CN108452807A - Coking naphtha desilication catalyst and preparation method thereof - Google Patents
Coking naphtha desilication catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN108452807A CN108452807A CN201711029445.2A CN201711029445A CN108452807A CN 108452807 A CN108452807 A CN 108452807A CN 201711029445 A CN201711029445 A CN 201711029445A CN 108452807 A CN108452807 A CN 108452807A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- coking naphtha
- desilicification
- carrier
- preparation
- Prior art date
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- Granted
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000004939 coking Methods 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims description 20
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000002131 composite material Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 15
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 11
- 238000005470 impregnation Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 7
- 238000002803 maceration Methods 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 150000002604 lanthanum compounds Chemical class 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229910017569 La2(CO3)3 Inorganic materials 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- NZPIUJUFIFZSPW-UHFFFAOYSA-H lanthanum carbonate Chemical compound [La+3].[La+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O NZPIUJUFIFZSPW-UHFFFAOYSA-H 0.000 claims description 3
- 229960001633 lanthanum carbonate Drugs 0.000 claims description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 3
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 2
- 230000001788 irregular Effects 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- 239000007767 bonding agent Substances 0.000 claims 1
- 210000004556 brain Anatomy 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000004575 stone Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 241000219782 Sesbania Species 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 5
- 229940010552 ammonium molybdate Drugs 0.000 description 5
- 235000018660 ammonium molybdate Nutrition 0.000 description 5
- 239000011609 ammonium molybdate Substances 0.000 description 5
- 235000015165 citric acid Nutrition 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 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
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8871—Rare earth metals or actinides
-
- 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
- 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)
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten 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
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A catalyst for desiliconizing the coked naphtha is composed of carrier, the main active metal loaded on said carrier, Ni and Mo as main active metals, and Al2O3‑TiO2‑La2O3-graphene composite oxide as a carrier; the specific surface area of the catalyst is 250-500 m2The catalyst has specific pore diameter and larger pore volume, and can efficiently remove the coking naphthaOrganosilicon, protecting the main hydrofining catalyst.
Description
Technical field
The present invention relates to a kind of coking naphtha desilicification catalysts and preparation method thereof, burnt suitable for petroleum refining field
The desiliconization agent of main refining agent is protected in naphtha unifining process, the removing for organosilicon in coking naphtha fraction.
Background technology
It is added in delayed coking containing silicon defoaming agent, generates cyclosiloxane at high temperature containing silicon defoaming agent, lead to it
Product, coking naphtha silicone content are higher.
Cyclosiloxane is the main refining agent poisonous substance of coker gasoline, and long-term accumulation causes main refined activity to decline, cycle of operation contracting
It is short.
Domestic coking naphtha hydrogenation plant uses periodic replacement major catalyst mostly without using desilicification catalyst
Method, result in waste of resources.
Invention content
It is an object of the invention to develop a kind of coking naphtha desilicification catalyst, using Ni, Mo as active metal, use
Al2O3-TiO2-La2O3Graphene composite oxides are carrier, make Al2O3Carrier obtains modification appropriate, significantly improves catalysis
The activity of agent reaches the main refining agent of protection, extends device operation especially suitable for the removing of organosilicon in coking naphtha fraction
The purpose in period.
The present invention provides a kind of coking naphtha desilicification catalyst, including carrier and main active metal, and main active metal is negative
It is loaded on carrier, wherein：
With Ni, Mo for main active metal, Al2O3-TiO2-La2O3Graphene composite oxides are carrier；
The specific surface area of catalyst is 250~500m2/ g, hole hold 0.5~0.8mL/g.
Coking naphtha desilicification catalyst of the present invention, wherein：In terms of oxide, main active metal preferably accounts for catalysis
5.5~12.5wt% of agent gross mass.
Coking naphtha desilicification catalyst of the present invention, wherein：Based on the weight percent of catalyst, NiO contents
Preferably 0.5~2.5wt%, MoO3Content is preferably 5.0~10.0wt%.
Coking naphtha desilicification catalyst of the present invention, wherein：On the basis of carrier gross mass, by weight percentage
Meter, TiO2Content is preferably 1~10wt%, La2O3Content is preferably 1~10wt%, and graphene content is preferably 0.01~
5wt%, remaining is Al2O3。
Coking naphtha desilicification catalyst of the present invention, wherein：The shape of catalyst is preferably sheet, spherical shape, circle
Column, irregular strip, graininess or tooth are spherical.
Coking naphtha desilicification catalyst of the present invention, wherein：The diameter of catalyst is preferably 0.8mm~2.0mm
Slice or thick item more than 2.5mm.
Coking naphtha desilicification catalyst of the present invention, wherein：The diameter of catalyst be more preferably 1.0mm~
The slice of 1.8mm.
The present invention also provides a kind of preparation methods of coking naphtha desilicification catalyst, are above-mentioned coking naphtha desiliconizations
The preparation method of catalyst, includes the following steps：
(1) titanium-containing compound is added in alumina powder, contains lanthanum compound, and graphene adds extrusion aid after mixing
And adhesive, it is uniformly mixed, extruded moulding, is freeze-dried again, carrier is made after roasting；
(2) it is made into maceration extract with the compound containing main active metal, carrier obtained is subjected to incipient impregnation, freezing
It is dry, coking naphtha desilicification catalyst is made after roasting.
The preparation method of coking naphtha desilicification catalyst of the present invention, wherein：Carrier obtained by step (1)
In, on the basis of carrier gross mass, by weight percentage, TiO2Content is preferably 1~10wt%, La2O3Content is preferably 1
~10wt%, graphene content are preferably 0.01~5wt%, remaining is Al2O3。
The preparation method of coking naphtha desilicification catalyst of the present invention, wherein：The titanium-containing compound is preferably
One or more of titanium oxide, metatitanic acid, titanium trichloride, titanium tetrachloride, tetrabutyl titanate and iso-butyl titanate；Chemical combination containing lanthanum
Object is preferably one or more of lanthanum nitrate, lanthanum carbonate, lanthanum chloride and lanthanum acetate.
The preparation method of coking naphtha desilicification catalyst of the present invention, wherein：The extrusion aid be preferably starch,
One or more of sesbania powder, polyvinyl alcohol, methylcellulose and polyethylene glycol.
The preparation method of coking naphtha desilicification catalyst of the present invention, wherein：Described adhesive be preferably nitric acid,
One or more of citric acid, ethanedioic acid and tartaric acid.
The preparation method of coking naphtha desilicification catalyst of the present invention, wherein：When step (2) medium volume impregnation
Between preferably 0.5~5 hour；Roasting condition is preferably in step (2)：It is roasted 2~6 hours at 450-600 DEG C.
The present invention can be with details are as follows：
Coking naphtha desilicification catalyst of the present invention is using Ni, Mo as active metal, Al2O3-TiO2-La2O3Graphene is compound
Oxide is carrier.Silicon trap for coker naphtha specific surface area is 250~500m2/ g, hole hold 0.5~0.8m2/g。
Coking naphtha desilicification catalyst of the present invention, based on the weight percent of catalyst, NiO contents in active component
For 0.5~2.5%, MoO3Content is 5.0~10.0%.
Al used in coking naphtha desilicification catalyst of the present invention2O3-TiO2-La2O3Graphene carrier, by weight hundred
Divide than meter TiO2Content is 1~10%, La2O3Content is 1%~10%, and graphene content is 0.01~5%, remaining is Al2O3。
Coking naphtha desilicification catalyst preparation process of the present invention is as follows：It is 1~10% that content is added in alumina powder
Titanium-containing compound (with TiO2Meter), content be 1%~10% containing lanthanum compound (with La2O3Meter), content is 0.01~5%
Graphene, add appropriate extrusion aid and adhesive after mixing, be uniformly mixed again.Extruded moulding, shape can be items
Shape, cloverleaf pattern, graininess or tooth are spherical.After freeze-drying, roasts and carrier is made.It is made into the compound containing active metal
Maceration extract.Carrier obtained is subjected to incipient impregnation, coking naphtha desilicification catalyst is made in freeze-drying after roasting.
Above-mentioned titanium-containing compound can be different for titanium oxide, metatitanic acid, titanium trichloride, titanium tetrachloride, tetrabutyl titanate, metatitanic acid
Or mixtures thereof butyl ester can be or mixtures thereof lanthanum nitrate, lanthanum carbonate, lanthanum chloride, lanthanum acetate containing lanthanum compound, and graphene can
Think or mixtures thereof graphene oxide, graphene.
Above-mentioned extrusion aid can be starch, sesbania powder, polyvinyl alcohol, methylcellulose, one kind in polyethylene glycol or several
Kind, it is subject to each component total weight, additive amount is 1%~5%, preferably 2%~4%.
Above-mentioned adhesive can be one or more of nitric acid, citric acid, ethanedioic acid, tartaric acid, with each component gross weight
Subject to amount, additive amount is 1%~5%, preferably 2%~4%.
The carrier impregnation time is 0.5~5 hour, preferably 1~3 hour in the present invention.It is dry that impregnated carrier carries out freezing
Dry, carrier roasts 2~6 hours, preferably 3~5 hours at 550 DEG C, and coking naphtha desilicification catalyst is made.
Coking naphtha desilicification catalyst of the present invention can be used for the removing of organosilicon in coking naphtha.Reaction condition is anti-
It is 220~350 DEG C to answer temperature, and hydrogen partial pressure is 1.0~6.0MPa, hydrogen to oil volume ratio 100:1~500:1, volume space velocity be 0.5~
3.0h-1。
Beneficial effects of the present invention：
The present invention provides a kind of preparation method of coking naphtha desilicification catalyst, passes through TiO2、La2O3With graphene tune
Become the acidity of alumina support, weakens the interaction of carrier and active component, be prepared for bigger serface, high desiliconization activity is urged
Agent.
Specific implementation mode
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, gives 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.
Aluminium oxide used in the present invention is commercially available boehmite.
Titanium-containing compound used in the present invention containing lanthanum compound, graphene is commercially available.
The catalyst of the present invention can be used before the main refining agent of coking naphtha, play the role of the main refining agent of protection.
The following examples will be further described a kind of coking naphtha desilicification catalyst provided by the invention,
But it is not thereby limiting the invention.
Embodiment 1
200g boehmites are taken, tetrabutyl titanate 1.4g is added, and (weight is with TiO2Meter), lanthanum nitrate 1.4g (weight with
La2O3Meter), graphene 0.14g, be uniformly mixed.1.6g sesbania powders are added, are uniformly mixed, nitric acid containing 0.8g, 0.8g lemons is added dropwise
The aqueous solution kneading of acid, extrusion is at the cylinder bar shaped of 1.5mm, and freeze-drying, then 550 DEG C of roasting 4h, are made carrier.Nitre is used again
Catalyst A is made in the maceration extract incipient impregnation that sour nickel, ammonium molybdate are prepared, freeze-drying, 450 DEG C of roasting 6h.
Embodiment 2
200g boehmites are taken, metatitanic acid 10g is added, and (weight is with TiO2Meter), (weight is with La by lanthanum nitrate 10g2O3Meter),
Graphene 1g is uniformly mixed.8g sesbania powders are added, are uniformly mixed, the aqueous solution kneading of nitric acid containing 4g, 4g citric acids is added dropwise, squeeze
Item is at the cloverleaf pattern of 1.5mm, and freeze-drying, then 550 DEG C of roasting 4h, are made carrier.Nickel nitrate, ammonium molybdate is used to prepare again
Catalyst B is made in maceration extract incipient impregnation, freeze-drying, 550 DEG C of roasting 4h.
Embodiment 3
200g boehmites are taken, tetrabutyl titanate 10g is added, and (weight is with TiO2Meter), (weight is with La by lanthanum nitrate 10g2O3
Meter), graphene 1g, be uniformly mixed.8g sesbania powders are added, are uniformly mixed, it is mixed that nitric acid containing 4g, the aqueous solution of 4g citric acids is added dropwise
It pinches, extrusion is at the cloverleaf pattern of 1.5mm, and freeze-drying, then 550 DEG C of roasting 4h, are made carrier.Nickel nitrate, ammonium molybdate are used again
Catalyst C is made in the maceration extract incipient impregnation of preparation, freeze-drying, 550 DEG C of roasting 4h.
Embodiment 4
200g boehmites are taken, tetrabutyl titanate 18.7g is added, and (weight is with TiO2Meter), lanthanum nitrate 18.7g (weight with
La2O3Meter), graphene 9.3g, be uniformly mixed.9.8g sesbania powders are added, are uniformly mixed, nitric acid containing 4.9g, 4.9g citric acids is added dropwise
Aqueous solution kneading, extrusion is spherical at the tooth of 1.5mm, freeze-drying, and then 550 DEG C of roasting 4h, are made carrier.Nitric acid is used again
Catalyst D is made in the maceration extract incipient impregnation that nickel, ammonium molybdate are prepared, freeze-drying, 600 DEG C of roasting 2h.
Comparative example 1
A kind of routine coking naphtha desiliconization agent E, hydrogenation active metals are molybdenum, nickel.This catalyst using aluminium oxide as carrier,
The co-impregnated solution dipping prepared with nickel nitrate and ammonium molybdate, 100 DEG C~120 DEG C dry 4h, 500 DEG C~600 DEG C roast 4h and are made.
The physicochemical properties of 1 catalyst of table
Embodiment 5
This example introduces the micro anti-evaluation result of above-mentioned catalyst.
The catalytic amount that micro anti-evaluation uses is 5g, and the xylene solution to contain cyclosiloxane (in terms of silicon 10 μ g/g) is to comment
Valence raw material, carries out desiliconization performance comparison test, and reaction condition is 300 DEG C, hydrogen partial pressure 4.0MPa of reaction temperature, hydrogen to oil volume ratio
500:1, volume space velocity 2.0h-1.The micro anti-evaluation of catalyst the results are shown in Table 2.
Table 2 is micro- instead to add hydrogen evaluation result
As can be seen from Table 2, A, B, C, D catalyst desiliconization activity are greatly increased than reference agent E.The present invention
Coking naphtha desilicification catalyst has the characteristics that large specific surface area, active metal utilization rate are high, and desiliconization activity is significantly improved,
It has a good application prospect.
Claims (13)
1. a kind of coking naphtha desilicification catalyst, including carrier and main active metal, main active metal are carried on carrier,
It is characterized in that：
With Ni, Mo for main active metal, Al2O3-TiO2-La2O3Graphene composite oxides are carrier；
The specific surface area of catalyst is 250~500m2/ g, hole hold 0.5~0.8mL/g.
2. coking naphtha desilicification catalyst according to claim 1, it is characterised in that：In terms of oxide, main activity gold
Belong to the 5.5~12.5wt% for accounting for catalyst gross mass.
3. coking naphtha desilicification catalyst according to claim 1, it is characterised in that：By the weight percent of catalyst
Meter, NiO contents are 0.5~2.5wt%, MoO3Content is 5.0~10.0wt%.
4. coking naphtha desilicification catalyst according to claim 1, it is characterised in that：On the basis of carrier gross mass,
By weight percentage, TiO2Content is 1~10wt%, La2O3Content be 1~10wt%, graphene content be 0.01~
5wt%, remaining is Al2O3。
5. coking naphtha desilicification catalyst according to claim 1, it is characterised in that：The shape of catalyst be sheet,
Spherical shape, cylindrical bars, irregular strip, graininess or tooth are spherical.
6. coking naphtha desilicification catalyst according to claim 1, it is characterised in that：A diameter of 0.8mm of catalyst
The slice of~2.0mm or thick item more than 2.5mm.
7. coking naphtha desilicification catalyst according to claim 6, it is characterised in that：A diameter of 1.0mm of catalyst
The slice of~1.8mm.
8. a kind of preparation method of coking naphtha desilicification catalyst is claim 1~7 any one of them coking stone brain
The preparation method of oily desilicification catalyst, includes the following steps：
(1) titanium-containing compound is added in alumina powder, contains lanthanum compound, and graphene adds extrusion aid and glues after mixing
Mixture is uniformly mixed again, extruded moulding, and carrier is made in freeze-drying after roasting；
(2) it is made into maceration extract with the compound containing main active metal, carrier obtained is subjected to incipient impregnation, freezing is dry
It is dry, coking naphtha desilicification catalyst is made after roasting.
9. the preparation method of coking naphtha desilicification catalyst according to claim 8, it is characterised in that：Step (1) institute
In carrier obtained, on the basis of carrier gross mass, by weight percentage, TiO2Content is 1~10wt%, La2O3Content is
1~10wt%, graphene content are 0.01~5wt%, remaining is Al2O3。
10. the preparation method of coking naphtha desilicification catalyst according to claim 8, which is characterized in that the titaniferous
Compound is one or more of titanium oxide, metatitanic acid, titanium trichloride, titanium tetrachloride, tetrabutyl titanate and iso-butyl titanate；
It is one or more of lanthanum nitrate, lanthanum carbonate, lanthanum chloride and lanthanum acetate containing lanthanum compound.
11. the preparation method of coking naphtha desilicification catalyst according to claim 8, which is characterized in that it is described help it is crowded
Agent is one or more of starch, sesbania powder, polyvinyl alcohol, methylcellulose and polyethylene glycol.
12. the preparation method of coking naphtha desilicification catalyst according to claim 8, which is characterized in that the bonding
Agent is one or more of nitric acid, citric acid, ethanedioic acid and tartaric acid.
13. the preparation method of coking naphtha desilicification catalyst according to claim 8, which is characterized in that in step (2)
The incipient impregnation time is 0.5~5 hour；Roasting condition is in step (2)：It is roasted 2~6 hours at 450-600 DEG C.
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