CN106955730B - A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil - Google Patents

A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil Download PDF

Info

Publication number
CN106955730B
CN106955730B CN201610010223.5A CN201610010223A CN106955730B CN 106955730 B CN106955730 B CN 106955730B CN 201610010223 A CN201610010223 A CN 201610010223A CN 106955730 B CN106955730 B CN 106955730B
Authority
CN
China
Prior art keywords
desulfurization
weight
hydrocarbon oil
sicn
oxide
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.)
Active
Application number
CN201610010223.5A
Other languages
Chinese (zh)
Other versions
CN106955730A (en
Inventor
林伟
田辉平
王振波
王磊
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.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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 Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201610010223.5A priority Critical patent/CN106955730B/en
Publication of CN106955730A publication Critical patent/CN106955730A/en
Application granted granted Critical
Publication of CN106955730B publication Critical patent/CN106955730B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • 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
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • 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
    • 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
    • B01J2229/26—After treatment, characterised by the effect to be obtained to stabilize the total catalyst structure

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses the methods of a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil.On the basis of the total weight of the desulfurization of hydrocarbon oil catalyst, which contains: 1) at least one metal oxide selected from IIB, VB and group vib element of 10~80 weight %；2) heat-resistant inorganic oxide of 3~35 weight %；3) SiCN of 5~40 weight %；4) molecular sieve with FAU and/or BEA structure of 1~20 weight %；5) metallic promoter agent of 5~30 weight %, the metallic promoter agent are selected from least one of cobalt, nickel, iron and manganese.The desulfurization of hydrocarbon oil catalyst has better stability and higher desulphurizing activated, and better abrasion resistance properties, the service life is longer.

Description

A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
Technical field
The present invention relates to the methods of a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil, and in particular, to A kind of desulfurization of hydrocarbon oil catalyst, the desulfurization of hydrocarbon oil catalyst for preparing the method for desulfurization of hydrocarbon oil catalyst and being obtained by this method, with And the method using desulfurization of hydrocarbon oil catalyst progress desulfurization of hydrocarbon oil.
Background technique
As people are to the pay attention to day by day of environmental protection, environmental regulation is also increasingly stringent, and reduces the sulphur of gasoline and diesel oil Content is considered as improving one of the most important measure of air quality.Most of sulphur in China's gasoline products are from hot-working Gasoline blending component, such as catalytically cracked gasoline.Therefore the reduction of sulfur content helps to reduce the production of China's gasoline in hot-working petroleum The sulfur content of product.The existing gasoline products standard GB 17930-2011 " motor petrol " in China was required on December 31st, 2013, Sulfur content must drop to 50 μ g/g in gasoline products.And following gasoline product quality standard will be more stringent.At this In the case of kind, catalytically cracked gasoline, which has to pass through deep desulfuration just, can make gasoline products meet environmentally friendly requirement.
Currently, mainly selective catalytic desulfurhydrogenation and catalytic hydrogenation adsorb two kinds of desulfurization to the process for deep desulphurization of oil product Method.Catalytic hydrogenation absorption desulfurization is to inhale the sulfide in hydrocarbon ils in certain temperature, pressure and realizing under conditions of face hydrogen Attached removing, it is low and not high to the purity requirement of hydrogen which has the characteristics that hydrogen consumes, so that the technology is in terms of fuel desulfuration It has broad application prospects.
CN1355727A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel Object is made of zinc oxide, silica, oxidation al and ni, and wherein for nickel substantially to restore valence state presence, amount can be from de- Sulphur is removed in the cracking gasoline or diesel fuel stream contacted under the conditions of sulphur with the nickeliferous adsorbent composition.The composition is logical It crosses and is granulated to form particle by the compound particles that zinc oxide, silica and aluminium oxide are formed, use nickel or nickeliferous chemical combination after dry, roasting Object dipping, re-dry, roasting, reduction obtain.
CN1382071A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel Object is made of zinc oxide, silica, aluminium oxide and cobalt, and wherein for cobalt substantially to restore valence state presence, amount can be from de- Sulphur is removed in the cracking gasoline or diesel fuel stream contacted under the conditions of sulphur with the adsorbent composition containing cobalt.
US6150300 discloses a kind of method for preparing adsorbent, including prepares spheric granules: will (a) contain silica Composition, the composition containing dispersion metal oxide in an aqueous medium and the composition containing zinc oxide mix shape First mixture is not squeezed out at the first mixture and；(b) forming first mixture at spherical shape has diameter 10- The particle of 1000mm.Wherein step (a) further includes mixing with metallic promoter agent.
CN1422177A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel Object is made of zinc oxide, expanded perlite, aluminium oxide and promoter metals, wherein the promoter metals are substantially to restore Valence state and contact under desulfurization conditions in Shi Nengcong cracking gasoline or diesel fuel stream remove sulphur amount exist.
CN1627988A discloses one kind suitable for the removing elementary sulfur from cracking gasoline and diesel fuel and vulcanization conjunction The adsorbent composition of object, the adsorbent composition includes: zinc oxide, expanded perlite, aluminate and promoter metals, Described in promoter metals will lead to when making cracking gasoline or diesel fuel stream and it is contacted under desulfurization conditions from cracking The amount of desulfurization in the stream of gasoline or diesel fuel exists, and at least partly described promoter metals exist with 0 valence state.
CN1856359A discloses a kind of method for producing composition, comprising: a) mixing liquid, zinc compound, contain two Silica material, aluminium oxide and co-catalyst, to form its mixture；B) dry mixture, to form dried mixing Object；C) the dried mixture is calcined, to form the mixture through calcining；D) under suitable condition with reducing agent appropriate By mixture reduction through calcining, to produce the composition and e) of the co-catalyst content in it with reduction valence state Recycling changes composition.Co-catalyst contains selected from various metals such as nickel.
CN1871063A discloses a kind of method for producing composition, this method comprises: a) by liquid, zinc compound, It is mixed containing earth silicon material, aluminium oxide to form its mixture；B) dry this of the mixture is mixed to form first Through drying composite；C) described first is calcined through drying composite to form first through calcining mixt；D) by promotor knot Close described first through within calcining mixt or on formed be promoted mixture；E) mixture and choosing are promoted described in making It contacts from the acid of citric acid, tartaric acid and combinations thereof to be formed through contact mixture；F) by it is described through contact mixture it is dry with Second is formed through drying composite；G) described second is calcined through drying composite to form second through calcining mixt；H) exist Suitable reducing agent reduction described second is used wherein to promote containing reduction valence state through calcining mixt to produce under the conditions of appropriate Into agent content composition and i) recycle the composition.
Although published adsorbent has certain desulfurization performance, with the raising of gasoline quality standard, to product Content of sulfur in gasoline requires also constantly stringent.And such catalyst is easy to happen abrasion in use, needs to be continuously replenished Catalyst improves operating cost.It can be seen that, it is desirable to provide it is a kind of to be urged with more high desulfurization activity and the novel of abrasion resistance properties Agent.
Summary of the invention
The purpose of the invention is to overcome the desulphurizing activated low, structural instability of the adsorbent of the prior art and wear resistance Can difference defect, provide the method for a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil.
To achieve the goals above, the present invention provides a kind of desulfurization of hydrocarbon oil catalyst, with the total of the desulfurization of hydrocarbon oil catalyst On the basis of weight, which contains: 1) at least one of 10~80 weight % is selected from IIB, VB and group vib element Metal oxide；2) heat-resistant inorganic oxide of 3~35 weight %；3) SiCN of 5~40 weight %；4) 1~20 weight % The molecular sieve with FAU and/or BEA structure；5) metallic promoter agent of 5~30 weight %, the metallic promoter agent be selected from cobalt, At least one of nickel, iron and manganese.
The present invention also provides the methods for preparing desulfurization of hydrocarbon oil catalyst of the invention, comprising: (1a) is by SiCN, heat-resisting nothing Machine adhesive oxides, water and acidic liquid contact to form slurries, by the slurries and point with FAU and/or BEA structure Son sieve, at least one metal oxide selected from IIB, VB and group vib element are mixed to get carrier pulp；Or (1b) will be heat-resisting Inorganic oxide binder, water and acidic liquid contact to form slurries, by the slurries and point with FAU and/or BEA structure Son sieve, at least one metal oxide, SiCN selected from IIB, VB and group vib element are mixed to get carrier pulp；It (2) will be described Carrier pulp is formed, first dry, the first roasting, obtains carrier；(3) before introducing metallic promoter agent in the carrier Then body carries out second dry and the second roasting, obtains catalyst precarsor；(4) in a hydrogen atmosphere by the catalyst precarsor Reduction, obtains desulfurization of hydrocarbon oil catalyst.
The present invention also provides desulfurization of hydrocarbon oil catalyst made from method of the invention.
The present invention also provides a kind of methods of desulfurization of hydrocarbon oil, comprising: in a hydrogen atmosphere, by hydrocarbon oil containing surphur and the present invention The desulfurization of hydrocarbon oil catalyst of offer carries out desulphurization reaction at 350~500 DEG C, 0.5~4MPa.
Containing the stable SiCN of chemical property (carbonitride of silicium) in the composition of desulfurization of hydrocarbon oil catalyst provided by the invention, subtract Lack the dependent interaction with metal oxides such as zinc oxide, avoids the formation such as silicic acid zinc material, such as the implementation that Fig. 1 is shown The characteristic peak of zinc silicate is not present in XRD spectra after the hydrothermal aging for the desulfurization of hydrocarbon oil catalyst A1 that example 1 obtains.The present invention mentions The desulfurization of hydrocarbon oil catalyst of confession has better stability and higher desulphurizing activated, can be more effective during desulfurization of hydrocarbon oil Sulphur in hydrocarbon ils is adsorbed on desulfurization of hydrocarbon oil catalyst by ground, obtains the lower hydrocarbon ils of sulfur content.And hydrocarbon provided by the invention Oily desulphurization catalyst has better abrasion resistance properties, and catalyst attrition is lower in sweetening process, and the service life is longer.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is XRD spectrum of the obtained desulfurization of hydrocarbon oil catalyst A1 of embodiment 1 before and after hydrothermal aging；
Fig. 2 is XRD spectrum of the obtained desulfurization of hydrocarbon oil catalyst B1 of comparative example 1 before and after hydrothermal aging.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of desulfurization of hydrocarbon oil catalyst, on the basis of the total weight of the desulfurization of hydrocarbon oil catalyst, the hydrocarbon ils Desulphurization catalyst contains: 1) at least one metal oxide selected from IIB, VB and group vib element of 10~80 weight %；2)3 The heat-resistant inorganic oxide of~35 weight %；3) SiCN of 5~40 weight %；4) 1~20 weight %'s has FAU and/or BEA The molecular sieve of structure；5) metallic promoter agent of 5~30 weight %, the metallic promoter agent in cobalt, nickel, iron and manganese at least It is a kind of.
Preferably, on the basis of the total weight of the desulfurization of hydrocarbon oil catalyst, the total weight with the desulfurization of hydrocarbon oil catalyst is Benchmark, the desulfurization of hydrocarbon oil catalyst contain the metal oxide of 25~70 weight %, the heat resistant inorganic oxygen of 6~25 weight % Compound, the molecular sieve with FAU and/or BEA structure of the SiCN of 10~30 weight %, 2~15 weight %, 8~25 weight % The metallic promoter agent.
It is highly preferred that on the basis of the total weight of the desulfurization of hydrocarbon oil catalyst, with the total weight of the desulfurization of hydrocarbon oil catalyst On the basis of, which contains the metal oxide of 40~60 weight %, the heat resistant inorganic of 8~15 weight % Oxide, the molecular sieve with FAU and/or BEA structure of the SiCN of 12~25 weight %, 2~10 weight %, 12~20 weights Measure the metallic promoter agent of %.
In the present invention, the content of each component in the desulfurization of hydrocarbon oil catalyst can be measured by XRD crystal phase analysis method.
According to the present invention, in the spectrogram that the desulfurization of hydrocarbon oil catalyst is obtained through XRD analysis 2 θ be 36.7 ° and 60.0 ° There are the crystal phase peaks of SiCN at place.
Contain the SiCN with hexagonal crystallographic texture in desulfurization of hydrocarbon oil catalyst provided by the invention as structural component, by There is very high hydrothermal stability in structure SIC N, the catalyst can be effectively prevented from during carrying out desulfurization of hydrocarbon oil Such as silicic acid zinc material is formed in composition, guarantees that the catalyst has better desulphurizing activated and stability.Preferably, the hydrocarbon ils is de- Sulfur catalyst is not have the feature of zinc silicate at 22.0,25.54,48.9 and 59.4 in 2 θ in the XRD spectra after hydrothermal aging Peak.The hydrothermal aging is 500-700 DEG C of temperature, steam partial pressure 10-30kPa, and the processing time is 10-24h.
According to the present invention, the FAU structure molecular screen is faujasite-type molecular sieve, and the type molecular sieve has three-dimensional ten Two membered ring channels, aperture areThe FAU structure molecular screen is mainly the molecular sieve of X-type and Y type, general next Say SiO2/Al2O3Molar ratio is that 2.2-3.0 is X-type molecular sieve, SiO2/Al2O3It is Y type molecular sieve that molar ratio, which is greater than 3.0,.X The skeleton structure of type and Y type molecular sieve belongs to hexagonal crystal system, and space group structure is Fd3m, the cell parameter of X-type molecular sieveThe cell parameter of Y type molecular sieve
According to the present invention, the molecular sieve with FAU structure further includes the modified molecular sieve with FAU structure. Method of modifying may include hydro-thermal method, method of chemical treatment (such as mineral acid logos, fluosilicic acid aluminium-eliminating and silicon-replenishing method and SiC14Gas Phase method) or hydro-thermal combined with chemical treatment.Modified obtained molecular sieve includes but is not limited to super-stable Y molecular sieves (USY), REUSY, REHY, REY containing rare earth element and phosphorous PUSY, PREHY, PREY etc..Point with FAU structure The SiO of son sieve2: Al2O3Molar ratio be 1-4:1；Preferably, the SiO of the molecular sieve with FAU structure2: Al2O3Rub You are than being 1.5-3:1.
According to the present invention, the BEA structure molecular screen is mainly beta-molecular sieve, and structural formula is (Nan[AlnSi64-nO128], N < 7), it is the mixed crystal formed by two structures are different but are closely related polymorph A and B, both there is twelve-ring three Pore canal system is tieed up, polymorph A forms a pair of of enantiomer, and space group is P4122 and P4322, and cell parameter isPolymorph B belongs to achirality space group C2/c, cell parameterβ=114.5 °.Twelve-ring pore size is in BEA structure molecular screen<100 direction>and <001 direction>.The molecular sieve with BEA structure SiO2: Al2O3Molar ratio be 5-10:1；Preferably, the SiO of the molecular sieve with BEA structure2: Al2O3Molar ratio be 7-9:1.
In the case of, according to the invention it is preferred to, the molecular sieve with FAU and/or BEA structure is X-type molecular sieve, Y type At least one of molecular sieve, USY, REUSY, REHY, REY, PUSY, PREHY, PREY and beta-molecular sieve.
According to the present invention, at least one metal oxide selected from IIB, VB and group vib element can for zinc oxide, At least one of cadmium oxide, vanadium oxide, niobium oxide tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide, it is described under preferable case Metal oxide is at least one of zinc oxide, molybdenum oxide and vanadium oxide；It is highly preferred that the metal oxide is oxidation Zinc.
In accordance with the present invention it is preferred that the metallic promoter agent is nickel and/or cobalt, the desulfurization of hydrocarbon oil catalyst can have There is higher desulphurizing activated and regenerability；The more preferable metallic promoter agent is nickel.
In the case of, according to the invention it is preferred to, the heat-resistant inorganic oxide be aluminium oxide, titanium dioxide, zirconium dioxide and At least one of stannic oxide.Preferably, the heat-resistant inorganic oxide is each component in the desulfurization of hydrocarbon oil catalyst Between cementation is provided.Wherein, the aluminium oxide be gama-alumina, η-aluminium oxide, θ-aluminium oxide and χ-aluminium oxide in extremely Few one kind；Preferably, the aluminium oxide is gama-alumina.
The present invention also provides the methods for preparing desulfurization of hydrocarbon oil catalyst of the invention, comprising: (1a) is by SiCN, heat-resisting nothing Machine adhesive oxides, water and acidic liquid contact to form slurries, by the slurries and point with FAU and/or BEA structure Son sieve, at least one metal oxide selected from IIB, VB and group vib element are mixed to get carrier pulp；Or (1b) will be heat-resisting Inorganic oxide binder, water and acidic liquid contact to form slurries, by the slurries and point with FAU and/or BEA structure Son sieve, at least one metal oxide, SiCN selected from IIB, VB and group vib element are mixed to get carrier pulp；It (2) will be described Carrier pulp is formed, first dry, the first roasting, obtains carrier；(3) before introducing metallic promoter agent in the carrier Then body carries out second dry and the second roasting, obtains catalyst precarsor；(4) in a hydrogen atmosphere by the catalyst precarsor Reduction, obtains desulfurization of hydrocarbon oil catalyst.
According to the present invention, the SiCN used selects specific structure that can provide desulfurization of hydrocarbon oil catalyst with preferably wear-resisting Performance and desulphurizing activated.Under preferable case, SiCN has hexagonal crystallographic texture, in the form of sheets or column structure.Preferably, SiCN Grain diameter is 1~20 μm, preferably 3~15 μm.Preferably, the specific surface area of SiCN is 1~30m2/g.Preferably, SiCN N2 adsorption pore volume be 0.02~0.12cm3/g；It is further preferred that the N2 adsorption pore volume of SiCN is 0.03~0.10cm3/g。
In preparation method of the invention, being added for the metal oxide can be for the powder shape of the metal oxide Formula is added, and is added in form of slurry again after water can also being added to be mixed into slurries the metal oxide.
In the present invention, at least one metal oxide selected from IIB, VB and group vib element can be zinc oxide, oxygen At least one of cadmium, vanadium oxide, niobium oxide tantalum oxide, chromium oxide, molybdenum oxide and tungsten oxide；Preferably zinc oxide, oxidation At least one of molybdenum and vanadium oxide；More preferably zinc oxide.
According to the present invention, the FAU structure molecular screen is faujasite-type molecular sieve, and the type molecular sieve has three-dimensional ten Two membered ring channels, aperture areThe FAU structure molecular screen is mainly the molecular sieve of X-type and Y type, general next Say SiO2/Al2O3Molar ratio is that 2.2-3.0 is X-type molecular sieve, SiO2/Al2O3It is Y type molecular sieve that molar ratio, which is greater than 3.0,.X The skeleton structure of type and Y type molecular sieve belongs to hexagonal crystal system, and space group structure is Fd3m, the cell parameter of X-type molecular sieveThe cell parameter of Y type molecular sieve
According to the present invention, the molecular sieve with FAU structure further includes the modified molecular sieve with FAU structure. Method of modifying may include hydro-thermal method, method of chemical treatment (such as mineral acid logos, fluosilicic acid aluminium-eliminating and silicon-replenishing method and SiC14Gas Phase method) or hydro-thermal combined with chemical treatment.Modified obtained molecular sieve includes but is not limited to super-stable Y molecular sieves (USY), REUSY, REHY, REY containing rare earth element and phosphorous PUSY, PREHY, PREY etc..Point with FAU structure The SiO of son sieve2: Al2O3Molar ratio be 1-4:1；Preferably, the SiO of the molecular sieve with FAU structure2: Al2O3Rub You are than being 1.5-3:1.
According to the present invention, the BEA structure molecular screen is mainly beta-molecular sieve, and structural formula is (Nan[AlnSi64-nO128], N < 7), it is the mixed crystal formed by two structures are different but are closely related polymorph A and B, both there is twelve-ring three Pore canal system is tieed up, polymorph A forms a pair of of enantiomer, and space group is P4122 and P4322, and cell parameter isPolymorph B belongs to achirality space group C2/c, cell parameterβ=114.5 °.Twelve-ring pore size is in BEA structure molecular screen<100 direction>and <001 direction>.The molecular sieve with BEA structure SiO2: Al2O3Molar ratio be 5-10:1；Preferably, the SiO of the molecular sieve with BEA structure2: Al2O3Molar ratio be 7-9:1.
In the case of, according to the invention it is preferred to, the molecular sieve with FAU and/or BEA structure is X-type molecular sieve, Y type At least one of molecular sieve, USY, REUSY, REHY, REY, PUSY, PREHY, PREY and beta-molecular sieve.
In the case of, according to the invention it is preferred to, it is viscous that heat-resistant inorganic oxide binder is selected from alumina binder, titanium dioxide Tie at least one of agent, zirconium dioxide binder and stannic oxide binder.
Preferably, the alumina binder can be changed into for aluminium oxide or under conditions of the described first roasting γ-Al2O3Substance.Under preferable case, the alumina binder can be selected from SB powder, hydrated alumina, Aluminum sol, a water In softening aluminium stone (boehmite), false boehmite (boehmite), hibbsite and amorphous hydroted alumina extremely Few one kind；Preferably, the alumina binder is at least one of SB powder, boehmite and Aluminum sol.
Preferably, the titanium dioxide binder is to hydrolyze in the acidic liquid, and in first roasting condition Under be changed into the substance of anatase titanium dioxide.Further, the titanium dioxide binder can be selected from titanium tetrachloride, titanium At least one of acetoacetic ester, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide.
Preferably, the zirconium dioxide binder is to hydrolyze in the acidic liquid, and in first roasting condition Under be changed into the substance of zirconium dioxide.Further, the zirconium dioxide binder can selected from zirconium chloride, zirconium oxychloride, At least one of acetic acid zirconium, hydrous zirconium oxide(HZO) and amorphous zirconium dioxide.
Preferably, the stannic oxide binder is to hydrolyze in the acidic liquid, and in first roasting condition Under be changed into the substance of stannic oxide.Further, the stannic oxide binder can be selected from tin tetrachloride, four isopropanols At least one of tin, tin acetate, aqua oxidation tin and stannic oxide.
In the present invention, the titanium dioxide binder, zirconium dioxide binder and stannic oxide binder are molten with excess acid Liquid contact, can hydrolyze and generate caking property colloidal solution.
According to the present invention, the acidic liquid can be acid or the aqueous solution of acid, and the acid can be selected from water-soluble Inorganic acid and/or organic acid, the preferably described acid can be at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
In the case of, according to the invention it is preferred to, the dosage of the acidic liquid makes the pH value 1~5 of the carrier pulp, excellent It is selected as 1.5~4.
In the present invention, step (1a) and (1b) middle amount that water is added can be not specially limited, as long as can obtain described Carrier pulp.Such as it is 5:1~10:1 that the amount of water and the weight ratio of the heat-resistant inorganic oxide binder, which is added,；Or The weight ratio that the amount of water and the weight summation of the heat-resistant inorganic oxide binder and SiCN is added is 5:1~10:1.
In the present invention, the obtained carrier pulp can be the forms such as paste or slurries.It can be by the carrier pulp Dry reshaping after thickening.The more preferable carrier pulp is slurry form, and it is 20-200 that granularity can be formed by spray drying The microballoon of micron, reaches molding purpose.For the ease of spray drying, the solid content of the dry preceding carrier pulp can be 10 ~50 weight %, preferably 20~50 weight %.It can also include that water is added during obtaining the carrier pulp, water There is no particular limitation for additional amount, as long as obtained carrier pulp meets above-mentioned solid content.
In the present invention, the first drying means and condition in step (2) are known to those skilled in the art, such as dry Method can be dry, dry, forced air drying.Under preferable case, the described first dry temperature can be room temperature~400 DEG C, preferably 100~350 DEG C；Described first dry time be 0.5h or more, preferably 0.5~100h, more preferably 2~ 20h。
In the present invention, the first roasting condition in step (2) is also known to those skilled in the art, under preferable case, The temperature of first roasting is 400~700 DEG C, preferably 450~650 DEG C；The time of first roasting is at least 0.5h, Preferably 0.5~100h, more preferably 0.5~10h.
According to the present invention, for step (3) for metallic promoter agent to be added, the metallic promoter agent is as previously shown.The metal The precursor of promotor is the substance that can be changed into the oxide of metallic promoter agent under the second roasting condition；Under preferable case, The precursor of the metallic promoter agent can be selected from acetate, carbonate, nitrate, sulfate, the rhodanate of metallic promoter agent At least one of with oxide.It is preferred that the precursor of the metallic promoter agent can be at least one of cobalt, nickel, iron and manganese At least one of acetate, carbonate, nitrate, sulfate, rhodanate and oxide；The preferably vinegar of nickel and/or cobalt At least one of hydrochlorate, carbonate, nitrate, sulfate, rhodanate and oxide；Can be preferably nickel nitrate and/or Cobalt nitrate；More preferably at least one of the acetate of nickel, carbonate, nitrate, sulfate, rhodanate and oxide； Particularly preferably nickel nitrate.
In the case of, according to the invention it is preferred to, the method that the precursor of metallic promoter agent is introduced on carrier is dipping or precipitating. The dipping can be the solution or suspension impregnation carrier with the precursor of metallic promoter agent；The precipitating can be to promote metal Solution or suspension into the precursor of agent are mixed with carrier, and ammonium hydroxide is then added by the precursor precipitation of metallic promoter agent in carrier On.
In the case of, according to the invention it is preferred to, the described second dry temperature is 50~300 DEG C, preferably 100~250 DEG C； Described second dry time was 0.5~8h, preferably 1~5h.
Preferably, the temperature of second roasting is 300~800 DEG C, preferably 450~750 DEG C；Second roasting Time is 0.5h or more, preferably 1~3h.Second roasting can carry out in the presence of oxygen or oxygen-containing gas, until Volatile materials is removed and the precursor of metallic promoter agent is converted into the oxide form of metallic promoter agent, obtains catalyst Precursor.
According to the present invention, in step (4), the oxide of the metallic promoter agent in the catalyst precarsor is changed into metal The catalyst precarsor can be restored under hydrogen atmosphere, deposit metallic promoter agent substantially with reduction-state by simple substance Obtaining catalyst of the invention.The condition of the reduction is only by the oxide of the metallic promoter agent in the catalyst precarsor It is changed into metal simple-substance, and the metal oxide in the carrier will not change.Under preferable case, the temperature of the reduction is 300~600 DEG C, preferably 400~500 DEG C；The time of the reduction is 0.5~6h, preferably 1~3h；The hydrogen gas The content of hydrogen is 10~60 volume % in atmosphere.
In the present invention, step (4) can carry out catalyst precarsor reduction immediately after catalyst precarsor is made, can also be with It is carried out (before being adsorbed for desulfurization) before use.Metal since metallic promoter agent is easy to oxidize, and in catalyst precarsor promotees Exist in the form of an oxide into agent, therefore to be readily transported, catalyst precarsor is restored and carrying out desulfurization absorption by preferred steps (4) Preceding progress.It is described to be reduced to make the metal in the oxide of metallic promoter agent substantially to exist with reduction-state, it obtains of the invention Desulphurization catalyst.
In the case of, according to the invention it is preferred to, the heat-resistant inorganic oxide binder, SiCN, the metal oxide and In the desulfurization of hydrocarbon oil catalyst that the additional amount of the precursor of the metallic promoter agent makes, with the desulfurization of hydrocarbon oil catalyst On the basis of total weight, the desulfurization of hydrocarbon oil catalyst contains the metal oxide of 10~80 weight %, preferably comprise 25~ 70 weight %, further preferably 40~60 weight %；Heat-resistant inorganic oxide containing 3~35 weight %, preferably comprises 6~25 Weight %, further preferably 8~15 weight %；SiCN containing 5~40 weight % preferably comprises 10~30 weight %, more excellent Choosing contains 12~25 weight %；The molecular sieve with FAU and/or BEA structure containing 1~20 weight %, preferably comprises 2~15 Weight %, further preferably 2~10 weight %；The metallic promoter agent containing 5~30 weight %, preferably comprises 8~25 weights Measure %, further preferably 12~20 weight %.
The present invention also provides desulfurization of hydrocarbon oil catalyst made from method of the invention.
The present invention also provides a kind of methods of desulfurization of hydrocarbon oil, this method comprises: in a hydrogen atmosphere, by hydrocarbon oil containing surphur with Desulfurization of hydrocarbon oil catalyst provided by the invention carries out desulphurization reaction at 350~500 DEG C, 0.5~4MPa；Preferably, 400~ 450 DEG C, carry out desulphurization reaction under 1.0~2.0MPa.The sulphur in hydrocarbon ils is adsorbed on catalyst in the process, to obtain The hydrocarbon ils of low sulfur content.
In the present invention, the catalyst after reaction can be reused after regeneration.The regeneration carries out under oxygen atmosphere, Regenerated condition includes: that regenerated pressure is normal pressure, and regenerated temperature is 400~700 DEG C, preferably 500~600 DEG C.
In the present invention, the catalyst after regeneration is before re-starting desulfurization of hydrocarbon oil, it is also necessary to it is restored under hydrogen atmosphere, The reducing condition of catalyst after regeneration includes: that temperature is 350~500 DEG C, preferably 400~450 DEG C；Pressure be 0.2~ 2MPa, preferably 0.2~1.5MPa.
In the present invention, the hydrocarbon ils includes cracking gasoline and diesel fuel, wherein " cracking gasoline " means that boiling range is 40 It is from making biggish hydrocarbon molecule be cracked into heat or catalytic process compared with small molecule DEG C to 210 DEG C of hydrocarbon or its any fraction Product.Applicable thermal cracking process includes but is not limited to coking, thermal cracking and visbreaking etc. and combinations thereof.Applicable catalysis The example of cracking process includes but is not limited to fluid catalystic cracking and heavy oil catalytic cracking etc. and combinations thereof.Therefore, applicable Catalytically cracked gasoline include but is not limited to coker gasoline, pressure gasoline, visbreaker gasoil, fluid catalystic cracking gasoline and Heavy oil cracked gasoline and combinations thereof.In some cases, in the methods of the invention be used as hydrocarbon-containifluids fluids when can before desulfurization incite somebody to action The cracking gasoline fractionation and/or hydrotreating.The hydrocarbon that " diesel fuel " means that boiling range is 170 DEG C to 450 DEG C mixes The liquid of object or its any fractional composition.Such hydrocarbon-containifluids fluids include but is not limited to light cycle oil, kerosene, straight-run diesel oil and add hydrogen Handle diesel oil etc. and combinations thereof.
Term used herein " sulphur " represents any type of element sulphur such as hydrocarbon-containifluids fluids such as cracking gasoline or diesel engine combustion The organosulfur compound being commonly present in material.Sulphur present in hydrocarbon-containifluids fluids of the present invention includes but is not limited to carbonyl sulfide (COS), two Nitric sulfid (CS2), mercaptan or other thiophenes etc. and combinations thereof, especially include thiophene, benzothiophene, alkylthrophene, The bigger thiophene-based chemical combination of the molecular weight being commonly present in alkyl benzothiophenes and methyldibenzothiophene and diesel fuel Object.
Contain SiCN component in the composition of desulfurization of hydrocarbon oil catalyst provided by the invention, the component is in the multiple anti-of catalyst Should with the effect of reacting with zinc oxide component is not easy in regenerative process, will not produce silicic acid zinc material make the desulfurization of hydrocarbon oil be catalyzed Agent reduces desulphurizing activated because losing zinc oxide.Catalyst of the present invention has very high desulphurizing activated, while also having apparent The property for increasing catalyst abrasion strength resistance is applicable to the reaction repeatedly of catalytically cracked gasoline or diesel fuel and regenerated Sweetening process.
The present invention will be described in detail by way of examples below.
The desulfurization of hydrocarbon oil catalyst that embodiment and comparative example obtains uses X-ray diffractometer (Siemens company D5005 type) XRD spectra is obtained, structure determination, Cu target, K α radiation, solid probe, tube voltage 40kV, tube current 40mA are carried out；
SiCN used in embodiment is SiCN-1, SiCN-2 and SiCN-3, by Sinopec catalyst Co., Ltd south Capital branch company provides, and specific structural features are shown in Table 1,
Table 1
Structure feature SiCN-1 SiCN-2 SiCN-3
Structure Hexagonal, sheet Hexagonal, column Hexagonal, sheet
Average particle size *, μm 9.5 3.6 15.0
Specific surface area, m2/g 10.0 26.0 3.2
N2 adsorption pore volume, cm3/g 0.08 0.10 0.03
* it is measured by laser particle analyzer (Mastersizer 2000 of Malvern company).
In the following Examples and Comparative Examples, the composition of desulfurization of hydrocarbon oil catalyst is calculated according to feeding intake.
Embodiment 1
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
(1) carrier is prepared.By Zinc oxide powder (Headhorse company, 99.7 weight % of purity), the 0.88kg of 4.43kg Beta-molecular sieve (catalyst asphalt in Shenli Refinery, contain butt 0.70kg) and the deionized water of 6.57kg mix, must after stirring 30 minutes To the mixed serum of zinc oxide and beta-molecular sieve；
Take the SiCN-1 stirring of boehmite 1.33kg (catalyst Nanjing branch company contains butt 1.00kg) and 2.06kg Then mixing is added deionized water 4.6kg and is uniformly mixed after slurries, to add the hydrochloric acid of the 30 weight % of 360ml (chemistry Pure, Beijing Chemical Plant produces) make slurries pH=2.1,80 DEG C of aging 2h are warming up to after stirring acidification 1h, add zinc oxide and β Stirring 1h obtains carrier pulp after the mixed serum mixing of molecular sieve；
The carrier pulp is used into Niro Bowen Nozzle TowerTMThe spray dryer of model is done by spraying Dry, spray drying pressure is 8.5 to 9.5MPa, and 500 DEG C of inlet temperature is hereinafter, outlet temperature is about 150 DEG C.By being spray-dried The first 1h dry at 180 DEG C of the microballoon arrived, then roasts 1h at 635 DEG C and obtains carrier；
(2) catalyst precarsor processed.By the carrier of 3.2kg with the Nickelous nitrate hexahydrate of 3.51kg (Beijing chemical reagents corporation, 98.5 weight % of purity >) and 0.6kg deionized water solution dipping, obtained dipping object is after 180 DEG C of dry 4h, in sky Catalyst precarsor is made in 635 DEG C of roasting 1h of gas atmosphere；
(3) it restores.By catalyst precarsor in hydrogen atmosphere reductase 12 h at 425 DEG C, obtain desulfurization of hydrocarbon oil catalyst A1.
The chemical composition of A1 are as follows: zinc oxide content is that 44.3 weight %, SiCN contents are 20.6 weight %, and beta-molecular sieve contains Amount is 7.0 weight %, and alumina content is 10.0 weight %, and nickel content is 18.1 weight %.
Embodiment 2
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
By the SiCN-2 stirring of boehmite 1.56kg (catalyst Nanjing branch company contains butt 1.17kg) and 1.50kg Then mixing is added deionized water 8.2kg and is uniformly mixed after slurries, to add the hydrochloric acid of the 30 weight % of 260ml and making slurries 80 DEG C of aging 2h are warming up to after pH=1.9, stirring acidification 1h.After temperature reduction after add 5.52kg Zinc oxide powder and The REUSY molecular sieve (catalyst asphalt in Shenli Refinery contains butt 0.3kg) of 0.38kg, and stir 1h and obtain carrier pulp.
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction To desulfurization of hydrocarbon oil catalyst A2.
The chemical composition of A2 are as follows: zinc oxide content is that 55.2 weight %, SiCN contents are 15.0 weight %, REUSY molecules Sieve content is 3.0 weight %, and alumina content is 11.7 weight %, and nickel content is 15.1 weight %.
Embodiment 3
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
By the USY molecular sieve of the Zinc oxide powder of 4.93kg, 0.63kg, (catalyst asphalt in Shenli Refinery contains butt 0.50kg), the SiCN-3 and 8.8kg of 2.1kg deionized water mixing, stirring 30 minutes after obtain zinc oxide, USY molecular sieve and The mixed serum of SiCN；
Boehmite 1.80kg (Shandong Aluminum Plant produces, and contains butt 1.36kg) and deionized water 4.6kg is taken to be uniformly mixed After slurries, the hydrochloric acid (chemistry is pure, and Beijing Chemical Plant produces) that the 30 weight % of 300ml are added makes slurries pH=2.5, stirring acid 80 DEG C of aging 2h are warming up to after changing 1h.Stirring 1h is carried after adding the mixed serum of zinc oxide, USY molecular sieve and SiCN-3 Somaplasm liquid.
The spray drying forming of carrier pulp is carried out referring to the method for embodiment 1.
Catalyst precarsor and catalyst are prepared referring to the method for embodiment 1, unlike, it is molten with nickel nitrate and cobalt nitrate Liquid substitutes Nickelous nitrate hexahydrate impregnated carrier, introduces active component nickel and cobalt, desulfurization of hydrocarbon oil catalyst A3 is obtained after reduction.
The chemical composition of A3 are as follows: zinc oxide content is that 49.3 weight %, SiCN contents are 16.0 weight %, USY molecular sieve Content is 5.0 weight %, and alumina content is 13.5 weight %, and nickel content is 8.1 weight %, and cobalt content is 8.1 weight %.
Embodiment 4
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
By the USY molecular sieve of the Zinc oxide powder of 4.93kg, 0.63kg, (catalyst asphalt in Shenli Refinery contains butt 0.50kg), the SiCN-1 and 8.8kg of 2.1kg deionized water mixing, stirring 30 minutes after obtain zinc oxide, USY molecular sieve and The mixed serum of SiCN；
Boehmite 1.80kg (Shandong Aluminum Plant produces, and contains butt 1.36kg) and deionized water 4.6kg is taken to be uniformly mixed After slurries, the hydrochloric acid that the 30 weight % of 300ml are added makes slurries pH=2.5, is warming up to 80 DEG C of aging 2h after stirring acidification 1h. Stirring 1h obtains carrier pulp after adding the mixed serum of zinc oxide, USY molecular sieve and SiCN.
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction To desulfurization of hydrocarbon oil catalyst A4.
The chemical composition of A4 are as follows: zinc oxide content is that 49.3 weight %, SiCN contents are 16.0 weight %, USY molecular sieve Content is 5.0 weight %, and alumina content is 13.5 weight %, and nickel content is 16.2 weight %.
Embodiment 5
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
The titanium tetrachloride (Beijing Chemical Plant analyzes pure, 99.7 weight %) of 2.40kg is slowly added to 5 weights of 4.6kg The dilute hydrochloric acid for measuring %, is slowly stirred and crystalline titanium dioxide is avoided to be precipitated, obtain the titanium colloidal sol pH=2.0 of pale yellow transparent；
By the Zinc oxide powder (Headhorse company, 99.7 weight % of purity) of 4.43kg, 0.88kg beta-molecular sieve, The deionized water of the SiCN-1 and 8.80kg of 2.06kg mix, and stirring obtains the mixed of zinc oxide, beta-molecular sieve and SiCN after 30 minutes Close slurries；Then above-mentioned titanium colloidal sol is added, 1h is stirred after mixing and obtains carrier pulp；
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction To desulfurization of hydrocarbon oil catalyst A5.
The chemical composition of A5 are as follows: zinc oxide content is that 44.3 weight %, SiCN contents are 20.6 weight %, and beta-molecular sieve contains Amount is 7.0 weight %, and content of titanium dioxide is 10.0 weight %, and nickel content is 18.1 weight %.
Embodiment 6
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
Titanium dioxide 1.25kg (Detitanium-ore-type contains butt 1.17kg) is taken to be slowly added to 3.0kg's in the case of stirring In the hydrochloric acid (chemistry is pure, and Beijing Chemical Plant produces) of 30 weight %, pH=1.9 is stirred to react 1h, obtains the titanium of pale yellow transparent Colloidal sol；
By the REUSY molecular sieve of SiCN-2,0.38kg of 1.50kg (catalyst asphalt in Shenli Refinery contains butt 0.30kg), The Zinc oxide powder of 5.52kg and the deionized water of 10.0kg mix under stiring, obtain zinc oxide, REUSY molecular sieve and The mixed serum of SiCN, is then added above-mentioned titanium colloidal sol and stirs 1h and obtain carrier pulp；
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction To desulfurization of hydrocarbon oil catalyst A2.
The chemical composition of A2 are as follows: zinc oxide content is that 55.2 weight %, SiCN contents are 15.0 weight %, and titanium dioxide contains Amount is that 11.7 weight %, REUSY molecular sieve contents are 3.0 weight %, and nickel content is 15.1 weight %.
Embodiment 7
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
Tetraethyl titanate 3.90kg (Aldrich analyzes pure, 99 weight %) is taken to be slowly added into the case of stirring In nitric acid (analysis is pure, and Beijing Chemical Plant produces) solution of the 10 weight % of 3.8kg, pH=2.3, and 1h is stirred, it obtains yellowish The transparent titanium colloidal sol of color；
By the USY molecular sieve of the Zinc oxide powder of 4.93kg, 0.63kg, (catalyst asphalt in Shenli Refinery contains butt 0.50kg), the deionized water mixing of the SiCN-3 and 10.8kg of 1.6kg, stirring obtained zinc oxide, USY molecular sieve after 30 minutes With the mixed serum of SiCN, titanium colloidal sol is then added and stirs 1h and obtains carrier pulp；
The spray drying forming of carrier pulp is carried out referring to the method for embodiment 1.
Catalyst precarsor and catalyst are prepared referring to the method for embodiment 1, unlike, it is molten with nickel nitrate and cobalt nitrate Liquid substitutes Nickelous nitrate hexahydrate impregnated carrier, introduces active component nickel and cobalt, desulfurization of hydrocarbon oil catalyst A7 is obtained after reduction.
The chemical composition of A7 are as follows: zinc oxide content is that 49.3 weight %, SiCN contents are 16.0 weight %, and titanium dioxide contains Amount is 13.5 weight %, and USY molecular sieve content is 5.0 weight %, and nickel content is 8.1 weight %, and cobalt content is 8.1 weight %.
Embodiment 8
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
Tetraethyl titanate 3.90kg (Aldrich analyzes pure, 99 weight %) is taken to be slowly added into the case of stirring In nitric acid (analysis is pure, and Beijing Chemical Plant produces) solution of the 10 weight % of 3.8kg, pH=2.3, and 1h is stirred, it obtains yellowish The transparent titanium colloidal sol of color；
By USY molecular sieve (the catalyst Shandong point public affairs of the Zinc oxide powder of 4.93kg, SiCN-1,0.63kg of 1.6kg Department, the deionized water mixing containing butt 0.50kg) and 10.8kg, stirring obtained zinc oxide, USY molecular sieve and SiCN after 30 minutes Mixed serum；Then titanium colloidal sol is added and stirs 1h and obtains carrier pulp；
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction To desulfurization of hydrocarbon oil catalyst A8.
The chemical composition of A8 are as follows: zinc oxide content is that 49.3 weight %, SiCN contents are 16.0 weight %, and titanium dioxide contains Amount is 13.5 weight %, and USY molecular sieve content is 5.0 weight %, and nickel content is 16.2 weight %.
Embodiment 9
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
The zirconium chloride (Beijing Chemical Plant analyzes pure, 99 weight %) of 2.60kg is slowly added to the 5 weight % of 4.6kg Nitric acid solution in, be slowly stirred avoid zirconium oxide crystallization be precipitated, obtain the zirconium colloidal sol pH=2.1 of pale yellow transparent；
By the Zinc oxide powder (Headhorse company, 99.7 weight % of purity) of 4.43kg, 1.90kg SiCN-2, The USY molecular sieve (catalyst asphalt in Shenli Refinery contains butt 0.50kg) and the deionized water of 6.57kg of 0.63kg mixes, stirring 30 Zinc oxide and the mixed serum of SiCN are obtained after minute；Then above-mentioned zirconium colloidal sol is added, 1h is stirred after mixing and obtains carrier pulp；
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction To desulfurization of hydrocarbon oil catalyst A9.
The chemical composition of A9 are as follows: zinc oxide content is that 44.3 weight %, SiCN contents are 19.0 weight %, USY molecular sieve Content is 5.0 weight %, and zirconium dioxide content is 13.6 weight %, and nickel content is 18.1 weight %.
Embodiment 10
This example demonstrates that the preparation method of desulfurization of hydrocarbon oil catalyst of the invention.
By the tin tetrachloride (SnCl of 3.21kg4·5H2O, Alfa company, 99%) it is slowly added to the 5 weight %'s of 4.6kg Nitric acid solution is slowly stirred and oxidation tin crystals is avoided to be precipitated, obtains colorless and transparent tin oxide sol pH=2.1；
By the Zinc oxide powder (Headhorse company, 99.7 weight % of purity) of 4.43kg, 1.90kg SiCN-3, The USY molecular sieve (catalyst asphalt in Shenli Refinery contains butt 0.50kg) and the deionized water of 6.57kg of 0.63kg mixes, stirring 30 Zinc oxide and the mixed serum of SiCN are obtained after minute；Then above-mentioned tin oxide sol is added, 1h is stirred after mixing and obtains carrier pulp；
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction To desulfurization of hydrocarbon oil catalyst A10.
The chemical composition of A10 are as follows: zinc oxide content is that 44.3 weight %, SiCN contents are 19.0 weight %, USY molecular sieve Content is 5.0 weight %, and stannic oxide content is 13.6 weight %, and nickel content is 18.1 weight %.
Comparative example 1
The deionized water of the Zinc oxide powder of 4.43kg and 6.57kg are mixed, stirring obtained zinc oxide paste after 30 minutes Liquid；
Take the expanded perlite of boehmite 1.81kg (catalyst Nanjing branch company contains butt 1.36kg) and 2.46kg (catalyst Nanjing branch company contains butt 2.40kg) is stirred, and deionized water 4.6kg is then added and is uniformly mixed, adds The hydrochloric acid of the 30 weight % of 360ml makes slurries pH=2.1, is warming up to 80 DEG C of aging 2h after stirring acidification 1h, adds zinc oxide Stirring 1h obtains carrier pulp after slurries mixing.
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction To desulfurization of hydrocarbon oil catalyst B1.
The chemical composition of B1 are as follows: zinc oxide content is 44.3 weight %, and expanded perlite content is 24.0 weight %, oxidation Aluminium content is 13.6 weight %, and nickel content is 18.1 weight %.
Comparative example 2
Boehmite 1.56kg (Shandong Aluminum Plant produces, and contains butt 1.17kg) and the diatomite of 1.85kg is taken (to contain butt It 1.80kg) is stirred, deionized water 8.2kg is then added and is uniformly mixed, the hydrochloric acid for adding the 30 weight % of 260ml makes to starch 80 DEG C of aging 2h are warming up to after liquid pH=1.9, stirring acidification 1h.The Zinc oxide powder of 5.52kg is added simultaneously after temperature reduction Stirring 1h obtains carrier pulp.
Method referring to embodiment 1 carries out the spray drying forming of carrier pulp and introduces active component nickel, after reduction To desulfurization of hydrocarbon oil catalyst B2.
The chemical composition of B2 are as follows: zinc oxide content is 55.2 weight %, and diatomite content is 18.0 weight %, and aluminium oxide contains Amount is 11.7 weight %, and nickel content is 15.1 weight %.
Comparative example 3
The deionized water of the Zinc oxide powder of 4.93kg and 5.57kg are mixed, stirring obtained zinc oxide paste after 30 minutes Liquid；
Take boehmite 1.80kg's (Shandong Aluminum Plant produces, and contains butt 1.35kg) and 2.16kg to go to the diatomite (world Mining company contains butt 2.10kg) it is stirred, deionized water 4.6kg is then added and is uniformly mixed, adds the 30 of 300ml The hydrochloric acid of weight % makes slurries pH=2.5, is warming up to 80 DEG C of aging 2h after stirring acidification 1h.After adding the mixing of zinc oxide slurries Stirring 1h obtains carrier pulp.
Method referring to embodiment 3 carries out the spray drying forming of carrier pulp and introduces active component nickel and cobalt, restores After obtain desulfurization of hydrocarbon oil catalyst B3.
The chemical composition of B3 are as follows: zinc oxide content is 49.3 weight %, and diatomite content is 21.0 weight %, and aluminium oxide contains Amount is 13.5 weight %, and nickel content is 8.1 weight %, and cobalt content is 8.1 weight %.
Comparative example 4
The deionized water of the Zinc oxide powder of 4.93kg and 5.57kg are mixed, stirring obtained zinc oxide paste after 30 minutes Liquid；
Taking boehmite 1.80kg (Shandong Aluminum Plant produces, and contains butt 1.35kg) and the kaolin of 2.84kg, (Suzhou is high Ling Tu factory contains butt 2.10kg) it is stirred, deionized water 3.6kg is then added and is uniformly mixed, adds 30 weights of 300ml The hydrochloric acid of amount % makes slurries pH=2.5, is warming up to 80 DEG C of aging 2h after stirring acidification 1h.It is stirred after adding the mixing of zinc oxide slurries It mixes 1h and obtains carrier pulp.
Method referring to embodiment 1 carries out the spray drying forming of mixing taste and introduces active component nickel, obtains after reduction Desulfurization of hydrocarbon oil catalyst B4.
The chemical composition of B4 are as follows: zinc oxide content is 49.3 weight %, and kaolin content is 21.0 weight %, and aluminium oxide contains Amount is 13.5 weight %, and nickel content is 16.2 weight %.
Comparative example 5
According to the method for embodiment 1, it unlike, is prepared according to embodiment 2 in CN101774593A ordered porous Carbonitride of silicium material obtains desulfurization of hydrocarbon oil with the SiCN-1 of the ordered porous carbonitride of silicium material substitution 2.06kg of 2.06kg Catalyst B5.
The chemical composition of B5 are as follows: zinc oxide content is 44.3 weight %, and ordered porous carbonitride of silicium material content is 20.6 Weight %, beta-molecular sieve content are 7.0 weight %, and alumina content is 10.0 weight %, and nickel content is 18.1 weight %.
Embodiment 11
(1) abrasion strength resistance is evaluated.Abrasion strength resistance test is carried out to desulfurization of hydrocarbon oil catalyst A1-A10 and B1-B5.It adopts Method is worn with straight tube, method the results are shown in Table 2 with reference to RIPP 29-90 in " petrochemical analysis method (RIPP) experimental method ". It is smaller to test obtained numerical value, shows that abrasion strength resistance is higher.It is when wearing under certain condition that abrasion index is corresponding in table 2 The percentage that fine powder generates.
(2) desulfurization performance is evaluated.To desulfurization of hydrocarbon oil catalyst A1-A10 and B1-B5 using the micro- anti-experimental provision of fixed bed into Row HDS evaluation experiment, by 16 grams of desulfurization of hydrocarbon oil Catalyst packing in the fixed bed reactors that internal diameter is 30mm, a length of 1m. Raw material hydrocarbon ils is the catalytically cracked gasoline of sulphur concentration 780ppm, reaction pressure 1.38MPa, hydrogen flowing quantity 6.3L/h, gasoline Flow is 80mL/h, and reaction temperature is 410 DEG C, and the weight space velocity of raw material hydrocarbon ils is 4h-1, carry out the desulphurization reaction of hydrocarbon oil containing surphur. It is measured with sulfur content in product gasoline desulphurizing activated.Sulfur content is prompt using peace by offline chromatogram analysis method in product gasoline The GC6890-SCD instrument of logical sequence company is measured.In order to which accurate characterization goes out desulfurization of hydrocarbon oil catalyst in industrial actual motion Activity, the catalyst after the completion of HDS evaluation experiment carry out regeneration treatment under 550 DEG C of air atmosphere.Desulfurization of hydrocarbon oil is catalyzed Agent carries out HDS evaluation experiment, its activity settles out substantially after regenerating 6 circulations, after the 6th stable circulation of catalyst Sulfur content in product gasoline indicates the activity of catalyst, and sulfur content is as shown in table 2 in product gasoline after stablizing.
GB/T 503-1995 and GB/T 5487-1995 is respectively adopted to measure before reaction and gasoline after the 6th stable circulation Motor octane number (MON) and research octane number (RON) (RON), the results are shown in Table 2.
Table 2
Note: the data in table in relation to octane number are the variable quantities of the octane number compared to feed gasoline."-" indicate compared to The octane number of feed gasoline reduces.
1, the sulfur content of feed gasoline is 780ppm, RON 93.0, MON 82.7.
2, △ MON indicates the value added of product MON；
3, △ RON indicates the value added of product RON；
4, △ (RON+MON)/2 is the difference of product anti-knock index and raw material anti-knock index.
It can be seen that in desulfurization of hydrocarbon oil catalyst provided by the invention from the result data of table 2 containing SiCN component, hydrocarbon ils The sulfur content for reducing gasoline still can be well realized after carrying out multiple circulation desulfurization in desulphurization catalyst, illustrates that the catalyst has There is better desulphurizing activated and activity stability.And the abrasion index of the desulfurization of hydrocarbon oil catalyst is lower, illustrates to have more preferable Abrasion strength resistance, so as to so that the desulfurization of hydrocarbon oil catalyst has longer service life.Desulfurization of hydrocarbon oil in comparative example 5 is urged Agent contains ordered porous carbonitride of silicium material, the SiCN without containing the application, therefore abrasion index and is made much higher than embodiment Catalyst abrasion index, illustrate that desulfurization of hydrocarbon oil catalyst provided by the invention can have better wear-resisting property.
Embodiment 12
Aging, condition are carried out to desulfurization of hydrocarbon oil catalyst A1-A10 and B1-B5 are as follows: catalyst is placed in 600 DEG C, water steaming 16h is handled under the atmosphere that gas partial pressure is 20kPa.
To before and after aging A1 and B1 carry out XRD spectra analysis, wherein XRD spectra such as Fig. 1 institute before and after A1 hydrothermal aging Show, fresh dose there are the crystal phase peaks of SiCN at 2 θ=36.7 ° and 60.0 ° with aging agent；XRD spectrum before and after B1 hydrothermal aging Figure is as shown in Figure 2.Do not occur in Fig. 1, in the XRD spectra after A1 hydrothermal aging zinc silicate 2 θ=22.0,25.54, 48.9 and 59.4 characteristic peak；In Fig. 2, occurs the features described above peak of zinc silicate in the XRD spectra after B1 hydrothermal aging.It adopts With the silicic acid Zn content in the XRD spectra of crystal content quantitative analysis B1-B5, it the results are shown in Table 3.
The desulfurization performance that A1-A10 and B1-B5 after aging are evaluated with evaluation method identical with embodiment 11, is as a result shown in Table 3.
Table 3
Note: the data in table in relation to octane number are the variable quantities of the octane number compared to feed gasoline."-" indicate compared to The octane number of feed gasoline reduces.
1, the sulfur content of feed gasoline is 780ppm, RON 93.0, MON 82.7.
2, △ MON indicates the value added of product MON；
3, △ RON indicates the value added of product RON；
4, △ (RON+MON)/2 is the difference of product anti-knock index and raw material anti-knock index.
From the results shown in Table 3, it after ageing process, is not generated in the desulfurization of hydrocarbon oil catalyst that embodiment obtains Zinc silicate, and the catalyst in comparative example 1-4, zinc oxide can generate zinc silicate with the material of silicon oxide-containing, to make catalyst Desulphurizing activated reduction.
The data of product gasoline can also be seen that the still available high product of method provided by the invention from table 2 and 3 Yield of gasoline, the octane number of gasoline can also improve.

Claims (15)

1. a kind of desulfurization of hydrocarbon oil catalyst, on the basis of the total weight of the desulfurization of hydrocarbon oil catalyst, which contains Have:
1) zinc oxide of 10~80 weight %；
2) heat-resistant inorganic oxide of 3~35 weight %；
3) SiCN of 5~40 weight %；
4) molecular sieve with FAU and/or BEA structure of 1~20 weight %；
5) metallic promoter agent of 5~30 weight %, the metallic promoter agent are selected from least one of cobalt, nickel, iron and manganese；
Wherein, the heat-resistant inorganic oxide is at least one of aluminium oxide, titanium dioxide, zirconium dioxide and stannic oxide；
The SiCN has hexagonal crystallographic texture, in the form of sheets or column structure；The grain diameter of the SiCN is 1~20 μm； The specific surface area of SiCN is 1 m2The m of/g~302/g；The N2 adsorption pore volume of SiCN is 0.02 cm3The cm of/g~0.123/g。
2. desulfurization of hydrocarbon oil catalyst according to claim 1, wherein using the total weight of the desulfurization of hydrocarbon oil catalyst as base Standard, the desulfurization of hydrocarbon oil catalyst contain the zinc oxide of 40~60 weight %, the heat-resistant inorganic oxide of 8~15 weight %, and 12 The molecular sieve with FAU and/or BEA structure of the SiCN of~25 weight %, 2~10 weight %；The metal of 12~20 weight % Promotor.
3. desulfurization of hydrocarbon oil catalyst according to claim 1 or 2, wherein the desulfurization of hydrocarbon oil catalyst is obtained through XRD analysis To spectrogram in 2 θ be 36.7 ° and 60.0 ° at there are the crystal phase peaks of SiCN.
4. desulfurization of hydrocarbon oil catalyst according to claim 1 or 2, wherein the molecule with FAU and/or BEA structure It sieves as at least one in X-type molecular sieve, Y type molecular sieve, USY, REUSY, REHY, REY, PUSY, PREHY, PREY and beta-molecular sieve Kind.
5. the method for preparing desulfurization of hydrocarbon oil catalyst described in any one of claim 1-4, comprising:
SiCN, heat-resistant inorganic oxide binder, water and acidic liquid are contacted and to form slurries by (1a), by the slurries and tool There are the molecular sieve of FAU and/or BEA structure, zinc oxide to be mixed to get carrier pulp；
Or
(1b) contacts heat-resistant inorganic oxide binder, water and acidic liquid to form slurries, by the slurries and has FAU And/or the molecular sieve of BEA structure, zinc oxide, SiCN are mixed to get carrier pulp；
(2) carrier pulp is formed, first dry, the first roasting, obtains carrier；
(3) precursor of metallic promoter agent is introduced in the carrier, is then carried out second dry and the second roasting, is obtained catalyst Precursor；
(4) catalyst precarsor is restored in a hydrogen atmosphere, obtains desulfurization of hydrocarbon oil catalyst；
Wherein, the heat-resistant inorganic oxide is at least one of aluminium oxide, titanium dioxide, zirconium dioxide and stannic oxide.
6. SiCN has hexagonal crystallographic texture according to the method described in claim 5, wherein, in the form of sheets or column structure.
7. method according to claim 5 or 6, wherein the grain diameter of SiCN is 1~20 μm；The specific surface area of SiCN For 1 m2The m of/g~302/g；The N2 adsorption pore volume of SiCN is 0.02 cm3The cm of/g~0.123/g。
8. according to the method described in claim 7, wherein, the grain diameter of SiCN is 3~15 μm；The N2 adsorption pore volume of SiCN For 0.03 cm3/ g~0.10cm3/g。
9. according to the method described in claim 5, wherein, the heat-resistant inorganic oxide binder be selected from alumina binder, At least one of titanium dioxide binder, zirconium dioxide binder and stannic oxide binder；The alumina binder is Selected from least one of hydrated alumina, Aluminum sol and amorphous hydroted alumina；The titanium dioxide binder is selected from tetrachloro Change at least one of titanium, tetraethyl titanate, isopropyl titanate, acetic acid titanium, hydrous titanium oxide and anatase titanium dioxide；It is described Zirconium dioxide binder in zirconium chloride, zirconium oxychloride, acetic acid zirconium, hydrous zirconium oxide(HZO) and amorphous zirconium dioxide extremely Few one kind；The stannic oxide binder is selected from tin tetrachloride, four isopropanol tin, tin acetate, aqua oxidation tin and stannic oxide At least one of.
10. according to the method described in claim 9, wherein, the hydrated alumina is selected from boehmite, false boehmite At least one of with hibbsite.
11. according to the method described in claim 5, wherein, the precursor of the metallic promoter agent is selected from the acetic acid of metallic promoter agent At least one of salt, carbonate, nitrate, sulfate, rhodanate and oxide.
12. according to the method described in claim 5, wherein, the dosage of the acidic liquid makes the pH value 1 of the carrier pulp ~5；The acidic liquid is the aqueous solution of acid or acid, and the acid is selected from water-soluble inorganic acid and/or organic acid.
13. according to the method described in claim 5, wherein, the described first dry temperature is room temperature~400 DEG C, described first The dry time is 0.5~8 h；The temperature of first roasting is 400~700 DEG C, and the time of first roasting is 0.5 h More than；Described second dry temperature is 50~300 DEG C, and the described second dry time was 0.5~8 h；Second roasting Temperature be 300~800 DEG C, it is described second roasting time be 0.5~4 h；The temperature of the reduction is 300~600 DEG C, institute The time for stating reduction is 0.5~6h, and hydrogen content is 10~60 volume % in the hydrogen atmosphere.
14. desulfurization of hydrocarbon oil catalyst made from method described in any one of claim 5-13.
15. a kind of method of desulfurization of hydrocarbon oil, comprising: in a hydrogen atmosphere, will be any in hydrocarbon oil containing surphur and claim 1-5 and 14 Desulfurization of hydrocarbon oil catalyst described in one carries out desulphurization reaction at 350~500 DEG C, 0.5~4MPa.
CN201610010223.5A 2016-01-08 2016-01-08 A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil Active CN106955730B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610010223.5A CN106955730B (en) 2016-01-08 2016-01-08 A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610010223.5A CN106955730B (en) 2016-01-08 2016-01-08 A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil

Publications (2)

Publication Number Publication Date
CN106955730A CN106955730A (en) 2017-07-18
CN106955730B true CN106955730B (en) 2019-04-16

Family

ID=59480476

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610010223.5A Active CN106955730B (en) 2016-01-08 2016-01-08 A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil

Country Status (1)

Country Link
CN (1) CN106955730B (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1627988A (en) * 2002-04-11 2005-06-15 科诺科菲利浦公司 Desulfurization and sorbents for same
CN1871063A (en) * 2003-08-25 2006-11-29 科诺科菲利浦公司 Desulfurization and novel methods for same
CN102343249A (en) * 2010-07-29 2012-02-08 中国石油化工股份有限公司 Hydrocarbon oil desulphurization adsorbent, its preparation method and its application
CN102688783A (en) * 2011-03-25 2012-09-26 中国石油化工股份有限公司 Alkyne selective hydrogenation catalyst carrier and preparation method and catalyst thereof
CN103724034A (en) * 2013-07-23 2014-04-16 太仓派欧技术咨询服务有限公司 Silicon carbide whisker reinforced silicon nitride ceramic composite material and preparation method thereof
CN104294203A (en) * 2014-09-11 2015-01-21 芜湖鼎瀚再制造技术有限公司 Al2O3-TiO2 nano coating and preparation method thereof
CN104877556A (en) * 2015-06-05 2015-09-02 贵阳明通炉料有限公司 Composite coating with wear resistance, heat resistance and corrosion resistance

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1627988A (en) * 2002-04-11 2005-06-15 科诺科菲利浦公司 Desulfurization and sorbents for same
CN1871063A (en) * 2003-08-25 2006-11-29 科诺科菲利浦公司 Desulfurization and novel methods for same
CN102343249A (en) * 2010-07-29 2012-02-08 中国石油化工股份有限公司 Hydrocarbon oil desulphurization adsorbent, its preparation method and its application
CN102688783A (en) * 2011-03-25 2012-09-26 中国石油化工股份有限公司 Alkyne selective hydrogenation catalyst carrier and preparation method and catalyst thereof
CN103724034A (en) * 2013-07-23 2014-04-16 太仓派欧技术咨询服务有限公司 Silicon carbide whisker reinforced silicon nitride ceramic composite material and preparation method thereof
CN104294203A (en) * 2014-09-11 2015-01-21 芜湖鼎瀚再制造技术有限公司 Al2O3-TiO2 nano coating and preparation method thereof
CN104877556A (en) * 2015-06-05 2015-09-02 贵阳明通炉料有限公司 Composite coating with wear resistance, heat resistance and corrosion resistance

Also Published As

Publication number Publication date
CN106955730A (en) 2017-07-18

Similar Documents

Publication Publication Date Title
CN105289706B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN105289701B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN105289705B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN105289683B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN107970941A (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN105312078B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN107970961B (en) Hydrocarbon oil desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method
CN106955735B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN105498830A (en) Desulfurization catalyst, preparation method thereof and method for desulfurizing hydrocarbon oil by employing same
CN105289632B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN107970994A (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN105854929B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN107970963B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN105289681B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN113731427B (en) Dual-function desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method
CN106955730B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN107970962A (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN105312084B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN106955732B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN106955723B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN105312073B (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil
CN107970993B (en) Hydrocarbon oil desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method
CN107970968B (en) Hydrocarbon oil desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method
CN107971030B (en) Hydrocarbon oil desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method
CN107970977A (en) A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil

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
GR01 Patent grant
GR01 Patent grant