CN106929091B - A kind of catalytic gasoline hydrogenation desulfurization method for modifying - Google Patents
A kind of catalytic gasoline hydrogenation desulfurization method for modifying Download PDFInfo
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- CN106929091B CN106929091B CN201511022173.4A CN201511022173A CN106929091B CN 106929091 B CN106929091 B CN 106929091B CN 201511022173 A CN201511022173 A CN 201511022173A CN 106929091 B CN106929091 B CN 106929091B
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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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates (SAPO compounds)
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Abstract
The present invention relates to a kind of catalytic gasoline hydrogenation desulfurization method for modifying, using fixed bed reactors；Used catalyst is the sulfur-carried hydrogenation catalyst of the stratified material containing zinc-aluminium, and on the basis of catalyst weight, the content of molecular sieve is 5-70wt%；Group vib tenor is calculated as 2-10wt% with oxide, and group VIII metal content is calculated as 1-5wt% with oxide, is 5-50% by the non-constant pH zinc-aluminium stratiform material content that alternately prepared by titration；Phosphorus content is calculated as 0-10wt% with oxide；Hydrodesulfurizationmodification modification process conditions are as follows: 170-350 DEG C of reaction temperature, reaction pressure 1.5-2.4MPa, volume space velocity 1.5-4.0h‑1, hydrogen to oil volume ratio 150-500:1.It is added to the zinc-aluminium stratified material with large specific surface area in catalyst, there is good hydrodesulfurization and Olefin decrease performance.
Description
Technical field
The present invention relates to a kind of catalytic gasoline hydrogenation desulfurization method for modifying, this method is suitable for catalytically cracked gasoline
In sulfide be hydrogenated into hydrogen sulfide, while converting high-octane rating hydro carbons for alkene orientation.
Background technique
For the catalytically cracked gasoline in China due to source complexity, change of properties is larger.For external gasoline,
General sulfur content is in 100-500mg/kg, and part material is also high-sulfur, high olefin feedstock, and sulfur content is in 500mg/kg or more, alkene
Hydrocarbon content is more than 40v%.Selective hydrodesulfurization technology inevitably will cause alkene portion when carrying out deep hydrodesulfurizationof
Divide saturation and reduce octane number, and is changed by the load sulfur type hydrodesulfurization of the compound preparation of hydrodesulfurization catalytic material and molecular sieve
Matter catalyst, which can reach hydrodesulfurization and convert antiknock component for alkene, reaches desulfurization, Olefin decrease, holding octane
The diversification purpose of value.
The composite material of zinc oxide and aluminium oxide is used for hydrodesulfurization field frequently as desulfurization catalyst material.The material at present
Common preparation method include infusion process, mechanical mixing, coprecipitation and peptisation.Wherein, since infusion process and machinery are mixed
Legal to use alumina material as predecessor, by adjusting the specific surface area of alumina material, both methods can be prepared
The composite material of high specific surface area, but due in composite material aluminium oxide and zinc oxide interaction it is weaker, used
It is easy to produce the loss of zinc oxide in journey, usually promotes the two to form spinelle using the method for high-temperature roasting to avoid aoxidizing
The loss of zinc；And coprecipitation and peptisation prepare zinc-aluminium precursor by precipitating or peptization using the compound containing aluminum and zinc,
Aluminum and zinc passes through the stronger interaction of reaction generation during the preparation process to be lost to avoid the zinc oxide in use process, but
Be peptisation prepare material specific surface area it is minimum, be restricted when using it as catalysis material.
US5525210 discloses a kind of method of FCC gasoline desulfurization, and main active component is to be carried on alumina support
On L acid, such as zinc oxide, used method is infusion process and coprecipitation, and wherein infusion process prepares material and roasts at 815 DEG C
Specific surface area 142m afterwards2/ g, coprecipitation prepare material specific surface area 74m after 704 DEG C of roastings2/g.Two methods maturing temperature
It is higher, it is relatively low to prepare zinc-aluminium material specific surface area.
CN200710045746.4 discloses a kind of assistant for calalytic cracking that can reduce content of sulfur in gasoline, which includes zinc
The composite oxides of aluminate and evenly dispersed zinc oxide and optionally at least one rare earth metal oxides, by
The mixture of zinc-aluminium bedded substance and optional rare earth hydrous oxide with hydrotalcite-like compound is fired and is made, chemistry
Formula is ZnAl2O4·(1-9)ZnO·(0-0.5)RE2O3；Preparation method is that sodium hydroxide and soluble inorganic sodium salt are added dropwise
Into the mixed solution of zinc salt, aluminium salt and rare earth ion, the pH value of solution is 8-11, in 500-1000 DEG C of roasting 1-4h.This is helped
It blends and is applied in catalytic cracking process with conventional FCC catalyst and/or active enhanced aid after agent molding, having reduces gasoline
Sulfur content function simultaneously has excellent hydrothermal stability.To obtain gahnite structure, which needs to roast in higher temperature
It burns, specific surface area is up to 120m after roasting2/g。
CN201210178395.5 discloses a kind of preparation method of nano zinc aluminum spinelle, and preparation method is by zinc salt
It is added to the water dissolution, silicon source is added, stir 10~30 minutes, expanding agent, stirring, at 20~100 DEG C 30~60 points of aging is added
Clock, dry, 500~1200 DEG C of roastings；Feed molar proportion is Zn: Al: water=1: 2: 16~35；It is with the quality of zinc oxide
100% calculates, and the additional amount of expanding agent is 0.5~30%；Expanding agent is sucrose, glycerine, ammonium carbonate, ammonium hydrogen carbonate, polyphenyl
One or more of vac emulsion, polyethylene glycol.The specific surface area of synthesized gahnite is from 60 to 300m2/g.It should
The zinc-aluminium that method feeds intake adds expanding agent with relatively low and preparation process, only obtains gahnite, does not include evenly dispersed
Zinc oxide.
CN201310625314.6 discloses the preparation side of the strong absorption of one kind, high visible degradation property catalysis material
Method, it is presoma that the present invention relates to a kind of with ternary houghite, the high-specific-surface mesoporous structure zinc obtained by high-temperature roasting
Aluminate and zinc oxide, nickel oxide nano composite photocatalyst material and preparation method thereof, the material are used for organic pollutant
Absorption and degradation.The present invention is raw material using zinc nitrate, nickel nitrate, aluminum nitrate, sodium carbonate and sodium hydroxid etc., is prepared respectively
It is mixed under 80 DEG C and magnetic agitation with constant flow pump at salting liquid and aqueous slkali；Reaction mixture is transferred to hydro-thermal reaction
In kettle, the hydro-thermal process 5-10h at 130-180 DEG C；It filters, wash, be drying to obtain presoma, forerunner is put into Muffle furnace
2-6 hours are roasted at 400-600 DEG C to get product, zinc, nickel, aluminium ion molar ratio are 1-3:1-3:1-3, and specific surface area is greater than
150m2/g.Need to carry out hydro-thermal process during this method synthesis of ternary houghite presoma, and handle the time compared with
It is long.
CN200310121344.X discloses a kind of preparation method of the Nano-class zinc oxide conductive powder body of adulterated al.The party
Method is by the soluble-salt of zinc and doped chemical aluminium, gallium, indium, yttrium, scandium, tin, germanium, the mixing salt solution of soluble-salt of silicon and heavy
Shallow lake agent is added drop-wise in water simultaneously, is generated altogether under conditions of controlling 40-75 DEG C of the temperature and pH value 7.0-7.5 of entire reaction system
Precipitating generates the zinc oxide precursor basic zinc carbonate of doping, by the roasting under the mixed atmosphere of hydrogen and argon gas, is made
The super fine zinc oxide conductive powder material of doping is obtained, but the material of this method preparation is to be applied to conductive material, doping
The addition mole of element is only the 0.1-10% of zinc and doped chemical integral molar quantity.
CN200510028233.3 discloses a kind of preparation method of high-performance sulfur transfer agent for catalytic cracking flue gas, this method with
Zinc, magnesium and aluminium are active component, using cerium and vanadium as auxiliary agent, under the conditions of 60-80 DEG C, pH value 8-10, by zinc salt, magnesium salts, aluminium salt
It is added drop-wise to the mixed solution of cerium salt in the mixed solution of sodium hydroxide and sodium carbonate, obtained coprecipitated product is in 400-600
DEG C roasting 6-8h, prepares zinc mangnesium-aluminium-cerium houghite by coprecipitation, zinc, magnesium, three kinds of metals of aluminium molar ratio be 1.0:
1.0-4.5:1.0-2.0, the sulfur transfer additive using material preparation have efficient SOxAbsorption and desorption performance and good machine
Tool intensity.
CN200910087590.5 discloses a kind of desulfurizing agent for reforming stock oil and preparation method thereof, method for preparing catalyst
It is related to blending method, eutectic method and coprecipitation, it is characterised in that its weight composition are as follows: ZnO:10%-40%, NiO:15%-
22%, Al2O3: 10%-17%, SiO2: 5%-22%, surplus are the impurity that can not exempt from.
CN201310089762.9 discloses a kind of nano-scale stratiform complex hydroxide and its fractional precipitation preparation side
Method is to use soluble-salt and the alkali of metal for raw material, distinguishes the metal ion for constituting LDH laminate by fractional precipitation reaction
Precipitating, and LDH is produced in second step precipitation process, specific surface area 140-280m2/g.Relative to coprecipitation, the invention
It is precipitated twice although using, the LDH material specific surface area of preparation is higher, but the invention reaction time is longer, implements
The reaction time provided in example was at 10 hours or more.
" synthesis of research-gahnite and its cracking desulfurization performance that reduce sulfur content of catalytic cracking gasoline auxiliary agent "
(author: Wang Peng；Sinopec Group, " petroleum journal (PETROLEUM PROCESSING) " 2 phases of volume 19 in 2003): disclose one
The preparation method of kind gahnite: sodium aluminate solution and zinc nitrate solution are pressed into m (Al2O3The ratio of)/m (ZnO)=9, point
It is not added drop-wise to identical rate in 40 DEG C of distilled water, adds 16% sodium hydroxide solution after mixing, adjusted molten
The pH value of liquid is 8.6, and the sediment of generation adds a small amount of sodium hydroxide solution after aging 15min, and adjusting pH value is 9.0.
Sediment is filtered, washed through 3 times or more repetitions, to remove Na+.Sediment is finally dried to 4h at 120 DEG C, then at 700
2h is roasted at DEG C.The specific surface area of sample is substantially all in 160m2/ g or so.
Therefore, it is necessary to develop the hydrodesulfurizationmodification modification technique that a kind of reaction condition is mild, adaptability to raw material is strong, make catalyst
Catalytically cracked gasoline raw material is handled under the operating condition of mitigation, obtains excellent hydro-upgrading effect.
Summary of the invention
The purpose of the present invention is to provide a kind of catalytic gasoline selective hydrodesulfurizationmodification modification method, this method is used
Load sulfur type catalyst including zinc-aluminium stratified material, suitable for catalytically cracked gasoline the selective hydrogenation of sulfide and alkene to
The orientation of high-octane rating hydro carbons converts.
The technical problem to be solved by the present invention is to carry sulfur type hydrodesulfurization by mild, quick pretreating process processing
Modifying catalyst obtains sulfide type catalyst, and catalyst is made to carry out hydrodesulfurizationmodification modification reaction under the operating condition of mitigation.
Catalytic gasoline hydrogenation desulfurization method for modifying provided by the invention, using fixed bed reactors；The catalyst
For the sulfur-carried hydrogenation catalyst of the stratified material containing zinc-aluminium, on the basis of catalyst weight, the content of molecular sieve is 5-70wt%,
It can be ZSM-5 and/or SAPO-11, preferably 30-65wt%；Group vib tenor is calculated as 2-10wt% with oxide, best
For tungsten and/or molybdenum, preferably 2-5wt%；Group VIII metal content is calculated as 1-5wt%, preferably nickel and/or cobalt with oxide, excellent
Select 1-3wt%；Sulfur content is 3-8wt%；It is 5- by the non-constant pH zinc-aluminium stratiform material content that alternately prepared by titration
50wt%；Phosphorus content is calculated as 0-10wt% with oxide.Hydrodesulfurizationmodification modification process conditions are as follows: 170-350 DEG C of reaction temperature, instead
Answer pressure 1.5-2.4MPa, volume space velocity 1.5-4.0h-1, hydrogen to oil volume ratio 150-500:1.
Catalytic gasoline hydrogenation desulfurization method for modifying provided by the invention, reactor can be fixed bed adiabatic reaction
Device is also possible to fixed bed isothermal reactor, preferably fixed bed adiabatic reactor；Temperature of reactor is preferably 240~350 DEG C,
Reaction pressure is preferably 1.8~2.2MPa, and volume space velocity is preferably 1.5~2.2h-1, hydrogen to oil volume ratio is preferably 200~300.
Catalyst used in hydrogenation desulfurization transmutation method of the invention is to be added to zinc-aluminium stratified material in molecular sieve to mix
It pinches molding and prepares carrier, will be configured to containing group vib metal, group VIII metal, the soluble-salt of P elements and ATS (Ammonium thiosulphate)
Maceration extract, preferably control ATS (Ammonium thiosulphate) dosage make sulphur and group vib metal molar ratio 2-5, and impregnated carrier is obtained containing zinc-aluminium
The catalyst precursor of stratified material is dried at 80-150 DEG C, in 450-550 DEG C of roasting 4-10h to get finished catalyst.It urges
It is added to the zinc-aluminium stratified material with large specific surface area in agent, and adds hydrogen with the load sulfur type of the compound preparation of molecular screen material
Desulfurization modifying catalyst has good hydrodesulfurization and Olefin decrease performance.
The present invention also provides a kind of preparation methods of zinc-aluminium stratified material:
1) soluble zinc salt is dissolved in water to obtain zinc-containing solution；
2) sodium metaaluminate and sodium carbonate are dissolved in water to obtain containing aluminum solutions；
3) 1) zinc-containing solution of inventory in is divided into 2-4 parts, take a copy of it 40-80 DEG C by 2) containing aluminum solutions
It is added dropwise wherein, stops being added dropwise containing aluminum solutions when pH value reaches 8.5-9.5；A copy of it zinc-containing solution is taken to be added drop-wise to the mixing again
In system；After zinc-containing solution all drips when the part, continue to be added dropwise the stopping when pH value reaches 8.5-9.5 containing aluminum solutions
It is added dropwise and contains aluminum solutions；Aluminum solutions will be contained according to the method described above and zinc-containing solution alternately titrates, until the zinc-containing solution of inventory is complete
Portion is added drop-wise in hybrid system, and last time, which is added dropwise, contains aluminum solutions, when pH value reaches 8.5-9.5, the alternating of non-constant pH value
Titration process terminates, and controls rate of titration in 0.5-6h；
4) after 75-95 DEG C of aging 2-8h, cooling washing to neutrality, dry 4-10h, is obtained in 80-140 DEG C of air atmosphere
To zinc-aluminium stratified material；
The load sulfur type hydrodesulfurizationmodification modification catalyst, the main composition of zinc-aluminium stratified material are expressed as by chemical formula
ZnxAly(OH)z(CO3)m·nH2O, wherein x is a number in 0.55-0.75, and y is a number in 0.13-0.7, and z is
A number in 1.55-2.50, m are a numbers in 0.15-0.20, and n is a number in 1-10, and the value of x/y is 0.75-
A number in 5.70, preferably x/y are a numbers in 0.93-2.50, and more preferable x/y is a number in 1.15-1.90；Than
Surface area is 150-280m2/ g, the preferred 180-280m of specific surface area2/ g, the more preferable 200-280m of specific surface area2/g.In control zinc
Al mole ratio x/y is in 0.93-2.50 range, specific surface area 180-280m2/g；In zinc-aluminium molar ratio x/y in 1.15-1.90 model
When enclosing, specific surface area 200-280m2/g。
Soluble zinc salt of the present invention is one of zinc nitrate, zinc acetate, zinc chloride or a variety of.
The present invention also provides a kind of preprocess methods of catalyst: in a nitrogen atmosphere, with the heating speed of 15-30 DEG C/h
Rate rises to 150 DEG C from room temperature；Be switched to hydrogen or hydrogen-containing gas and establish hydrogen-containing gas circulation pretreatment catalyst, hydrogen with
The volume ratio of catalyst is that 225-2000 with the heating rate of 10-20 DEG C/h rises to 316 DEG C from 150 DEG C, in temperature-rise period
230 DEG C, 260 DEG C, 316 DEG C stop 1-2h respectively；After pretreatment, it is adjusted to reaction process condition, is reacted into feedstock oil.It can
With the naphtha plus hydrogen essence during hydrogen or hydrogen-containing gas pretreatment catalyst, using olefin(e) centent no more than 5v%
Liquefaction establishes oil product circulation, and oil product air speed is 1.5-4.0h-1。
Compared with prior art, zinc-aluminium stratified material of the invention is by non-constant pH alternately titration preparation, i.e., non-
The alternating of sodium carbonate liquor and zinc-containing solution under the conditions of constant pH, containing aluminium titrates preparation, and therefore, it is necessary to divide zinc-containing solution
It is 2-4 parts.Sodium carbonate liquor containing aluminium is strong alkali solution, and the strong acid weak base salting liquid containing zinc is acid solution, aluminium zinc solution
Between it is multiple alternately titration swing pH value between soda acid, be conducive to aluminium zinc precursor object orderly accumulation be layer structure, obtain
To zinc-aluminium stratified material be uniformly dispersed and specific surface area can be in 150-280m2Regulate and control between/g, avoids using alkalinity
The problem of zinc-aluminium stratified material that one step of solution titration zinc-aluminium mixed solution obtains needs high-temperature roasting to fix zinc oxide, is also reduced
Hydrothermal treatment process.The material has biggish specific surface area, is suitable for catalysis material, with the compound preparation of molecular screen material
Carrying sulfur type hydrodesulfurizationmodification modification catalyst has good hydrodesulfurization and Olefin decrease performance.
Preprocess method provided by the invention makes catalyst in the condition for not adding sulfide additionally, can be in the short period
Interior completion vulcanizing treatment, pretreatment condition and reaction condition are mild, to the adaptable of different material；There is catalyst higher
Hydrodesulfurization activity and selectivity, be conducive to device and go into operation and long period steady running.
Detailed description of the invention
Fig. 1 is the XRD characterization figure for carrying sulfur type catalyst precursor A-D, contains Zn in XRD spectraxAly(OH)z
(CO3)m·nH2The XRD characteristic peak of O object phase illustrates to contain zinc-aluminium stratified material in catalyst precursor.
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.
Analysis method and standard:
Sulfur content in oil products analysis: SH/T0689-2000
Gasoline stocks property:
Raw material 1: Lanzhou Petrochemical catalytically cracked gasoline, sulfur content 300mg/kg, RON 91.5, alkene 40v%.
Raw material 2: Sichuan Stone fluidized catalytic cracking gasoline, sulfur content 60mg/kg, RON 90.5, alkene 37v%.
Catalyst preparation
Carry sulfur type catalyst 1
2.4kg zinc nitrate is dissolved in 12L water and is made into zinc-containing solution, by 0.32kg sodium metaaluminate and 0.40kg sodium carbonate
It is dissolved in 5L water and is made into containing aluminum solutions.Zinc-containing solution is divided into 4 parts, every part of 3L.Take 3L zinc-containing solution, control system temperature
It 75 DEG C, is added dropwise reaches 9.4 containing aluminum solutions to pH value thereto；Stop being added dropwise and contain aluminum solutions, then 3L zinc-containing solution is added dropwise to mixing
In system, continues dropwise addition containing aluminum solutions to pH value and reach 9.4；It is alternately titrated containing aluminum solutions and zinc-containing solution, until zinc-containing solution
It is all added in hybrid system, last time, which is added dropwise, reaches 9.4 containing aluminum solutions to pH, and titration time amounts to 2h.Obtained mixing
Object is after 75 DEG C of aging 4h, and cooling washing to neutrality, dry 2h, obtains zinc-aluminium stratified material 1 in 130 DEG C of air atmospheres, point
Minor is Zn0.60Al0.50(OH)2.33(CO3)0.185·4H2O, zinc-aluminium molar ratio 1.20, specific surface area 258m2/g。
1kg zinc-aluminium stratified material 1 is taken to mix extrusion into carrier with 1kg molecular sieve ZSM-5；Take 0.135kg ammonium molybdate,
0.072kg cobalt nitrate, 0.039kg ammonium dihydrogen phosphate are added in 0.2L ammonium hydroxide, then are diluted with 0.6L deionized water, according to sulphur molybdenum
Molar ratio 3.0 be added sodium thiosulfate be made into maceration extract impregnated carrier, obtained catalyst precursor A 90 DEG C drying after
550 DEG C of roasting 4h, obtain catalyst 1.
Carry sulfur type catalyst 2
1.9kg zinc chloride is dissolved in 20L water and is made into zinc-containing solution, by 0.40kg sodium metaaluminate and 0.80kg sodium carbonate
It is dissolved in 8.5L water and is made into containing aluminum solutions.8L zinc-containing solution is taken, 65 DEG C of control system temperature, is added dropwise thereto containing aluminum solutions extremely
PH value reaches 9.1；Remaining zinc-containing solution is divided into 3 parts, every part of 4L.It is alternately titrated containing aluminum solutions and zinc-containing solution, until containing zinc
Solution is all added in hybrid system, and last time, which is added dropwise, reaches 9.1 containing aluminum solutions to pH, and titration time amounts to 6h.It obtains
Mixture is after 76 DEG C of aging 8h, and cooling washing to neutrality, dry 10h, obtains zinc-aluminium stratified material in 90 DEG C of air atmospheres
2, molecular formula Zn0.67Al0.33(OH)2.03(CO3)0.150·4H2O, zinc-aluminium molar ratio 2.03, specific surface area 227m2/g。
0.3kg zinc-aluminium stratified material 2 is taken to mix extrusion into load with 0.3kg molecular sieve ZSM-5,0.3kg molecular sieve SAPO-11
Body；It takes 0.061kg ammonium molybdate, 0.056kg cobalt nitrate, 0.05kg ammonium nitrate to be dissolved in 0.35L deionized water, adds 0.4L
Ammonium hydroxide is added sodium thiosulfate according to sulphur molybdenum molar ratio 2.7 and is made into maceration extract impregnated carrier, and obtained catalyst precursor B exists
In 510 DEG C of roasting 6h after 100 DEG C of drying, catalyst 2 is obtained.
Carry sulfur type catalyst 3
800g zinc nitrate is dissolved in 4L water and is made into zinc-containing solution, 120g sodium metaaluminate and 120g sodium carbonate are dissolved in
It is made into 1.7L water containing aluminum solutions.2L zinc-containing solution is taken, control system temperature 60 C is added dropwise reaches containing aluminum solutions to pH value thereto
To 9, stop being added dropwise containing aluminum solutions, remaining 2L zinc-containing solution is added drop-wise in hybrid system, continues to be added dropwise containing aluminum solutions to pH
Value reaches 9, and titration time amounts to 4h.Obtained mixture is after 85 DEG C of aging 4h, and cooling washing is to neutrality, in 120 DEG C of air
Dry 5h, obtains zinc-aluminium stratified material 3, molecular formula Zn in atmosphere0.59Al0.63(OH)2.44(CO3)0.195·6H2O, zinc-aluminium rub
That ratio 0.94, specific surface area 260m2/g。
50g zinc-aluminium stratified material 3 is taken to mix extrusion into carrier with 125g molecular sieve ZSM-5,25g molecular sieve SAPO-11；It takes
21.6g ammonium molybdate, 12.1g cobalt nitrate are dissolved in 75ml ammonium hydroxide, and sodium thiosulfate is added according to sulphur molybdenum molar ratio 4.0 and is made into leaching
Stain liquid impregnated carrier, obtained catalyst precursor C obtain catalyst 3 in 480 DEG C of roasting 9h after 100 DEG C of drying.
Carry sulfur type catalyst 4
1.6kg zinc nitrate is dissolved in 8L water and is made into zinc-containing solution, by 0.11kg sodium metaaluminate and 0.38kg sodium carbonate
It is dissolved in 3.4L water and is made into containing aluminum solutions.Zinc-containing solution is divided into 4 parts, every part of 2L.Take 2L zinc-containing solution, control system temperature
75 DEG C of degree is added dropwise reaches 8.7 containing aluminum solutions to pH value thereto；Stop be added dropwise contain aluminum solutions, then be added dropwise 2L zinc-containing solution to mix
In collaboration system, continues dropwise addition containing aluminum solutions to pH value and reach 8.7；It is alternately titrated containing aluminum solutions and zinc-containing solution, until molten containing zinc
Liquid is all added in hybrid system, and last time, which is added dropwise, reaches 8.7 containing aluminum solutions to pH, and titration time amounts to 6h.What is obtained is mixed
Object is closed after 90 DEG C of aging 6h, cooling washing to neutrality, dry 6h, obtains zinc-aluminium stratified material 4 in 110 DEG C of air atmospheres,
Molecular formula is Zn0.74Al0.21(OH)1.72(CO3)0.165·6H2O, zinc-aluminium molar ratio 3.55, specific surface area 172m2/g。
1.1kg zinc-aluminium stratified material 4 is taken to mix extrusion into carrier with 0.9kg molecular sieve SAPO-11；Take 0.216kg molybdic acid
Ammonium, 0.346kg nickel acetate are dissolved in 0.75L ammonium hydroxide, and sodium thiosulfate is added according to sulphur molybdenum molar ratio 3.5 and is made into maceration extract leaching
Stain carrier, obtained catalyst precursor D obtain catalyst 4 in 460 DEG C of roasting 10h after 130 DEG C of drying.
Oxidation catalyst 5
1kg zinc-aluminium stratified material 1 is taken to mix extrusion into carrier with 1kg molecular sieve ZSM-5；Take 0.135kg ammonium molybdate,
0.072kg cobalt nitrate, 0.039kg ammonium dihydrogen phosphate are added in 0.2L ammonium hydroxide, then are made into dipping with the dilution of 0.6L deionized water
Liquid impregnated carrier obtains oxidation catalyst 5 in 550 DEG C of roasting 4h after 90 DEG C of drying.
Embodiment 1
Sulfur type catalyst 1 will be carried to be fitted into 1L fixed bed adiabatic reactor, in pressure 2.0MPa, in a nitrogen atmosphere with 20
DEG C/heating rate of h is warming up to 150 DEG C；Hydrogen and catalyst volume ratio 500:1 establish hydrogen circulation, naphtha air speed 2.0-1
Oil product circulation is established, 230 DEG C of stop 1h are warming up to 15 DEG C/h, are warming up to 260 DEG C of stop 1h, are warming up to 316 DEG C of stop 1h, in advance
Processing terminate；Naphtha is switched to raw material 1, reaction process condition are as follows: 320 DEG C of temperature of reactor, reaction pressure 2.0MPa, body
Product air speed 2.0h-1, hydrogen to oil volume ratio 250；Operate 100h, product desulfurization degree 92%, 5.7 percentage points of alkene drop amount, octane number
Lose 0.1 unit；Operate 1000h, product desulfurization degree 90%, 5.7 percentage points of alkene drop amount, 0.1 list of loss of octane number
Position.
Comparative example 1
Oxidation catalyst 5 is fitted into 1L fixed bed adiabatic reactor, in pressure 2.0MPa, in a nitrogen atmosphere with 20
DEG C/heating rate of h is warming up to 150 DEG C；Hydrogen and catalyst volume ratio 500:1 establish hydrogen circulation, contain 1.5% dimethyl two
The naphtha of thioether is with air speed 2.0-1Oil product circulation is established, 230 DEG C of stop 8h are warming up to 15 DEG C/h, are warming up to 260 DEG C of stops
8h, is warming up to 316 DEG C of stop 4h, and vulcanizing treatment terminates；Naphtha is switched to raw material 1, reaction process condition are as follows: reactor temperature
320 DEG C, reaction pressure 2.0MPa, volume space velocity 2.0h of degree-1, hydrogen to oil volume ratio 250；Operate 100h, product desulfurization degree 92%, alkene
5.7 percentage points of hydrocarbon drop amount, 0.2 unit of loss of octane number；Operate 1000h, product desulfurization degree 85%, alkene drop amount 5.7
Percentage point, 0.2 unit of loss of octane number.
Embodiment 2
Sulfur type catalyst 2 will be carried to be fitted into 600mL fixed bed adiabatic reactor, in pressure 2.2MPa, in a nitrogen atmosphere
150 DEG C are warming up to the heating rate of 25 DEG C/h；Hydrogen and catalyst volume ratio 300:1 establish hydrogen circulation, with 20 DEG C/h liter
Temperature is warming up to 260 DEG C of stop 1h, is warming up to 316 DEG C of stop 1h, pretreatment terminates to 230 DEG C of stop 2h；Naphtha is switched to
Raw material 1, reaction process condition are as follows: 350 DEG C of temperature of reactor, reaction pressure 2.2MPa, volume space velocity 1.5h-1, hydrogen to oil volume ratio
200；Operate 400h, product desulfurization degree 95%, 5.9 percentage points of alkene drop amount, 0.1 unit of loss of octane number.
Embodiment 3
Sulfur type catalyst 3 will be carried to be fitted into 200mL fixed bed isothermal reactor, in pressure 1.8MPa, in a nitrogen atmosphere
150 DEG C are warming up to the heating rate of 30 DEG C/h；Hydrogen and catalyst volume ratio 540:1 establish hydrogen circulation, with 10 DEG C/h liter
Temperature is warming up to 260 DEG C of stop 2h, is warming up to 316 DEG C of stop 1h, pretreatment terminates to 230 DEG C of stop 1h；Hydrofined oil is cut
It is changed to raw material 2, reaction process condition are as follows: 245 DEG C of temperature of reactor, reaction pressure 1.8MPa, volume space velocity 1.8h-1, hydrogen oil body
Product ratio 300；400h is operated, product desulfurization degree 80%, 4.8 percentage points of alkene drop amount, octane number does not lose.
Embodiment 4
Sulfur type catalyst 4 will be carried to be fitted into 200mL fixed bed isothermal reactor, in pressure 1.8MPa, in a nitrogen atmosphere
150 DEG C are warming up to the heating rate of 15 DEG C/h；Hydrogen and catalyst volume ratio 1400:1 establish hydrogen circulation, with 15 DEG C/h liter
Temperature is warming up to 260 DEG C of stop 1h, is warming up to 316 DEG C of stop 2h, pretreatment terminates to 230 DEG C of stop 1h；Hydrofined oil is cut
It is changed to raw material 2, reaction process condition are as follows: 195 DEG C of temperature of reactor, reaction pressure 2.2MPa, volume space velocity 3.5h-1, hydrogen oil body
Product ratio 400；400h is operated, product desulfurization degree 65%, 4.5 percentage points of alkene drop amount, octane number does not lose.
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 (13)
1. a kind of catalytic gasoline hydrogenation desulfurization method for modifying, which is characterized in that use fixed bed reactors；The catalyst
For the sulfur-carried hydrogenation catalyst of the stratified material containing zinc-aluminium, on the basis of catalyst weight, catalyst composition is as follows: molecular sieve
Content is 5-70wt%；Group vib tenor is calculated as 2-10wt% with oxide, and group VIII metal content is calculated as 1- with oxide
5wt% is 5-50wt% by the non-constant pH zinc-aluminium stratiform material content that alternately prepared by titration；Sulfur content is 3-8wt%, phosphorus
Content is calculated as 0-10wt% with oxide；Hydrodesulfurizationmodification modification process conditions are as follows: 170-350 DEG C of reaction temperature, reaction pressure
1.5-2.4MPa volume space velocity 1.5-4.0h-1, hydrogen to oil volume ratio 150-500:1.
2. catalytic gasoline hydrogenation desulfurization method for modifying according to claim 1, which is characterized in that temperature of reactor is
240~350 DEG C, reaction pressure is 1.8~2.2MPa.
3. catalytic gasoline hydrogenation desulfurization method for modifying according to claim 1, which is characterized in that volume space velocity is
1.5~2.2h-1。
4. catalytic gasoline hydrogenation desulfurization method for modifying according to claim 1, which is characterized in that molecular sieve ZSM-
5 and/or SAPO-11, content 30-65wt%.
5. catalytic gasoline hydrogenation desulfurization method for modifying according to claim 1, which is characterized in that the group vib gold
Belonging to is tungsten and/or molybdenum, and tungsten and/or the molybdenum content in terms of oxide are 2-5wt%.
6. catalytic gasoline hydrogenation desulfurization method for modifying according to claim 1, which is characterized in that group VIII metal is
Nickel and/or cobalt, nickel and/or the cobalt content in terms of oxide are 1-3wt%.
7. catalytic gasoline hydrogenation desulfurization method for modifying according to claim 1, which is characterized in that the catalyst system
Preparation Method is as follows: preparing kneading and compacting in molecular sieve is added to by the non-constant pH zinc-aluminium stratified material that alternately prepared by titration
Carrier will be configured to maceration extract containing group vib metal, group VIII metal, the soluble-salt of P elements and ATS (Ammonium thiosulphate), dipping
Carrier obtains the catalyst precursor containing zinc-aluminium stratified material, dries at 80-150 DEG C, in 450-550 DEG C of roasting 4-10h, i.e.,
Obtain finished catalyst.
8. catalytic gasoline hydrogenation desulfurization method for modifying according to claim 7, which is characterized in that sulphur and group vib gold
Category molar ratio is 2-5.
9. catalytic gasoline hydrogenation desulfurization method for modifying according to claim 1, which is characterized in that the zinc-aluminium stratiform
The main composition of material is expressed as Zn by chemical formulaxAly(OH)z(CO3)m·nH2O, wherein x is a number in 0.55-0.75,
Y is a number in 0.13-0.7, and z is a number in 1.55-2.50, and m is a number in 0.15-0.20, and n is in 1-10
A number, the value of x/y is a number in 0.75-5.70, specific surface area 150-280m2/g。
10. catalytic gasoline hydrogenation desulfurization method for modifying according to claim 9, which is characterized in that the zinc-aluminium layer
Shape material specific surface area is 200-280m2/g。
11. catalytic gasoline hydrogenation desulfurization method for modifying according to claim 9, which is characterized in that the zinc-aluminium layer
The zinc-aluminium molar ratio x/y of shape material is a number in 0.93-2.50, specific surface area 180-280m2/g。
12. catalytic gasoline hydrogenation desulfurization method for modifying according to claim 9, which is characterized in that the zinc-aluminium layer
The zinc-aluminium molar ratio x/y of shape material is a number in 1.15-1.90, specific surface area 200-280m2/g。
13. catalytic gasoline hydrogenation desulfurization method for modifying according to claim 9, which is characterized in that the zinc-aluminium layer
The preparation method of shape material includes the following steps: 1) to be dissolved in water soluble zinc salt to obtain zinc-containing solution；2) by meta-aluminic acid
Sodium and sodium carbonate are dissolved in water to obtain containing aluminum solutions；3) 1) zinc-containing solution of inventory in is divided into 2-4 parts, takes a copy of it
At 40-80 DEG C by being added dropwise wherein containing aluminum solutions in 2), stops being added dropwise when pH value reaches 8.5-9.5 and contain aluminum solutions；Take it again
Middle portion zinc-containing solution is added drop-wise in the hybrid system；After when the part, zinc-containing solution is all dripped, continue to be added dropwise molten containing aluminium
Liquid stops being added dropwise containing aluminum solutions when pH value reaches 8.5-9.5；Aluminum solutions will be contained according to the method described above and zinc-containing solution alternately drips
Fixed, until the zinc-containing solution of inventory is all added drop-wise in hybrid system, last time, which is added dropwise, contains aluminum solutions, when pH value reaches
When 8.5-9.5, the alternating titration process of non-constant pH value terminates, and controls rate of titration in 0.5-6h；4) in 75-95 DEG C of aging 2-
After 8h, cooling washing to neutrality, dry 4-10h, obtains zinc-aluminium stratified material in 80-140 DEG C of air atmosphere.
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| CN1485414A (en) * | 2002-09-26 | 2004-03-31 | 中国科学院大连化学物理研究所 | Method for non-hydroaromatizating and desulfurizing catalytically cracked gasoline |
| CN102851060A (en) * | 2012-05-22 | 2013-01-02 | 北京众诚汇微能源科技有限公司 | Method and apparatus for continuous oil product hydrodesulphurization by using microwaves |
| CN103320159A (en) * | 2013-06-24 | 2013-09-25 | 大连理工大学 | Method for removing mercaptan sulfur contained in catalytically cracked gasoline |
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| CN1485414A (en) * | 2002-09-26 | 2004-03-31 | 中国科学院大连化学物理研究所 | Method for non-hydroaromatizating and desulfurizing catalytically cracked gasoline |
| CN102851060A (en) * | 2012-05-22 | 2013-01-02 | 北京众诚汇微能源科技有限公司 | Method and apparatus for continuous oil product hydrodesulphurization by using microwaves |
| CN103320159A (en) * | 2013-06-24 | 2013-09-25 | 大连理工大学 | Method for removing mercaptan sulfur contained in catalytically cracked gasoline |
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