CN108246302A - A kind of catalytic gasoline faces hydrogen Hydrodearsenic Catalyst and its preparation method and application - Google Patents
A kind of catalytic gasoline faces hydrogen Hydrodearsenic Catalyst and its preparation method and application Download PDFInfo
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- CN108246302A CN108246302A CN201611238963.0A CN201611238963A CN108246302A CN 108246302 A CN108246302 A CN 108246302A CN 201611238963 A CN201611238963 A CN 201611238963A CN 108246302 A CN108246302 A CN 108246302A
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- hydrodearsenic catalyst
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- 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
- B01J23/883—Molybdenum and nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract
The present invention relates to a kind of catalytic gasolines to face hydrogen Hydrodearsenic Catalyst and its preparation method and application, and Hydrodearsenic Catalyst composition is：The NiO of 7~20wt%, the MoO of 2.5~4.9wt%3, 0~15wt% TiO2, remaining is Al2O3.The preparation method comprises the steps of：The mixture of aluminium oxide or aluminium oxide and titanium oxide with sesbania powder is uniformly mixed, adds in organic polymer pore creating material, binding agent and deionized water, kneading, extruded moulding are dry, and dearsenification agent carrier is made in high-temperature heat treatment；Dearsenification agent carrier is subjected to hydro-thermal process reaming, Hydrodearsenic Catalyst modified support is made；Active component nickel salt and molybdenum salt are dissolved in one or more of citric acid, ammonium hydroxide and deionized water, is made into stable two-part reactive metal complex solution, then impregnates Hydrodearsenic Catalyst modified support with it, Hydrodearsenic Catalyst finished product is made.The Hydrodearsenic Catalyst is for the higher catalytic gasoline dearsenification of olefin(e) centent, and appearance carbon ability is strong, and dearsenification activity is high (more than 90%), and dearsenification is selectively good (more than 99%), does not cause alkene saturation, no loss of octane number.
Description
Technical field
The present invention relates to a kind of gasoline Hydrodearsenic Catalyst and preparation method thereof, more particularly to a kind of for catalytic gasoline dearsenification
In particular Hydrodearsenic Catalyst with abundant mesopore is a kind of tool for being used for catalytic gasoline or being catalyzed heavy petrol raw material dearsenification
Have abundant mesopore faces hydrogen Hydrodearsenic Catalyst, does not cause alkene saturation and loss of octane number in gasoline during dearsenification.
Background technology
Hydrogen addition technology is one of main method of China's gasoline cleaning, and Petrochemical Enterprises generally reduce vapour using hydrogen addition technology
Sulfur content in oil.And the arsenide in feedstock oil is the toxic object of hydrogenation process, minimal amount of arsenide will make
Permanent poisoning and deactivation occurs for hydrogenation catalyst, and the shortening device long-term operation period brings larger shadow to refinery's economic benefit
It rings.In order to keep the activity of hydrogenation catalyst and stability, extend device service cycle, it is desirable that feedstock oil arsenic content ≯ 20ppb.
And China's catalytic gasoline arsenic content generally differs between 30 to hundreds of ppb, is both needed to before fraction containing arsenic is processed carry out raw material pre-
Dearsenification is handled.
There are mainly three types of the pre- arsenic removing methods industrially used at present：Absorption method, oxidizing process and hydrogenation method.And hydrogenation method by
It is received more and more attention in holding the features such as arsenic amount is big, and dearsenification effect is good, and the cycle of operation is long.
Chinese patent CN1040452C discloses a kind of arsenic removing method, and this method uses hydro-dearsenic catalyst, reaction pressure
Power is 1-8MPa, and temperature is controlled at 300-450 DEG C, and reaction solution air speed is 1-8h-1, hydrogen-oil ratio is 60-500, can drop arsenic content
Down to below 5ppb.This method carries out Hydrodearsenic Catalyst exploitation for the naphtha based on alkane, does not refer to that dearsenification causes in the process
Alkene saturated conditions, but since reaction temperature is higher, olefin saturation is easily occurred for catalytic gasoline dearsenification and causes octane
Value loss.
Chinese patent CN 1095749A disclose a kind of hydrocarbon dearsenicating catalyst, and an a kind of diaspore content is more than 65 heavy %
Aluminium hydroxide and aperture more than 100nm aluminium hydroxide press (0.2~5)：1 weight ratio is mixed, is molded, roasting obtains
γ-Al2O3After the carrier impregnation nickel salt and ammonium hydroxide are prepared maceration extract, Hydrodearsenic Catalyst is made through drying, roasting in carrier.This Hydrodearsenic Catalyst
Higher (the Ni of nickel content：12~40 heavy %), preparation process is complicated, and dearsenification reaction temperature is higher (280 DEG C), is unfavorable for being used for
Catalytic gasoline dearsenification is reacted, and olefin saturation easily occurs and causes loss of octane number.
A kind of hydro-dearsenic catalyst is disclosed in CN1212992A, the carrier of catalyst contains the titanium dioxide of 60-100%
The aluminium oxide of titanium and 0-40wt%, specific surface area 80-200m2/ g, Kong Rongwei 0.3-0.5ml/g, most probable pore size areThe Hydrodearsenic Catalyst low temperature active is high, suitable for the dearsenification of ethylene project cracking stock oil.But since Kong Rong is compared with little Rong charcoals
Energy force difference, is unfavorable for device long-period stable operation.
A kind of catalyst for removing arsentic from liquid hydrocarbon is disclosed in CN96100735.4.The Hydrodearsenic Catalyst preparation method is by nickeliferous work
Property component is loaded in the γ-Al being distributed with double hole channel2O3On carrier, aperture can several radiuses beThe dearsenification
For catalyst using preceding hydrogen reducing being needed to handle, product arsenic content is less than 5ppb.Compagnie Francise des Petroles patent CN1030440A and
CN1021340A be using nickel oxide be supported on macropore hold, the γ-Al of Large ratio surface2O3Hydrodearsenic Catalyst on carrier, Hydrodearsenic Catalyst use
Before be required to be handled with hydrogen reducing, at least 50% nickel becomes reduction-state.It is and big absolutely in catalyst used in hydrogenation process
Part is oxidation state or sulphided state, and the complexity to go into operation will be dramatically increased when reduction-state Hydrodearsenic Catalyst is used together, and
Higher sulfide can poison the activity of reduction-state Hydrodearsenic Catalyst in feedstock oil.
A kind of two-step method for the olefin gasolines desulfurization containing arsenic is disclosed in CN101445748A.Involved in this method
The desulfurating and dearsenic agent of arsenic is captured using aluminium oxide and silica-alumina as carrier, with 0.3~2.1%MoO3, 10~28%
NiO is active component, and acid additive P is 0.1~10%.The Hydrodearsenic Catalyst be Mo-Ni-P systems, MoO3Content is relatively low, reaction temperature
It spends higher, most preferably at 260-340 DEG C, is unfavorable for selective dearsenification reaction.
A kind of supported dearsenic agent and preparation method thereof is disclosed in CN105536689.The dearsenification agent carrier is porous nothing
Sizing aluminum-spinel, active component are CuO and/or NiO.The coal synthesis gas depth that the Hydrodearsenic Catalyst is suitable for coal chemical technology takes off
Arsenic, volume space velocity 3000-5000h-1, steam-to-gas ratio is 1.0~1.8, and reaction condition is not suitable for gasoline dearsenification.Meanwhile copper system
Hydrodearsenic Catalyst can be reduced to metallic copper in high temperature and while having reducibility gas and generate detonable acetylene copper, not be suitable for containing
Olefin catalytic gasoline dearsenification.
A kind of hydrocarbon dearsenicating catalyst and preparation method thereof is disclosed in CN1258719A.The Hydrodearsenic Catalyst is using titanium oxide as load
Body, 5~25%MoO3, 2~15%NiO be active component, acid additive P be 0.2~4%.Hydrodearsenic Catalyst MoO3Content is higher,
Alkene saturation easily is brought, mainly for the treatment of the straight-run naphtha of not olefin-containing, and for the higher catalytic gasoline of olefin(e) centent
Have no description.
In conclusion above-mentioned technology is mainly used in naphtha based on alkane, often pushes up gasoline and light diesel fuel is gentle
In the dearsenification reaction of state hydrocarbon, and not directed specifically in the high catalytic gasoline of gasoline, especially olefin(e) centent, existing literature data
The situation of change of alkene and octane number while only embodying its dearsenification activity, and do not embody hydro-dearsenic.Meanwhile prior art master
Will based on single Ni, Mo-Ni-P system, pore size distribution feature and oxide content height on dearsenification activity and selectivity influence compared with
Greatly.Since catalytic gasoline component contains certain alkadienes and a large amount of alkene, easily occur when face hydrogen dearsenification plus hydrogen saturation is anti-
Loss of octane number should be caused, while duct is blocked with diene polymerization green coke, accelerates Hydrodearsenic Catalyst carbon distribution inactivation, restricts dearsenification
Agent dearsenification activity and service life, it is particularly important that macropore of the exploitation with abundant mesopore faces hydrogen Hydrodearsenic Catalyst.
Invention content
The purpose of the present invention is to provide a kind of catalytic gasolines to face hydrogen Hydrodearsenic Catalyst and its preparation method and application.
To achieve the above object, a kind of catalytic gasoline of present invention offer faces hydrogen Hydrodearsenic Catalyst, and the Hydrodearsenic Catalyst is by following components
Composition：The NiO of 7~20wt%, the MoO of 2.5~4.9wt%3, 0~15wt% TiO2, remaining is Al2O3。
Further, the Hydrodearsenic Catalyst is composed of the following components：The NiO of 8~18wt%, the MoO of 3~4.8wt%3, 0~
The TiO of 15wt%2, remaining is Al2O3, wherein, nickel molybdenum atom ratio is 3~11.
Further, TiO2And Al2O3Specific surface be 100~200m20.5~1.0ml/g of/g, Kong Rongwei, average pore size
For 15~30nm, hole of the pore-size distribution more than 10nm accounts for more than 90%, and side pressure strength is more than 15N/cm.
Further, TiO2And Al2O3Specific surface be 120~180m20.6~0.9ml/g of/g, Kong Rongwei, average pore size
For 15~25nm, pore-size distribution is that the hole of 10~50nm accounts for more than 90%.
To achieve the above object, the present invention also provides the preparation method that a kind of catalytic gasoline faces hydrogen Hydrodearsenic Catalyst, comprising following
Step：
The mixture of aluminium oxide or aluminium oxide and titanium oxide is uniformly mixed by step 1 with sesbania powder, adds in organic polymer
Object pore creating material, binding agent and deionized water, kneading, extruded moulding, 100~150 DEG C of dry 3~6h, 650~1000 DEG C high warm
3~6h is handled, dearsenification agent carrier is made；
Step 2, by dearsenification agent carrier carry out hydro-thermal process reaming, 400~700 DEG C for the treatment of temperature, mass space velocity 0.5~
1.5h-1, 1~10h is handled, Hydrodearsenic Catalyst modified support is made；
Step 3 dissolves active component nickel salt and molybdenum salt in one or more of citric acid, ammonium hydroxide and deionized water,
Stable two-part reactive metal complex solution is made into, then with two-part reactive metal complex solution incipient impregnation Hydrodearsenic Catalyst
Modified support, dipping 12~for 24 hours, through 100~150 DEG C of dry 3~6h, after 400~600 DEG C of 3~6h of roasting, obtained Hydrodearsenic Catalyst into
Product.
Further, organic polymer pore creating material is one kind or several in polyethylene glycol, polyvinyl alcohol and polyacrylamide
Kind, grain size is 200 μm of -2mm, and pore creating material accounts for Hydrodearsenic Catalyst carrier quality and compares 3-5%.
Further, binding agent is one or more of nitric acid, acetic acid and oxalic acid.
Further, nickel salt is the one or several kinds in basic nickel carbonate, nickel nitrate and nickel acetate, and molybdenum salt is ammonium molybdate
One or both of with molybdenum oxide.
Further, the composition of Hydrodearsenic Catalyst finished product is the MoO of the NiO of 7~20wt%, 2.5~4.9wt%3, 0~
The TiO of 15wt%2, remaining is Al2O3。
Further, the composition of Hydrodearsenic Catalyst finished product is the MoO of the NiO of 8~18wt%, 3~4.8wt%3, 0~15wt%
TiO2, remaining is Al2O3, wherein, nickel molybdenum atom ratio is 3~11.
Further, the specific surface of dearsenification agent carrier is 100~200m2/ g, hole hold 0.5~1.0ml/g, average pore size 15
~30nm, hole of the pore-size distribution more than 10nm account for more than 90%, and side pressure strength is more than 15N/cm.
Further, the specific surface of dearsenification agent carrier is 120~180m2/ g, hole hold 0.6~0.9ml/g, average pore size 15
~25nm, pore-size distribution are that the hole of 10~50nm accounts for more than 90%.
To achieve the above object, the present invention also provides the application that a kind of catalytic gasoline faces hydrogen Hydrodearsenic Catalyst, the Hydrodearsenic Catalyst exists
Vulcanized before use, conditions of vulcanization is：230-320 DEG C of curing temperature, vulcanization time 12-36h, hydrogen-oil ratio 100:1-
300:1 and pressure 1.0-3.0MPa.
Further, the reaction condition applied to catalytic gasoline dearsenification is：1.0~3.0MPa of Hydrogen Vapor Pressure, temperature 180~
260 DEG C, 5.0~15.0h of air speed-1, hydrogen-oil ratio 100:1~500:1.
The beneficial effects of the invention are as follows：
(1) Hydrodearsenic Catalyst with abundant mesopore provided by the invention using preceding without hydrogen reducing, is urged with existing plus hydrogen
Agent is used cooperatively, and technique is flexible, and start-up process is simple, and operability is strong, is suitble to existing gasoline hydrogenation quality upgrading work
Skill flow；
(2) pore creating material that according to raw material needs, can add different-grain diameter carries out carrier preparation, big, golden with average pore size
Belong to the features such as content is low, appearance charcoal ability is strong.
(3) suitable for catalytic gasoline or the hydro-dearsenic reaction of catalysis heavy petrol, arsenic-removing rate reaches more than 90%, alkene damage
It loses percent by volume and is less than or equal to 0.2%, dearsenification selectively reaches more than 99%, and loss of octane number is less than or equal to 0.1.
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.
A kind of catalytic gasoline faces hydrogen Hydrodearsenic Catalyst, and the Hydrodearsenic Catalyst is composed of the following components：The NiO of 7~20wt%, 2.5~
The MoO of 4.9wt%3, 0~15wt% TiO2, remaining is Al2O3。
Further, the Hydrodearsenic Catalyst is composed of the following components：The NiO of 8~18wt%, the MoO of 3~4.8wt%3, 0~
The TiO of 15wt%2, remaining is Al2O3, wherein, nickel molybdenum atom ratio is 3~11.
Further, TiO2And Al2O3Specific surface be 100~200m20.5~1.0ml/g of/g, Kong Rongwei, average pore size
For 15~30nm, hole of the pore-size distribution more than 10nm accounts for more than 90%, and side pressure strength is more than 15N/cm.
Further, TiO2And Al2O3Specific surface be 120~180m20.6~0.9ml/g of/g, Kong Rongwei, average pore size
For 15~25nm, pore-size distribution is that the hole of 10~50nm accounts for more than 90%.
A kind of catalytic gasoline faces the preparation method of hydrogen Hydrodearsenic Catalyst, comprises the steps of：
The mixture of aluminium oxide or aluminium oxide and titanium oxide is uniformly mixed by step 1 with sesbania powder, adds in organic polymer
Object pore creating material, binding agent and deionized water, kneading, extruded moulding, 100~150 DEG C of dry 3~6h, 650~1000 DEG C high warm
3~6h is handled, dearsenification agent carrier is made；
Step 2, by dearsenification agent carrier carry out hydro-thermal process reaming, 400~700 DEG C for the treatment of temperature, mass space velocity 0.5~
1.5h-1, 1~10h is handled, Hydrodearsenic Catalyst modified support is made；
Step 3 dissolves active component nickel salt and molybdenum salt in one or more of citric acid, ammonium hydroxide and deionized water,
Stable two-part reactive metal complex solution is made into, then with two-part reactive metal complex solution incipient impregnation Hydrodearsenic Catalyst
Modified support, dipping 12~for 24 hours, through 100~150 DEG C of dry 3~6h, after 400~600 DEG C of 3~6h of roasting, obtained Hydrodearsenic Catalyst into
Product.
Further, organic polymer pore creating material is one kind or several in polyethylene glycol, polyvinyl alcohol and polyacrylamide
Kind, grain size is 200 μm of -2mm, and pore creating material accounts for Hydrodearsenic Catalyst carrier quality and compares 3-5%.
Further, binding agent is one or more of nitric acid, acetic acid and oxalic acid.
Further, nickel salt is the one or several kinds in basic nickel carbonate, nickel nitrate and nickel acetate, and molybdenum salt is ammonium molybdate
One or both of with molybdenum oxide.
A kind of catalytic gasoline faces the application of hydrogen Hydrodearsenic Catalyst, and the Hydrodearsenic Catalyst is vulcanized before use, conditions of vulcanization
For：230-320 DEG C of curing temperature, vulcanization time 12-36h, hydrogen-oil ratio 100:1-300:1 and pressure 1.0-3.0MPa.
Further, the reaction condition applied to catalytic gasoline dearsenification is：1.0~3.0MPa of Hydrogen Vapor Pressure, temperature 180~
260 DEG C, 5.0~15.0h of air speed-1, hydrogen-oil ratio 100:1~500:1.
Embodiment 1：
It weighs boehmite 100g, adds in 3.0g sesbania powders, add 3% aqueous solution of nitric acid, through kneading, extrusion,
Dry 4h at 120 DEG C, then through 750 DEG C of roasting 4h, dearsenification agent carrier A is made (property is shown in Table 1).It weighs 20.0g carriers and is put into burning
In cup, add in excessive deionized water and stand 3h, then remove carrier surface excessive moisture, compare carrier before impregnation quality w1 and leaching
Carrier quality w2 variations calculate its water absorption rate after stain, and then according to incipient impregnation method, activity is carried out according to carrier water absorption rate
The preparation of component maceration extract.60ml ammonium hydroxide is weighed first, then adds in 30g nickel acetates, 3.7g ammonium molybdates are stirred to dissolving, finally
Constant volume is carried out with ammonium hydroxide.Carrier is impregnated using incipient impregnation method, catalyst carrier is made to fully absorb active component
Maceration extract after then placing 12h, carries out 120 DEG C of dry 4h to catalyst, 4h is roasted at 600 DEG C, Hydrodearsenic Catalyst sample is made
T1。
Embodiment 2：
It weighs containing 3%TiO2Boehmite 100g, add in 3.0g sesbania powders, 5g grain sizes are 200 μm of organic polymer
Object pore creating material polyvinyl alcohol, adds 3% aqueous solution of nitric acid, through kneading, extrusion, the dry 4h at 120 DEG C, then through 750 DEG C of roastings
4h is burnt, then carries out hydro-thermal process, treatment conditions are：600 DEG C of reaction temperature, mass space velocity 0.5h-1, 4h, carrier B (property is made
1) matter is shown in Table.Metal active constituent dipping method, nickel salt, the impregnation increment of molybdenum salt and drying, roasting condition are made with embodiment 1
Hydrodearsenic Catalyst sample T2.
Embodiment 3：
Boehmite 100g is weighed, adds in 3.0g sesbania powders, 3g grain sizes are the organic polymer pore creating material polyethylene of 2mm
Alcohol adds 3% aqueous solution of nitric acid, through kneading, extrusion, the dry 4h at 120 DEG C, then through 750 DEG C of roasting 4h, hydrothermal treatment
Hydrodearsenic Catalyst modified support C is made in (with embodiment 2) (property is shown in Table 1).The leaching of metal active constituent dipping method, nickel salt, molybdenum salt
Hydrodearsenic Catalyst sample T3 is made with embodiment 1 in stain amount and drying, roasting condition.
Embodiment 4：
Boehmite 100g is weighed, adds in 3.0g sesbania powders, 4g grain sizes are 800 μm of the poly- second of organic polymer pore creating material
Enol adds 5% acetum, through kneading, extrusion, the dry 4h at 120 DEG C, then through 750 DEG C of roasting 4h, Hydrodearsenic Catalyst is made
Carrier；Modified support D is made in hydrothermal treatment (with embodiment 2) (property is shown in Table 1).Metal active constituent dipping method, nickel salt,
Hydrodearsenic Catalyst sample T4 is made with embodiment 1 in the impregnation increment of molybdenum salt and drying, roasting condition.
Embodiment 5：
Boehmite 100g is weighed, adds in 3.0g sesbania powders, 3.5g grain sizes are that 600 μm of organic polymer pore creating material gathers
Vinyl alcohol adds 3% acetum, 2% citric acid, 2% ammonium hydroxide, through kneading, extrusion, the dry 4h at 120 DEG C, then pass through
750 DEG C of roasting 4h, are made dearsenification agent carrier；Modified support E is made in hydrothermal treatment (with embodiment 2) (property is shown in Table 1).Metal
Hydrodearsenic Catalyst sample T5 is made with embodiment 1 in activity component impregnation method, nickel salt, the impregnation increment of molybdenum salt and drying, roasting condition.
Embodiment 6：
100g catalyst modification carriers are prepared according to the support preparation method in embodiment 5, then carry out activearm sub-dip
The preparation of stain liquid, preparation method are same as Example 5.60ml ammonium hydroxide is weighed first, then adds in 25.8g nickel acetates, 3.4g molybdenums
Sour ammonium is stirred to dissolving, finally carries out constant volume with ammonium hydroxide.Metal active constituent dipping method and drying, the same embodiment of roasting condition
5, catalyst sample T6 is made.
Embodiment 7：
100g catalyst carriers are prepared according to the support preparation method in embodiment 5, then carry out activity component impregnation liquid
Preparation, preparation method is same as Example 5.55ml ammonium hydroxide is weighed first, then adds in 50g nickel acetates, 5.5g ammonium molybdates stir
It mixes to dissolving, finally carries out constant volume with ammonium hydroxide.Metal active constituent dipping method and drying, roasting condition are made with embodiment 5
Catalyst sample T7.
Embodiment 8：
100g catalyst modification carriers are prepared according to the support preparation method in embodiment 5, then carry out activearm sub-dip
The preparation of stain liquid, in two steps dipping prepare catalyst.55ml deionized waters are weighed first, then add in 38g nickel nitrates, 3g molybdic acids
Ammonium is stirred to dissolving, finally carries out constant volume with deionized water.Metal active constituent dipping method and drying, roasting condition are the same as implementation
Single-steeping catalyst sample is made in example 5；Double-steeping is carried out to above-mentioned catalyst sample, 45ml ammonium hydroxide is weighed, then adds in
44g nickel acetates, 3.9g ammonium molybdates are stirred to dissolving, finally carry out constant volume with ammonium hydroxide.Metal active constituent dipping method and drying,
Catalyst sample T8 is made with embodiment 5 in roasting condition.
Embodiment 9：
This example demonstrates that applications of the catalyst T1-T8 prepared using the present invention in gasoline hydrogenation dearsenification.
Hydrodearsenic Catalyst evaluation procedure：Hydrodearsenic Catalyst with abundant mesopore is fitted into fixed bed reactors.First to dearsenification
Agent carries out presulfurization, and sulfurized oil is containing 3wt%CS2Direct steaming gasoline, sulfide stress 2.0MPa, hydrogen to oil volume ratio 300：1,230
DEG C, 320 DEG C of difference vulcanizing treatment about 8h.It after vulcanization, is reacted into feedstock oil, raw material oil nature is shown in Table 3, reaction condition
It is shown in Table 4.Each embodiment operating procedure condition is identical (being shown in Table 4), with the industrial Hydrodearsenic Catalyst performance comparison applied to naphtha dearsenification
It the results are shown in Table 5.
1 carrier physico-chemical property of table
2 Hydrodearsenic Catalyst physico-chemical property of table
3 catalytic gasoline property of table
4 operating procedure condition of table
5 embodiment data of table
The result shows that：With T1-T8 Hydrodearsenic Catalysts with handling catalytic gasoline for the industrial Hydrodearsenic Catalyst of naphtha dearsenification, in table 4
Under listed process conditions, gasoline arsenic content 20ng/g is down to by 200ng/g hereinafter, and alkene substantially without saturation, octane number is not
It reduces, dearsenification is selective up to more than 99%.Compared with the industrial Hydrodearsenic Catalyst for naphtha dearsenification, the dearsenification that provides in the present invention
Agent is particularly suited for the catalytic gasoline raw material rich in olefin component and carries out hydro-dearsenic.
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 (14)
1. a kind of catalytic gasoline faces hydrogen Hydrodearsenic Catalyst, which is characterized in that the Hydrodearsenic Catalyst is composed of the following components：7~20wt%'s
The MoO of NiO, 2.5~4.9wt%3, 0~15wt% TiO2, remaining is Al2O3。
2. catalytic gasoline according to claim 1 faces hydrogen Hydrodearsenic Catalyst, which is characterized in that the Hydrodearsenic Catalyst is by following components group
Into：The NiO of 8~18wt%, the MoO of 3~4.8wt%3, 0~15wt% TiO2, remaining is Al2O3, wherein, nickel molybdenum atom ratio
It is 3~11.
3. catalytic gasoline according to claim 1 faces hydrogen Hydrodearsenic Catalyst, which is characterized in that TiO2And Al2O3Specific surface be
100~200m20.5~1.0ml/g of/g, Kong Rongwei, average pore size are 15~30nm, and hole of the pore-size distribution more than 10nm accounts for 90%
More than, side pressure strength is more than 15N/cm.
4. catalytic gasoline according to claim 1 faces hydrogen Hydrodearsenic Catalyst, which is characterized in that TiO2And Al2O3Specific surface be
120~180m20.6~0.9ml/g of/g, Kong Rongwei, average pore size are 15~25nm, and pore-size distribution is that the hole of 10~50nm accounts for
More than 90%.
5. catalytic gasoline according to any one of claims 1 to 4 faces the preparation method of hydrogen Hydrodearsenic Catalyst, which is characterized in that includes
Following steps：
The mixture of aluminium oxide or aluminium oxide and titanium oxide is uniformly mixed by step 1 with sesbania powder, is added in organic polymer and is made
Hole agent, binding agent and deionized water, kneading, extruded moulding, 100~150 DEG C of dry 3~6h, 650~1000 DEG C of high-temperature heat treatments
Dearsenification agent carrier is made in 3~6h；
Dearsenification agent carrier is carried out hydro-thermal process reaming, 400~700 DEG C for the treatment of temperature, 0.5~1.5h of mass space velocity by step 2-1, 1~10h is handled, Hydrodearsenic Catalyst modified support is made；
Step 3 dissolves active component nickel salt and molybdenum salt in one or more of citric acid, ammonium hydroxide and deionized water, is made into
Then stable two-part reactive metal complex solution is modified with two-part reactive metal complex solution incipient impregnation Hydrodearsenic Catalyst
Carrier, dipping 12~for 24 hours, through 100~150 DEG C of dry 3~6h, after 400~600 DEG C roast 3~6h, Hydrodearsenic Catalyst finished product is made.
6. catalytic gasoline according to claim 5 faces the preparation method of hydrogen Hydrodearsenic Catalyst, which is characterized in that organic polymer is made
Hole agent is one or more of polyethylene glycol, polyvinyl alcohol and polyacrylamide, and grain size is 200 μm of -2mm, and pore creating material accounts for de-
Arsenical carrier quality compares 3-5%.
7. catalytic gasoline according to claim 5 faces the preparation method of hydrogen Hydrodearsenic Catalyst, which is characterized in that binding agent is nitre
One or more of acid, acetic acid and oxalic acid.
8. catalytic gasoline according to claim 5 faces the preparation method of hydrogen Hydrodearsenic Catalyst, which is characterized in that nickel salt is alkali formula carbon
One or several kinds in sour nickel, nickel nitrate and nickel acetate, molybdenum salt are one or both of ammonium molybdate and molybdenum oxide.
9. catalytic gasoline according to claim 5 faces the preparation method of hydrogen Hydrodearsenic Catalyst, which is characterized in that Hydrodearsenic Catalyst finished product
Form the MoO of NiO for 7~20wt%, 2.5~4.9wt%3, 0~15wt% TiO2, remaining is Al2O3。
10. catalytic gasoline according to claim 5 faces the preparation method of hydrogen Hydrodearsenic Catalyst, which is characterized in that Hydrodearsenic Catalyst finished product
Composition be the NiO of 8~18wt%, the MoO of 3~4.8wt%3, 0~15wt% TiO2, remaining is Al2O3, wherein, nickel molybdenum
Atomic ratio is 3~11.
11. catalytic gasoline according to claim 5 faces the preparation method of hydrogen Hydrodearsenic Catalyst, which is characterized in that dearsenification agent carrier
Specific surface be 100~200m2/ g, hole hold 0.5~1.0ml/g, 15~30nm of average pore size, and pore-size distribution is more than the hole of 10nm
More than 90% is accounted for, side pressure strength is more than 15N/cm.
12. catalytic gasoline according to claim 5 faces the preparation method of hydrogen Hydrodearsenic Catalyst, which is characterized in that dearsenification agent carrier
Specific surface be 120~180m2/ g, hole hold 0.6~0.9ml/g, 15~25nm of average pore size, and pore-size distribution is 10~50nm's
Hole accounts for more than 90%.
13. catalytic gasoline according to any one of claims 1 to 4 faces the application of hydrogen Hydrodearsenic Catalyst, which is characterized in that is needed before use
Vulcanized, conditions of vulcanization is：230-320 DEG C of curing temperature, vulcanization time 12-36h, hydrogen-oil ratio 100:1-300:1 and pressure
Power 1.0-3.0MPa.
14. catalytic gasoline according to claim 13 faces the application of hydrogen Hydrodearsenic Catalyst, which is characterized in that applied to catalytic gasoline
The reaction condition of dearsenification is：1.0~3.0MPa of Hydrogen Vapor Pressure, 180~260 DEG C of temperature, 5.0~15.0h of air speed-1, hydrogen-oil ratio
100:1~500:1.
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| CN113262795A (en) * | 2021-05-28 | 2021-08-17 | 中国海洋石油集团有限公司 | Catalyst for hydrodearsenicating and desulfurizing naphtha and preparation method thereof |
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