochemical industry, it is related to a kind of inferior heavy oil hydrogenation catalyst and preparation method thereof.
Background technique
Due to absorbent charcoal material specific surface area with higher, pore structure abundant and distinctive physicochemical properties,
Carrier as metallic catalyst, can be such that active metal obtains fully dispersed, can not only save metal consumption so that reduce at
This, while metallic being prevented to be sintered, improve the activity and stability of catalyst.In addition, active carbon is at low cost, can be modified,
Acid and alkali-resistance is excellent catalyst carrier.
It is carrier that catalyst, which generallys use active carbon, in ammonia synthesis industry, using ruthenium trichloride as ruthenium precursor, alkali metal and alkali
Earth metal is auxiliary agent, is made by infusion process.The method that CN1621148A, CN1270081A use hydrogen reducing,
CN1385238A replaces hydrogen to be restored using hydrazine hydrate, CN102950026A provide a kind of preparation process be not related to chlorine from
The method of son.In existing palladium-Pd/carbon catalyst preparation process, CN 103120936A, CN 103028398A, CN
1436595A, US2857337 etc. are directed to hydrofining crude terephthalic acid process, disclose palladium/carbon loaded type noble metal catalysis
The preparation method of agent, and point out that palladium is conducive to refinement of crude terephthalic acid reaction with the catalyst of eggshell formal distribution.In addition,
Pd/carbon catalyst is also used for unsaturated hydrocarbons selective hydrogenation process, and US 3138560,1952061 A of CN are directed to this process,
The improvement carried out in terms of improving noble metal distribution, preventing migration and aggregation to preparation method is disclosed respectively.
Current industrial inferior heavy oil catalyst carrier for hydrgenating is generally aluminium oxide, and specific surface area is limited by material, is led
Activation metal dispersion is uneven, and sintering aggregation is had in reaction process.Active metal dosage is big and aluminium oxide cost
Height can all increase cost.
Also, traditional inferior heavy oil hydrogenation process mostly uses fixed bed reactors, and shifting thermal energy power is poor, and bed temperature rise is big, office
Portion's hot spot is more, and coking is serious, causes bed pressure drop big, easily blocks, catalyst inactivation is fast, and operation cycle is short.And ebullated bed, suspension
In the reactors such as bed, slurry bed system, bulk bed, catalyst is kept in motion, jigging bed condition stable homogeneous, and reaction efficiency is high, temperature
Uniformly, hot spot is few, and catalyst inactivation is slow for degree.But the density of catalyst of conventional oxidation alumina supporter is big, is not suitable for suspending, so that
Device operation difficulty is big.
Summary of the invention
The object of the present invention is to provide one kind be suitable for the reactor types such as ebullated bed, suspension bed, slurry bed system, bulk bed into
The preparation method and the inferior heavy oil as made from the preparation method of the inferior heavy oil hydrogenation catalyst of row inferior heavy oil hydrogenation process
Hydrogenation catalyst, the catalyst under equivalent reaction condition, carry out inferior heavy oil hydrogenation process, desulfurization nitrogen, demetalization, take off it is residual
Charcoal significant effect.
For this purpose, the present invention provides a kind of preparation method of inferior heavy oil hydrogenation catalyst, include the following steps：
S1：Powdered active carbon and binder are mixed into ball particle charcoal；
S2：Pickling and charing process successively are carried out to spheric granules charcoal, the spheric granules charcoal that obtains that treated；
S3：By treated, spheric granules charcoal is immersed in solution containing Pt, obtains catalyst precursor；
S4：Catalyst precursor is activated and roasted simultaneously under reactive gaseous agent atmosphere, the catalysis is finally made
Agent.
The preparation method of inferior heavy oil hydrogenation catalyst of the present invention, in step S1, the ratio of the spheric granules charcoal
Surface area is preferably 500~1700m2/ g, it is preferably 0.1~2.0mL/g that hole, which holds, and partial size is preferably 2~100 mesh, further excellent
It is selected as 5~60 mesh.
The preparation method of inferior heavy oil hydrogenation catalyst of the present invention, in step S1, the powdered active carbon is excellent
It is selected as wood activated charcoal, coaly activated carbon or petroleum activated carbon.
The preparation method of inferior heavy oil hydrogenation catalyst of the present invention, in step S1, the binder preferably has
Machine binder or inorganic binder.
The preparation method of inferior heavy oil hydrogenation catalyst of the present invention, wherein the organic binder is preferably selected from
By at least one of phenolic resin, carboxymethyl cellulose and the formed group of polyvinyl alcohol.
The preparation method of inferior heavy oil hydrogenation catalyst of the present invention, in step S2, it is described treated spherical
The average pore size of grain charcoal is preferably 2~100nm, further preferably 10~50nm.
The preparation method of inferior heavy oil hydrogenation catalyst of the present invention, in step S2, the process of the pickling is preferred
For：With 2~20% nitric acid solution impregnate 1~for 24 hours, be then washed with water to pH=7, be dried for standby.
The preparation method of inferior heavy oil hydrogenation catalyst of the present invention, in step S2, the process of the charing is preferred
For：By active carbon under inert gas atmosphere 1000~2000 DEG C roasting 1~for 24 hours, it is spare to be then down to room temperature.
The preparation method of inferior heavy oil hydrogenation catalyst of the present invention, in step S3, the solution containing Pt is preferably
Chloroplatinic acid, the dipping are preferably excessive dipping or incipient impregnation, and the time of the dipping is preferably 1~for 24 hours.
The preparation method of inferior heavy oil hydrogenation catalyst of the present invention, in step S4, the reactive gaseous agent is preferred
The gaseous mixture being made of air and vapor.
The preparation method of inferior heavy oil hydrogenation catalyst of the present invention, in step S4, the item of the activation and roasting
Part is preferably：Temperature is 300~800 DEG C, processing 1~be down to room temperature afterwards for 24 hours.
It is including the ball as made from above-mentioned preparation method the present invention also provides a kind of inferior heavy oil hydrogenation catalyst
Shape particle charcoal and active metal Pt, on the basis of catalyst, in terms of the quality of Pt, the content of Pt is 0.1wt%~2wt%, excellent
It is selected as 0.5wt%~1.5wt%；The heap density of the catalyst is 0.4~0.6g/mL, preferably 0.45~0.55g/mL.
The present invention also provides a kind of detailed processes of the preparation method of inferior heavy oil hydrogenation catalyst, include the following steps：
Choose powdered active carbon, first with binder kneading and be shaped to spheric granules charcoal, later through overpickling and charing process,
Then by infusion process carried noble metal Pt, active carbon activation and catalyst roasting are finally carried out simultaneously under reactive gaseous agent environment
It burns, activated carbon supported precious metals pt catalyst is made.The specific steps are：
(1) powdered active carbon, and binder kneading, then at spheric granules charcoal are chosen.
It is compared to long strip type, the other shapes of the catalyst such as powder-type are analyzed from fluid-mechanics point of view, spherical preferably
In being suspended in liquid phase oil product, it is also just more suitable for ebullated bed, suspension bed, slurry bed system, in the reactor types such as bulk bed.And
Spheric granules intensity is bigger, facilitates to reduce catalyst abrasion in catalyst flow process.So first will in the present invention
Absorbent charcoal powder body and binder kneading, then at spheric granules charcoal.
Powdered activated carbon can be coconut husk or other shells or other wooden, coals quality, petroleum activated carbon, preferably shell
Charcoal and carbo lignius are conducive to catalyst suspension because its density is smaller；Binder can be various organic or inorganic binders, excellent
It selects phenolic resin (PR), the bond effect of carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), these three binders is good, made
Standby catalyst granules intensity is high, so that the abrasion that catalyst floats on a liquid is small.
Above-mentioned spheric granules charcoal, specific surface area are 500~1700m20.1~2.0mL/g of/g, Kong Rongwei, partial size 2~
100 mesh, preferably 5~60 mesh, preferably 5~30 mesh, suitable partial size are conducive to the suspension of catalyst.
(2) pickling is carried out to spheric granules charcoal, detailed process is：With 2~20% nitric acid solution impregnate 1~for 24 hours, then
It is washed with water to pH=7, is dried for standby.
(3) the spheric granules charcoal after pickling is carbonized, detailed process is：It places it in high temperature furnace, in inertia
Under gas atmosphere 1000~2000 DEG C roasting 1~for 24 hours, it is spare to be then down to room temperature.
Active carbon carbonization temperature is usually less than 1000 DEG C, happens is that dehydration, depickling, deoxidation, certain embodiments.Active carbon hole
In structure based on micropore, average pore size is less than 10nm, but carries out in inferior heavy oil hydrogenation process, and heavy oil molecules are bigger,
Need mesopore orbit.Carbonization temperature is increased to 1000~2000 DEG C, the charcoal in micropore gap can be burnt up and form bigger hole
Road reaches 10~50nm, is conducive to heavy oil macromolecular demetalization desulfurization nitrogen etc., more suitable for carrying out inferior heavy oil hydrogenation process.
(4) will treated that spheric granules charcoal is immersed in solution containing Pt, impregnate 1 at room temperature~for 24 hours, obtain catalyst
Presoma, dipping process is using excessive dipping or incipient impregnation.
(5) prepared catalyst precursor is activated and is roasted simultaneously under reactive gaseous agent atmosphere, gas is living
Property agent is the gaseous mixture being made of air and vapor, and the catalyst is finally made.
The activation of catalyst precursor and roasting carry out simultaneously, i.e., the pore-creating of spheric granules charcoal and catalyst roasting and meanwhile into
Row, not only simplifies catalyst preparation step, and save time cost and manufacturing cost.Actual conditions are：Temperature is
300~800 DEG C, processing 1~be down to room temperature afterwards for 24 hours.
The content of Pt (in terms of the quality of Pt) is 0.1wt%~2wt%, preferably 0.5wt%~1.5wt% in catalyst.
Pt load capacity within this range can not only guarantee there is enough activity, and little to the Effects of Density of finished catalyst,
It is suitable for being suspended in heavy oil.
The bulk density of final catalyst prod is 0.4~0.6g/mL, and preferably 0.45~0.55g/mL is as suitable for
Catalyst specification in the reactors such as ebullated bed, suspension bed, slurry bed system, bulk bed.It is used for ebullated bed, suspension bed, slurry
Suitable for the reactor types of inferior heavy oil hydrogenation process, reaction condition is for bed, bulk bed etc.：300~500 DEG C, 10~
20MPa, 0.1~10h-1, hydrogen-oil ratio 500~2000:1.Desulfurization nitrogen, demetalization, de- carbon residue significant effect, hence it is evident that bad better than tradition
Reduced fuel oil hydrogenation process.
It is compared to traditional using aluminium oxide as the hydrogenation catalyst of carrier, obtained activated carbon supported Pt in the present invention
Hydrogenation catalyst density is low, and the reactors such as preferably and ebullated bed, suspension bed, slurry bed system, bulk bed pass through and choose catalyst pellets
Diameter and operating condition, such as gas velocity can be such that catalyst is suspended in reactor, improve the biography of reaction stream and catalyst
Matter heat transfer efficiency, avoids sintering of catalyst and coking to a certain extent.In addition, active carbon has bigger specific surface area and Geng Feng
Rich pore structure is conducive to the dispersion of precious metals pt, improves reactivity.Moreover, active carbon is at low cost, precious metals pt is due to dividing
Divergence is high and dosage is few, reduces catalyst cost.
Specific embodiment
Following example is method in order to further illustrate the present invention, but be should not be limited thereto.
Embodiment 1
It chooses coconut activated carbon powder and carboxymethyl cellulose (CMC) mixes ball particle charcoal, specific surface area is
800m2/ g, Kong Rongwei 0.4mL/g, 20 mesh of partial size.10% nitric acid solution of spheric granules charcoal is impregnated into 2h first, is then used
Water washing is dried to pH=7；Later, the spheric granules charcoal after pickling is placed in high temperature furnace, under an inert atmosphere 1200
DEG C charing 12h, be down to room temperature, at this time the average pore size of spheric granules charcoal be 16nm；Chloroplatinic acid is dissolved in the water, dipping is made
Liquid.Using equi-volume impregnating, by treated, spheric granules charcoal impregnates 12h in maceration extract at room temperature, before obtaining catalyst
Drive body；Finally Pt/C catalyst precursor is placed in high temperature furnace, is passed through the gaseous mixture being made of air, vapor, at 600 DEG C
12h is handled, while being activated and being roasted, the inferior heavy oil hydrogenation catalyst of activated carbon supported precious metals pt is just made, so
After to be down to room temperature spare.On the basis of catalyst, in terms of the quality of Pt, the content of Pt is 0.56wt%, heap in the catalyst
Density is 0.44g/mL.
Obtained catalyst is filled in bulk bed reactor, feedstock oil is catalytic cracked oil pulp, property such as table 1
Shown, reaction condition and reaction result are as shown in table 2.
1 raw material oil nature of table
2 reaction condition of table and reaction result
| Reaction temperature | Reaction pressure | Air speed | S | N | Ni+V | Carbon residue |
| ℃ | MPa | h-1 | % | % | ppm | % |
| 380 | 15 | 0.5 | 0.08 | 0.21 | 0.2 | 1.04 |
By Tables 1 and 2 it can be calculated that desulfurization degree is 95%, denitrification percent 84%, demetallization per 98% takes off carbon residue
Rate is 86%.Reaction result shows activated carbon supported noble metal pt catalyst effect in bulk bed inferior heavy oil hydrogenation process
Highly significant.
Embodiment 2
It chooses coconut activated carbon powder and carboxymethyl cellulose (CMC) mixes ball particle charcoal, specific surface area is
800m2/ g, Kong Rongwei 0.4mL/g, 20 mesh of partial size.10% nitric acid solution of spheric granules charcoal is soaked into 2h first, then uses water
Washing is dried to pH=7；Later, the spheric granules charcoal after pickling is placed in high temperature furnace, 1500 DEG C under an inert atmosphere
12h is carbonized, room temperature is down to, average pore size is 20nm at this time；Chloroplatinic acid is dissolved in the water, maceration extract is made.Using isometric
Infusion process, by treated, spheric granules charcoal impregnates 12h in maceration extract at room temperature, obtains catalyst precursor；Finally by Pt/
C catalyst presoma is placed in high temperature furnace, is passed through the gaseous mixture being made of air, vapor, in 600 DEG C of processing 12h, while into
Row activation and roasting, are just made the inferior heavy oil hydrogenation catalyst of activated carbon supported precious metals pt, it is spare to be then down to room temperature.
On the basis of catalyst, in terms of the quality of Pt, the content of Pt is 1.07wt% in the catalyst, and heap density is 0.49g/mL.
Obtained catalyst is filled in bulk bed reactor, feedstock oil is catalytic cracked oil pulp, property such as table 1
Shown, reaction condition and reaction result are as shown in table 3.
3 reaction condition of table and reaction result
| Reaction temperature | Reaction pressure | Air speed | S | N | Ni+V | Carbon residue |
| ℃ | MPa | h-1 | % | % | ppm | % |
| 380 | 15 | 0.5 | 0.06 | 0.17 | 0.18 | 1.02 |
By table 1 and table 3 it can be calculated that desulfurization degree is 96%, denitrification percent 87%, demetallization per 98% takes off carbon residue
Rate is 86%.Reaction result shows activated carbon supported noble metal pt catalyst effect in bulk bed inferior heavy oil hydrogenation process
Highly significant.
Embodiment 3
It chooses coconut activated carbon powder and carboxymethyl cellulose (CMC) mixes ball particle charcoal, specific surface area is
800m2/ g, Kong Rongwei 0.4mL/g, 20 mesh of partial size.10% nitric acid solution of spheric granules charcoal is soaked into 2h first, then uses water
Washing is dried to pH=7；Later, the spheric granules charcoal after pickling is placed in high temperature furnace, 1800 DEG C under an inert atmosphere
12h is carbonized, room temperature is down to, average pore size is 27nm at this time；Chloroplatinic acid is dissolved in the water, maceration extract is made.Using isometric
The spheric granules charcoal handled well is impregnated in maceration extract 12h at room temperature, obtains catalyst precursor by infusion process；Finally by Pt/
C catalyst presoma is placed in high temperature furnace, is passed through the gaseous mixture being made of air, vapor, in 600 DEG C of processing 12h, while into
Row activation and roasting, are just made the inferior heavy oil hydrogenation catalyst of activated carbon supported precious metals pt, it is spare to be then down to room temperature.
On the basis of catalyst, in terms of the quality of Pt, the content of Pt is 1.52wt% in the catalyst, and heap density is 0.57g/mL.
Obtained catalyst is filled in bulk bed reactor, feedstock oil is catalytic cracked oil pulp, property such as table 1
Shown, reaction condition and reaction result are as shown in table 4.
4 reaction condition of table and reaction result
| Reaction temperature | Reaction pressure | Air speed | S | N | Ni+V | Carbon residue |
| ℃ | MPa | h-1 | % | % | ppm | % |
| 380 | 15 | 0.5 | 0.09 | 0.19 | 0.4 | 0.87 |
By table 1 and table 4 it can be calculated that desulfurization degree is 94%, denitrification percent 85%, demetallization per 96% takes off carbon residue
Rate is 88%.Reaction result shows activated carbon supported noble metal pt catalyst effect in bulk bed inferior heavy oil hydrogenation process
Highly significant.
Comparative example 1
It chooses coconut activated carbon powder and carboxymethyl cellulose (CMC) mixes ball particle charcoal, specific surface area is
800m2/ g, Kong Rongwei 0.4mL/g, 20 mesh of partial size.10% nitric acid solution of spheric granules charcoal is soaked into 2h first, then uses water
Washing is dried to pH=7；Later, the spheric granules charcoal after pickling is placed in high temperature furnace, 800 DEG C under an inert atmosphere
12h is carbonized, room temperature is down to, average pore size is 6nm at this time；Chloroplatinic acid is dissolved in the water, maceration extract is made.Using isometric leaching
Stain method, by treated, spheric granules charcoal impregnates 12h in maceration extract at room temperature, obtains catalyst precursor；Finally by Pt/C
Catalyst precursor is placed in high temperature furnace, is passed through the gaseous mixture being made of air, vapor, in 600 DEG C of processing 12h, while into
Row activation and roasting, are just made the hydrogenation catalyst of activated carbon supported precious metals pt, it is spare to be then down to room temperature.With catalyst
On the basis of, in terms of the quality of Pt, the content of Pt is 0.97wt% in the catalyst, and heap density is 0.51g/mL.
Obtained catalyst is filled in bulk bed reactor, feedstock oil is catalytic cracked oil pulp, property such as table 1
Shown, reaction condition and reaction result are as shown in table 5.
5 reaction condition of table and reaction result
| Reaction temperature | Reaction pressure | Air speed | S | N | Ni+V | Carbon residue |
| ℃ | MPa | h-1 | % | % | ppm | % |
| 380 | 15 | 0.5 | 0.20 | 0.46 | 1.69 | 1.85 |
By table 1 and table 5 it can be calculated that desulfurization degree is 88%, denitrification percent 64%, demetallization per 85% takes off carbon residue
Rate is 74%.When reaction result shows that active carbon carbonization temperature is 800 DEG C, fail to be formed inside active carbon enough mesoporous
Structure, effect is undesirable in bulk bed inferior heavy oil hydrogenation process.
Comparative example 2
Choose the alumina particle that partial size is 20 mesh, specific surface area 280m2/ g, Kong Rongwei 0.5mL/g.By chloroplatinic acid
It is dissolved in the water, maceration extract is made.Using equi-volume impregnating, aluminium oxide is impregnated into 12h in maceration extract at room temperature, is just made
The hydrogenation catalyst of alumina load precious metals pt, it is spare to be down to room temperature.On the basis of catalyst, in terms of the quality of Pt, this is urged
The content of Pt is 1.14wt% in agent, and heap density is 0.65g/mL.
Obtained catalyst is filled in bulk bed reactor, feedstock oil is catalytic cracked oil pulp, property such as table 1
Shown, reaction condition and reaction result are as shown in table 6.
6 reaction condition of table and reaction result
| Reaction temperature | Reaction pressure | Air speed | S | N | Ni+V | Carbon residue |
| ℃ | MPa | h-1 | % | % | ppm | % |
| 380 | 15 | 0.5 | 0.37 | 0.75 | 2.3 | 2.78 |
By table 1 and table 6 it can be calculated that desulfurization degree is 78%, denitrification percent 41%, demetallization per 80% takes off carbon residue
Rate is 62%.Reaction result show activated carbon supported noble metal pt catalyst in bulk bed inferior heavy oil hydrogenation process, performance
It is significantly better than the catalyst of alumina load.
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 modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to protection scope of the present invention.
Claims (16)
1. a kind of preparation method of inferior heavy oil hydrogenation catalyst, which is characterized in that include the following steps：
S1：Powdered active carbon and binder are mixed into ball particle charcoal；
S2：Pickling and charing process successively are carried out to spheric granules charcoal, the spheric granules charcoal that obtains that treated；
S3：By treated, spheric granules charcoal is immersed in solution containing Pt, obtains catalyst precursor；
S4：Catalyst precursor is activated and roasted simultaneously under reactive gaseous agent atmosphere, the catalyst is finally made.
2. the preparation method of inferior heavy oil hydrogenation catalyst according to claim 1, which is characterized in that in step S1, institute
The specific surface area for stating spheric granules charcoal is 500~1700m20.1~2.0mL/g of/g, Kong Rongwei, partial size are 2~100 mesh.
3. the preparation method of inferior heavy oil hydrogenation catalyst according to claim 2, which is characterized in that the spheric granules
The partial size of charcoal is 5~60 mesh.
4. the preparation method of inferior heavy oil hydrogenation catalyst according to claim 1, which is characterized in that in step S1, institute
Stating powdered active carbon is wood activated charcoal, coaly activated carbon or petroleum activated carbon.
5. the preparation method of inferior heavy oil hydrogenation catalyst according to claim 1, which is characterized in that in step S1, institute
Stating binder is organic binder or inorganic binder.
6. the preparation method of inferior heavy oil hydrogenation catalyst according to claim 5, which is characterized in that the organic adhesive
Agent is selected from by least one of phenolic resin, carboxymethyl cellulose and the formed group of polyvinyl alcohol.
7. the preparation method of inferior heavy oil hydrogenation catalyst according to claim 1, which is characterized in that in step S2, institute
The average pore size for spheric granules charcoal of stating that treated is 2~100nm.
8. the preparation method of inferior heavy oil hydrogenation catalyst according to claim 7, which is characterized in that described treated
The average pore size of spheric granules charcoal is 10~50nm.
9. the preparation method of inferior heavy oil hydrogenation catalyst according to claim 1, which is characterized in that in step S2, institute
The process for stating pickling is：With 2~20% nitric acid solution impregnate 1~for 24 hours, be then washed with water to pH=7, be dried for standby.
10. the preparation method of inferior heavy oil hydrogenation catalyst according to claim 1, which is characterized in that in step S2, institute
The process for stating charing is：By active carbon under inert gas atmosphere 1000~2000 DEG C roasting 1~for 24 hours, it is standby to be then down to room temperature
With.
11. the preparation method of inferior heavy oil hydrogenation catalyst according to claim 1, which is characterized in that in step S3, institute
Stating solution containing Pt is chloroplatinic acid, and the dipping is excessive dipping or incipient impregnation, the time of the dipping is 1~for 24 hours.
12. the preparation method of inferior heavy oil hydrogenation catalyst according to claim 1, which is characterized in that in step S4, institute
State the gaseous mixture that reactive gaseous agent is made of air and vapor.
13. the preparation method of inferior heavy oil hydrogenation catalyst according to claim 1, which is characterized in that in step S4, institute
The condition for stating activation and roasting is：Temperature is 300~800 DEG C, processing 1~be down to room temperature afterwards for 24 hours.
14. a kind of inferior heavy oil hydrogenation catalyst, be as made from the described in any item preparation methods of claim 1-13,
It is characterized in that, including spheric granules charcoal and active metal Pt, on the basis of catalyst, in terms of the quality of Pt, the content of Pt is
0.1wt%~2wt%；The heap density of the catalyst is 0.4~0.6g/mL.
15. inferior heavy oil hydrogenation catalyst according to claim 14, which is characterized in that the content of the Pt is
0.5wt%~1.5wt%.
16. inferior heavy oil hydrogenation catalyst according to claim 14, which is characterized in that the heap density be 0.45~
0.55g/mL。
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