CN109266387A - FCC gasoline selective hydrogenation processing method - Google Patents

FCC gasoline selective hydrogenation processing method Download PDF

Info

Publication number
CN109266387A
CN109266387A CN201811193176.8A CN201811193176A CN109266387A CN 109266387 A CN109266387 A CN 109266387A CN 201811193176 A CN201811193176 A CN 201811193176A CN 109266387 A CN109266387 A CN 109266387A
Authority
CN
China
Prior art keywords
catalyst
carrier
nickel
selective hydrogenation
content
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811193176.8A
Other languages
Chinese (zh)
Other versions
CN109266387B (en
Inventor
黄凤玉
黄志祥
张丽娥
张素珍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Lin Yajuan
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201811193176.8A priority Critical patent/CN109266387B/en
Publication of CN109266387A publication Critical patent/CN109266387A/en
Application granted granted Critical
Publication of CN109266387B publication Critical patent/CN109266387B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • B01J23/8873—Zinc, cadmium or mercury
    • 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
    • C10G45/32—Selective hydrogenation of the diolefin or acetylene compounds
    • C10G45/34—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used
    • C10G45/36—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/38—Selective hydrogenation of the diolefin or acetylene compounds characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum or tungsten metals, or compounds thereof
    • 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
    • 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
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The present invention relates to a kind of FCC gasoline selective hydrogenation processing methods, and using fixed bed reactors, catalyst includes silicaalumina carrier and the metal active constituent nickel, molybdenum, zinc and the lithium that are carried on carrier；Reaction process condition are as follows: 100-230 DEG C of reaction temperature, reaction pressure 1.1-5.5MPa, volume space velocity 1.2-5.0h‑1, hydrogen to oil volume ratio 7-28:1.The method of the present invention is used for FCC gasoline selective hydrogenation and removing mercaptan sulfur and alkadienes.

Description

FCC gasoline selective hydrogenation processing method
Technical field
The present invention relates to a kind of FCC gasoline selective hydrogenation processing methods.
Background technique
Increasingly strict with environmental regulation, countries in the world, which propose the quality of refinery products, to be increasingly stringenter It is required that being especially increasingly stringenter to the limitation of refinery products sulfur content.Vulcanize owner contained in oils It to be mercaptan (RSH), thioether (RSR) etc., wherein influence of the mercaptan to product quality is maximum, not only has foul smell, very strong Corrosivity also will affect the stability of product.
US6692635B2 discloses a kind of method for producing the low gasoline of sulfur content, uses new removal of mercaptans in this method Technology.Full distillation gasoline raw material is passed through a selective hydrogenation reactor by the technology, make alkene in mercaptan and gasoline or Alkadienes occurs etherification reaction and generates high boiling sulfur-containing compound, then in a fractionating column to selective hydrogenation product into Row fractionation is obtained without mercaptan and the lower light gasoline fraction of total sulfur content and the higher heavy naphtha of sulfur content.The technology The characteristics of be to realize that mercaptan is removed from effective in light gasoline fraction and to heavy petrol by the addition reaction of mercaptan and alkadienes The transfer of fraction, while the removing of mercaptan and the reduction of light petrol total sulfur content are realized, overcoming traditional Merox technique cannot Deep desulfuration and there are problems that alkaline residue discharge.
CN1229838A discloses a kind of method for transformation of hydrocarbon ils, and this method is to be catalyzed feedstock oil and a kind of hydrofinishing Agent removal of mercaptans under the process conditions of hydro-sweetening, the Hydrobon catalyst contain the oxygen of load on the alumina support Change tungsten (molybdenum), nickel oxide and cobalt oxide, wherein the content of tungsten oxide (molybdenum) is 4~10wt%, the content of nickel oxide is 1~ 5wt%, the content of cobalt oxide are 0.01~0.1wt%, the total atom number and nickel of nickel and cobalt, cobalt, tungsten (molybdenum) total atom number it Than being 0.3~0.9.CN102451694A discloses a kind of hydrodesulfurization alcohol catalyst and its preparation method and application.The catalysis Agent is using aluminium oxide or silicon-containing alumina as carrier, using phosphorus as adjuvant component, using copper and zinc as active component, is with catalyst quality Benchmark, the content of auxiliary agent phosphorus are 0.5~3.0wt%, and the content of zinc oxide is 3~15wt%, the content of copper oxide is 5~ 30wt%.Because the catalyst has very strong hydrogenation activity, for when handling full fraction FCC gasoline, mercaptans content to be by 38 μ g/ G is reduced to 3 μ g/g, while olefin(e) centent is also reduced to 20v% by 25v%, and RON loss is up to 1.3 units. CN00136870.2 provides a kind of for removing the selectively mercaptan-eliminating catalyst of mercaptan sulfur and its preparation side in aviation fuel Method.Catalyst includes following component: 1. molybdenum oxide 7-20 according to parts by weight；2. cobalt oxide 0.1-5；3. nickel oxide 0-5 is 4. Silica 0-10；5. phosphorus or boron or fluorine 0-4；6. aluminium oxide 0-40；7. titanium dioxide 60-100.The preparation side of catalyst Method is to impregnate catalyst carrier maceration extract 1-2 hours, then dry at 100-130 DEG C；Finally at 400-550 DEG C Obtain catalyst within roasting 2-6 hours.This catalyst has good removal effect and preferable to the mercaptan sulfur in jet fuel Low temperature active.CN201210393263.4 is related to a kind of preparation method and application of new type gasoline removal of mercaptans adsorbent.The gasoline The preparation method of removal of mercaptans adsorbent is old the following steps are included: solvent, metal ion presoma, mesoporous material are uniformly mixed Change, organic ligand is added, carries out hydrothermal crystallizing processing；Then, the product of hydrothermal crystallizing processing filtered, washed, dried, Obtain zeolite imidazole class framework material/mesoporous material compound；To the zeolite imidazole class framework material/mesoporous material compound Compression molding, crushing and screening are carried out, demercaptaning for gasoline adsorbent is obtained.Zeolite imidazole class framework material/Jie provided by the invention In Porous materials compound, the specific surface area of zeolite imidazole class framework material is high, while being in high dispersion state on mesoporous material, has It solves to effect and spreads limitation caused by reunion.The solvent is in deionized water, methanol, ethyl alcohol and n,N-Dimethylformamide One or more of combinations；The metal ion is Zn2+、Cu2+And Co2+One or more of combination. CN200910082945.1 is related to a kind of selective hydrogenation catalyst for catalytic cracking gasoline and preparation method thereof.Catalyst of the present invention By Al2O3-TiO2Composite oxide carrier and reactive metal oxides composition, based on the weight percent to catalyst, activity NiO content in metal oxide is 10~20w%, MoO3Content is 5~12w%；Wherein carrier Al2O3-TiO2Oxide TiO2∶Al2O3Weight ratio be 0.01~1: 1.Catalyst of the present invention low temperature (100~200 DEG C), low pressure (1~3.0MPa), Under conditions of low hydrogen/gasoline ratio (hydrogen to oil volume ratio 5: 1~100: 1), catalytically cracked gasoline is handled, very high de- diolefin is shown And removal of mercaptans activity, selectivity and stability.CN200910187903.4 discloses a kind of hydrodesulfurization alcohol catalyst and its system Preparation Method and application.The catalyst with HZSM-5 molecular sieve be main carrier component, using copper and zinc as active component.Active component In terms of oxide weight, the content of copper oxide is 5%~27%, and the content of zinc oxide is 3%~15%, using saturation total immersion skill Art preparation.Catalyst of the invention is suitable for carrying out the reaction of selective hydrodesulfurization alcohol to light-end products, has removal of mercaptans activity The features such as height, low hydrogenation of olefins activity, and liquid yield height, loss of octane number are seldom after reaction.CN201610187374.8 is mentioned For the light hydrocarbons mercaptan-eliminating catalyst and its preparation method regulated and controled based on aluminium oxide crystal face, which is with hydro-thermal of the present invention Gama-alumina after processing regulation is carrier, using nickel and molybdenum as active metal.Light hydrocarbons mercaptan-eliminating catalyst of the present invention For high activity and high-selectivity catalyst, it can be used for being catalyzed mercaptan and alkadienes effect in light hydrocarbons and generate macromolecular vulcanization Object, and it can be also catalyzed the selective hydrogenation saturation of diolefin, compared with existing catalyst, catalyst provided by the present invention is de- Thiol active is high, diolefin hydrogenation selectivity is high, and active component is not lost, not easy in inactivation, thus the catalyst runs period is long. The present invention relates to the catalyst of mercaptan sulfur in a kind of low temperature removing catalytically cracked gasoline and its preparation sides by CN201310251750.1 Method belongs to field of gasoline desulfurization.A kind of low temperature removes the catalyst of mercaptan sulfur in catalytically cracked gasoline, with aluminium oxide or nanometer HZSM-5 molecular sieve and alumina composite solid acid are carrier, based on the mass percent for accounting for catalyst gross mass, comprising: oxidation Zinc 5%~20%, iron oxide 5%~15%, lanthana 0.5%~5%, phosphorous oxide 0.5%~5%.Catalyst of the invention Suitable for carrying out the reaction of low temperature hydrodesulfurisation alcohol to catalytically cracked gasoline, have removal of mercaptans activity high, olefins hydrogenation activity Low, liquid receives the features such as high and octane number does not lose substantially.
The composition and comparision contents of above-mentioned catalyst are more, and preparation process is complicated, and produce catalyst prod matter in enormous quantities Amount is difficult to control.
The prior art changes support chemistry composition and type, and addition coagent mainly to promote catalyst performance Energy.For the defect for overcoming the above prior art, a kind of completely new hydrodesulfurization alcohol catalyst is found, removal of mercaptans activity is high, diene The problem of hydrocarbon hydrogenation selectivity is high, and stability is good, and the low characteristic of loss of octane number is those skilled in the art's urgent need to resolve it One.
Summary of the invention
The present invention provides FCC gasoline selective hydrogenation processing method, removes mercaptan and alkadienes, and side reaction is few, and activity is high, Loss of octane number is low.
The present invention provides a kind of FCC gasoline selective hydrogenation processing method, and using fixed bed reactors, catalyst includes oxygen SiClx-alumina support and metal active constituent nickel, molybdenum, zinc and the lithium being carried on carrier, on the basis of the weight of catalyst, The content of nickel oxide is 2%~15wt%, and the content of molybdenum oxide is 2~18wt%, and the content of zinc oxide is 0.1~5wt%, oxygen The content for changing lithium is 0.1~2.5wt%；Silicaalumina carrier content is 65-85wt%, in silicaalumina carrier Silica comprising 0.1~12wt%, the nickel doped lanthanum ferrite of 0.1~10wt%, the potassium of 0.1~2.5wt%, carrier is mesoporous to be accounted for The 3~75% of total hole, macropore accounts for the 1.5~60% of total hole, micropore, mesoporous, macropore uneven distribution in carrier；Reaction process item Part are as follows: 100-230 DEG C of reaction temperature, reaction pressure 1.1-5.5MPa, volume space velocity 1.2-5.0h-1, hydrogen to oil volume ratio 7-28:1.
Preferably, reaction process condition are as follows: 100-200 DEG C of reaction temperature, reaction pressure 1.1-4.0MPa, volume space velocity 1.5-3.5h-1, hydrogen to oil volume ratio 7-22:1.
Preferably, include following components on the basis of the total weight of catalyst: the content of nickel oxide is 4%~15wt%, The content of molybdenum oxide is 5~16wt%.Carrier is mesoporous to account for the 3~65% of total hole, and macropore accounts for the 1.5~50% of total hole.
In the preparation method of catalyst of the present invention, the compound of nickel used and molybdenum can be prior art disclosed A kind of what compound suitable for catalyst processed, such as nickel nitrate, nickel sulfate, nickel acetate, ammonium molybdate, molybdenum oxide.
The silicaalumina carrier the preparation method is as follows: boehmite and sesbania powder are added to kneader In be uniformly mixed, inorganic acid solution and organic polymer is added, mediates uniformly, then adds nickel doped lanthanum ferrite, mixing is equal It is even to obtain alumina precursor, it is spare；Silicon source is added in the acid solution of organic polymer and boehmite is uniformly mixed, obtains Silicon source-boehmite-organic polymer mixture, the organic polymer of unit content is more quasi- than silicon source-in alumina precursor The high 2 times or more of content of organic polymer in boehmite-organic polymer mixture (brief note silicon-aluminium-organic admixture), Then by silicon source -- boehmite-organic polymer mixture is mixed with alumina precursor, adds potassium resource, through extrusion, Molding, dry, roasting, obtain silicaalumina carrier.The silicon source is silica gel, sodium metasilicate or silicon powder.Silicon-aluminium-is organic Aluminium oxide accounts for 1~35wt% of aluminium oxide in carrier in object mixture.
The preparation process of above-mentioned silicaalumina carrier, the organic polymer are polyvinyl alcohol, polyacrylic acid, gather One or more of sodium acrylate, polyethylene glycol, polyacrylate.
Preferably, in above-mentioned silicaalumina carrier nickel doped lanthanum ferrite be 0.1~12wt%, more preferable 0.2~ 8wt%, nickel accounts for 0.1~8wt% of cadmium ferrite in nickel doped lanthanum ferrite.
The preparation method of the nickel doped lanthanum ferrite: citric acid is dissolved in stirring and dissolving in deionized water, then by nitric acid Lanthanum and ferric nitrate are added in citric acid, and Sodium Polyacrylate, polyacrylate or polyacrylic acid, polyacrylic acid is added in stirring and dissolving The additional amount of sodium, polyacrylate or polyacrylic acid is the 0.1~10wt%, preferably 0.1~8.0wt% of nickel doped lanthanum ferrite. Nickel compound containing is added, stirs, obtains finished product through drying, roasting, grinding.The nickel compound containing includes nickel nitrate, acetic acid Nickel etc..
Solution containing active component can be impregnated, be sprayed to using the methods of dipping, spraying by the preparation method of catalyst On silica-carrier, then catalyst is dried, roasts and obtains the catalyst.Such as it can make according to the following steps Standby catalyst: preparing solution oxide impregnation silicon-alumina support containing active component and adjuvant component, dries through 110~160 DEG C 3~9 hours, 400~650 DEG C roasted 4~9 hours, finally obtained catalyst prod.
Compared to cadmium ferrite, nickel doped lanthanum ferrite is added in silicaalumina carrier, effectively improves anti-arsenic, sulfur resistance, The nickel molybdenum zinc system catalyst of preparation effectively improves diolefin hydrogenation selectivity and removal of mercaptans activity, the system of silicaalumina carrier During standby, the organic polymer of unit content is than organic polymer in silicon-aluminium-organic admixture in alumina precursor The high 2 times or more of content, can not only improve the pore structure of carrier, make carrier micropore, mesoporous, macropore uneven distribution, effectively press down Active olefin polymerization processed and monoolefine saturation (hydrogen is not added to the alkene in raw material), improve catalyst anticol mass-energy power, improve The stability and service life of catalyst, are conducive to device long-term operation；And carrier surface is promoted to produce more work Property position load centre, improve catalyst HDS alcohol activity.
Mercaptan-eliminating catalyst of the present invention be suitable for removing liquefied petroleum gas, FCC gasoline, catalytic cracking gasoline and/or Mercaptan and/or alkadienes in coker gasoline；Catalyst choice is good.The octane number RON of gasoline loses 0.3~0.4 point or so. Catalyst desulfurizing alcohol activity is high, and diolefin hydrogenation selectivity is high, and alkene saturation factor is low, and loss of octane number is low.The FCC gasoline choosing Selecting property method of hydrotreating removes mercaptan sulfur and alkadienes, adaptable to different material.
Specific embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as to limit of the invention System.
Prepare primary raw material source used in catalyst: source chemicals used in the present invention are commercial product.
Embodiment 1
1, nickel doped lanthanum ferrite is prepared
Under stirring condition, 2.51mol lanthanum nitrate is dissolved in 120mL water, citric acid stirring and dissolving is added；It adds Then 4.79mol ferric nitrate adds 190g Sodium Polyacrylate, add the aqueous solution of the nickel nitrate containing 42g, continue to stir 30min, drying, roasting, grinding obtain nickel doped lanthanum ferrite.
2, silicaalumina carrier is prepared
5g Sodium Polyacrylate is dissolved in nitric acid, is added 38g silicon powder and 50g boehmite powder, is stirred evenly, obtain To silicon powder-boehmite-Sodium Polyacrylate mixture (brief note silicon-aluminium-organic admixture), take 1/8 amount spare, It is spare that citric acid is added in 4.5g nickel doped lanthanum ferrite.300g boehmite powder and 25.0g sesbania powder are added to kneading In machine, nitric acid is added, adds 40.2g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, adds above-mentioned silicon powder-poly- third Olefin(e) acid sodium mixture is mediated uniformly, nickel doped lanthanum ferrite and 2.5g potassium nitrate is then added, is uniformly mixed, by kneading-extrusion It is shaped to clover shape.8 hours dry at 120 DEG C, 650 DEG C roast 6 hours, obtain the silica-of nickeliferous doped lanthanum ferrite The carrier 1 of aluminium oxide.The mesoporous of carrier accounts for the 55.4% of total hole, and macropore accounts for the 28.6% of total hole.
3, catalyst is prepared
Nickeliferous, zinc, lithium, molybdenum solution impregnated carrier 1 are configured, 6 hours dry at 140 DEG C, 560 DEG C roast 5 hours, obtain Catalyst 1.The composition of catalyst is shown in Table 1.
Embodiment 2
260g Sodium Polyacrylate, silicaalumina carrier is only added with embodiment 1 in the preparation of nickel doped lanthanum ferrite Preparation with embodiment 1, in silicaalumina carrier include 4.4wt% silica, the nickel doped lanthanum ferrite of 5.7wt%, The potassium of 1.6wt%, carrier is mesoporous to account for the 64.2% of total hole, and macropore accounts for the 25.6% of total hole.Unit content in alumina precursor Sodium Polyacrylate it is 3 times higher than the content of Sodium Polyacrylate in silicon source-organic polymer mixture.The preparation method of catalyst 2 With embodiment 1.
Embodiment 3
220g polyacrylic acid is only added with embodiment 1 in the preparation of nickel doped lanthanum ferrite, silicaalumina carrier Preparation includes the silica of 8.4wt% with embodiment 1, in silicaalumina carrier, the nickel doped lanthanum ferrite of 2.6wt%, The potassium of 0.8wt%, carrier is mesoporous to account for the 54.6% of total hole, and macropore accounts for the 33.5% of total hole.Unit content in alumina precursor Polyacrylic acid it is 3.3 times higher than the content of polyacrylic acid in silicon source-organic polymer mixture.The preparation method of catalyst 3 is same Embodiment 1.
Embodiment 4
280g Sodium Polyacrylate, silicaalumina carrier is only added with embodiment 1 in the preparation of nickel doped lanthanum ferrite Preparation with embodiment 1, in silicaalumina carrier include 8.4wt% silica, the nickel doped lanthanum ferrite of 2.6wt%, The potassium of 2.5wt%, carrier is mesoporous to account for the 49.3% of total hole, and macropore accounts for the 39.4% of total hole.Unit content in alumina precursor Polyacrylate it is 3.3 times higher than the content of polyacrylate in silicon source-organic polymer mixture.The preparation method of catalyst With embodiment 1.
Comparative example 1
1, cadmium ferrite is prepared
Under stirring condition, 2.51mol lanthanum nitrate is dissolved in 120mL water, citric acid stirring and dissolving is added；It adds Then 4.79mol ferric nitrate adds 190g Sodium Polyacrylate, stir 30min, drying, roasting, grinding obtain nickel doping iron Sour lanthanum.
2, silicaalumina carrier is prepared
5g Sodium Polyacrylate is dissolved in nitric acid, is added 38g silicon powder and 50g boehmite powder, is stirred evenly, obtain To silicon powder-boehmite-Sodium Polyacrylate mixture (brief note silicon-aluminium-organic admixture), take 1/8 amount spare, It is spare that citric acid is added in 4.5g cadmium ferrite.300g boehmite powder and 25.0g sesbania powder are added in kneader, added Enter nitric acid, add 40.2g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, it is mixed to add above-mentioned silicon powder-Sodium Polyacrylate Object is closed, mediates uniformly, cadmium ferrite and 2.5g potassium nitrate is then added, be uniformly mixed, is cloverleaf pattern by kneading-extruded moulding Shape.8 hours dry at 120 DEG C, 650 DEG C roast 6 hours, obtain the carrier 1-1 of the silica-alumina of Fe-laden acid lanthanum.
3, comparative catalyst 1 is prepared
Nickeliferous, zinc, lithium, molybdenum solution impregnated carrier 1-1 are configured, 6 hours dry at 140 DEG C, 560 DEG C roast 5 hours, obtain To comparative catalyst 1.
Comparative example 2
1, nickel doped lanthanum ferrite is prepared
Under stirring condition, 2.51mol lanthanum nitrate is dissolved in 120mL water, citric acid stirring and dissolving is added；It adds Then 4.79mol ferric nitrate adds 190g Sodium Polyacrylate, add the aqueous solution of the nickel nitrate containing 42g, continue to stir 30min, drying, roasting, grinding obtain nickel doped lanthanum ferrite.
2, silicaalumina carrier is prepared
It is spare that citric acid is added in 4.5g nickel doped lanthanum ferrite, 350g boehmite powder and 25.0g sesbania powder are added Enter into kneader, nitric acid is added, adds 40.7g Sodium Polyacrylate nitric acid solution, and be uniformly mixed, it is micro- to add 4.8g silicon Powder is mediated uniformly, nickel doped lanthanum ferrite and 2.5g potassium nitrate is then added, is uniformly mixed, and is three leaves by kneading-extruded moulding Careless shape.8 hours dry at 120 DEG C, 650 DEG C roast 6 hours, obtain the load of the silica-alumina of nickeliferous doped lanthanum ferrite Body 1-2.
3, comparative catalyst 2 is prepared
Nickeliferous, zinc, lithium, molybdenum solution impregnated carrier 1-2 are configured, 6 hours dry at 140 DEG C, 560 DEG C roast 5 hours, obtain To comparative catalyst 2.
Catalyst 1-4 and comparative example Catalyst packing are subjected to evaluation catalyst reaction into fixed bed reactors respectively Performance.Presulfurization, sulfide stress 3.2MPa, hydrogen to oil volume ratio 300, vulcanization oil volume sky are carried out to catalyst with sulfurized oil Speed is 3.5h-1, vulcanization program is respectively in 240 DEG C, 280 DEG C of vulcanizing treatment 6h.After to vulcanizing treatment, it is switched to full fraction Then FCC gasoline replacement Treatment 6h is adjusted to reaction process condition, carry out removal of mercaptans and diene hydrocarbon reaction.FCC feedstock gasoline sulfur 487 μ g/g of content, mercaptan sulfur 42.8 μ g/g, arsenic content 31ppb, olefin(e) centent 35.4v%, RON 90.1.Reaction process item Part are as follows: 130 DEG C of temperature of reactor, volume space velocity 3.5h-1, hydrogen to oil volume ratio 16:1, reaction pressure 2.8MPa.After reacting about 60h Sampling analysis, reaction result are shown in Table 2.
1 embodiment of table/comparative example catalyst composition/wt%
Embodiment/comparative example Molybdenum oxide Nickel oxide Zinc oxide Lithia
Embodiment 1 13.6 10.9 2.4 0.1
Embodiment 2 15.7 9.8 1.6 0.2
Embodiment 3 11.2 13.7 0.8 0.1
Embodiment 4 9.5 11.6 2.8 0.2
Comparative example 1 13.6 10.9 2.4 0.1
Comparative example 2 13.6 10.9 2.4 0.1
2 embodiments of table/comparative example reaction 60h result
The result of 3 embodiment of table reaction 600h
Embodiment Mercaptan sulfur content/μ g/g Olefin(e) centent v% Loss of octane number Yield of gasoline wt%；
Embodiment 1 0.3 41.9 0.3 98.2
Embodiment 2 0.4 42.0 0.3 98.3
Reaction result shows that olefin(e) centent is basically unchanged, and reaction loss of octane number is 0.3~0.4, catalyst diolefin hydrogenation Selectivity and removal of mercaptans activity are high, and anti-arsenic, sulfur resistance are good, and loss of octane number is low.Comparative example catalyst activity is low, and catalyst can Can plastic even coking and activity decline.
Stability test is carried out to catalyst, reaction operation 600h reaction result is shown in Table 3, and olefin(e) centent is basically unchanged, and is urged It is good that agent is not easy plastic even coking and deactivation, stability.
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 (10)

1. a kind of FCC gasoline selective hydrogenation processing method, which is characterized in that use fixed bed reactors, catalyst includes oxygen SiClx-alumina support and metal active constituent nickel, molybdenum, zinc and the lithium being carried on carrier, on the basis of the weight of catalyst, The content of nickel oxide is 2%~15wt%, and the content of molybdenum oxide is 2~18wt%, and the content of zinc oxide is 0.1~5wt%, oxygen The content for changing lithium is 0.1~2.5wt%；Silicaalumina carrier content is 65-85wt%, in silicaalumina carrier Silica comprising 0.1~12wt%, the nickel doped lanthanum ferrite of 0.1~10wt%, the potassium of 0.1~2.5wt%, carrier is mesoporous to be accounted for The 3~75% of total hole, macropore accounts for the 1.5~60% of total hole, micropore, mesoporous, macropore uneven distribution in carrier；Reaction process item Part are as follows: 100-230 DEG C of reaction temperature, reaction pressure 1.1-5.5MPa, volume space velocity 1.2-5.0h-1, hydrogen to oil volume ratio 7-28:1.
2. FCC gasoline selective hydrogenation processing method according to claim 1, which is characterized in that reaction process condition are as follows: 100-200 DEG C of reaction temperature, reaction pressure 1.1-4.0MPa, volume space velocity 1.5-3.5h-1, hydrogen to oil volume ratio 7-22:1.
3. FCC gasoline selective hydrogenation processing method according to claim 1, which is characterized in that the carrier is mesoporous to be accounted for The 3~65% of total hole, macropore accounts for the 1.5~50% of total hole；The catalyst includes following components on the basis of total weight: oxidation The content of nickel is 4%~15wt%, and the content of molybdenum oxide is 5~16wt%.
4. FCC gasoline selective hydrogenation processing method according to claim 1, which is characterized in that the silica-oxidation Being uniformly mixed the preparation method is as follows: boehmite and sesbania powder are added in kneader for alumina supporter, it is molten to be added inorganic acid Liquid and organic polymer are mediated uniformly, then add nickel doped lanthanum ferrite, are uniformly mixed and obtain alumina precursor, spare； Silicon source is added in the acid solution of organic polymer and boehmite is uniformly mixed, obtains silicon source-boehmite-organic polymer Object mixture, the organic polymer of unit content is than silicon source-boehmite-organic polymer mixture in alumina precursor The high 2 times or more of the content of middle organic polymer, then by silicon source -- before boehmite-organic polymer mixture and aluminium oxide Body mixing is driven, potassium resource is added, through extrusion, molding, drying, roasting, obtains silicaalumina carrier.
5. FCC gasoline selective hydrogenation processing method according to claim 4, which is characterized in that the silicon source be silica gel, Sodium metasilicate or silicon powder, in silicon source-boehmite-organic polymer mixture aluminium oxide account for aluminium oxide in carrier 1~ 35wt%.
6. FCC gasoline selective hydrogenation processing method according to claim 4, which is characterized in that the organic polymer For one or more of polyvinyl alcohol, polyacrylic acid, Sodium Polyacrylate, polyethylene glycol, polyacrylate.
7. FCC gasoline selective hydrogenation processing method according to claim 4, which is characterized in that the silica-oxidation Nickel doped lanthanum ferrite is 0.1~12wt% in alumina supporter.
8. described in any item FCC gasoline selective hydrogenation processing methods according to claim 1~7, which is characterized in that the nickel The preparation method of doped lanthanum ferrite: being dissolved in stirring and dissolving in deionized water for citric acid, and then lanthanum nitrate and ferric nitrate are added In citric acid, stirring and dissolving is added Sodium Polyacrylate, polyacrylate or polyacrylic acid, Sodium Polyacrylate, polyacrylate or The additional amount of polyacrylic acid is 0.1~10wt% of nickel doped lanthanum ferrite, adds nickel compound containing, is stirred, through drying, roasting It burns, grinding obtains finished product.
9. described in any item FCC gasoline selective hydrogenation processing methods according to claim 1~7, which is characterized in that described to urge The preparation method of agent includes the following steps: that the maceration extract dipping of active component will be contained, sprays on carrier, then to catalyst It is dried, roasts and obtain the catalyst.
10. FCC gasoline selective hydrogenation processing method according to claim 9, which is characterized in that the system of the catalyst Standby process is as follows: nickeliferous, zinc, lithium, molybdenum solution oxide impregnation silicon-alumina support are configured, it is small through 110~160 DEG C of drying 3~9 When, 400~650 DEG C roast 4~9 hours, finally obtain catalyst prod.
CN201811193176.8A 2018-10-14 2018-10-14 FCC gasoline selective hydrotreating method Active CN109266387B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811193176.8A CN109266387B (en) 2018-10-14 2018-10-14 FCC gasoline selective hydrotreating method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811193176.8A CN109266387B (en) 2018-10-14 2018-10-14 FCC gasoline selective hydrotreating method

Publications (2)

Publication Number Publication Date
CN109266387A true CN109266387A (en) 2019-01-25
CN109266387B CN109266387B (en) 2020-12-11

Family

ID=65197246

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811193176.8A Active CN109266387B (en) 2018-10-14 2018-10-14 FCC gasoline selective hydrotreating method

Country Status (1)

Country Link
CN (1) CN109266387B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3130830B1 (en) * 2021-12-17 2024-08-16 Ifp Energies Now Process for capturing mercaptans using a mesoporous capture mass
FR3130827B1 (en) * 2021-12-17 2024-08-16 Ifp Energies Now Process for capturing mercaptans using a capture mass having undergone a CO2 passivation step
FR3130829B1 (en) * 2021-12-17 2024-08-16 Ifp Energies Now Process for capturing mercaptans with temperature selection and specific Ni/NiO ratio
FR3130828B1 (en) * 2021-12-17 2024-08-16 Ifp Energies Now Process for capturing mercaptans using a macro and mesoporous capture mass

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885983A (en) * 2010-07-02 2010-11-17 中国石油大学(北京) Efficient coupling hydro-upgrading method for producing gasoline with ultra-low sulfur and high octane number
CN105642299A (en) * 2016-02-05 2016-06-08 常州大学 Nickel-doped lanthanum ferrite/clay nano-structure composite and preparation method and application thereof
CN106867576A (en) * 2017-03-17 2017-06-20 钦州学院 A kind of hydrodesulfurizationprocess process of gasoline
CN107754820A (en) * 2017-11-24 2018-03-06 福州大学 A kind of heavy oil floating bed hydrocracking catalyst and preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885983A (en) * 2010-07-02 2010-11-17 中国石油大学(北京) Efficient coupling hydro-upgrading method for producing gasoline with ultra-low sulfur and high octane number
CN105642299A (en) * 2016-02-05 2016-06-08 常州大学 Nickel-doped lanthanum ferrite/clay nano-structure composite and preparation method and application thereof
CN106867576A (en) * 2017-03-17 2017-06-20 钦州学院 A kind of hydrodesulfurizationprocess process of gasoline
CN107754820A (en) * 2017-11-24 2018-03-06 福州大学 A kind of heavy oil floating bed hydrocracking catalyst and preparation method

Also Published As

Publication number Publication date
CN109266387B (en) 2020-12-11

Similar Documents

Publication Publication Date Title
CN109266387A (en) FCC gasoline selective hydrogenation processing method
WO2017166046A1 (en) Light hydrocarbon sweetening catalyst on the basis of alumina crystal surface regulation and preparation method therefor
CN101619234B (en) Method for producing low sulfur gasoline by using light weight gasoline
CN101722014B (en) Hydrodesulfurization catalyst and preparation method and application thereof
CN101376835B (en) Gasoline hydrofinishing startup method and gasoline hydrofinishing operation method
CN102284300B (en) Inferior diesel oil hydrotreating catalyst and preparation method thereof
CN101724442B (en) Method for reducing octane number loss of gasoline deep hydrodesulphurization
CN109207188A (en) A kind of light FCC gasoline mercaptan etherification method
CN109207191A (en) A kind of method of demercaptaning for gasoline by catalyst cracking
CN109331830A (en) A kind of method of demercaptaning for gasoline
CN109370647A (en) A kind of catalytic gasoline selective method of hydrotreating
CN109370637A (en) A kind of method of FCC gasoline hydro-sweetening
CN103263945B (en) Reforming pre-hydrogenation catalyst with aromatization property and preparation method thereof
CN103468311B (en) A kind of method of producing low-sulphur oil
CN109395737A (en) One kind being used for FCC gasoline mercaptan etherification catalyst and preparation method
CN109261161A (en) A kind of catalyst and preparation method of FCC gasoline hydro-sweetening
CN109364966A (en) A kind of catalyst and preparation method of demercaptaning for gasoline
CN109331829A (en) A kind of method of light FCC gasoline hydro-sweetening
CN109331828A (en) A kind of catalyst and preparation method for demercaptaning for gasoline
CN109261160A (en) FCC gasoline selective hydrocatalyst and preparation method
CN109266386A (en) Light FCC gasoline selective hydrogenation processing method
CN109331827A (en) A kind of method of gasoline light fraction removal of mercaptans
CN103059964A (en) Method for producing ultra-low sulfur gasoline
CN102453532B (en) Method for producing low-sulfur gasoline
CN109201107A (en) FCC gasoline mercaptan etherification catalyst and preparation method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20201126

Address after: No.113, Dongtang, Yangxia village, Guhuai Town, Changle District, Fuzhou City, Fujian Province

Applicant after: Lin Yajuan

Address before: 362100 Qianbao 67, Qianhuang Town, Quanzhou City, Fujian Province

Applicant before: Huang Fengyu

GR01 Patent grant
GR01 Patent grant