CN107970977A - 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 PDFInfo
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- CN107970977A CN107970977A CN201610920674.2A CN201610920674A CN107970977A CN 107970977 A CN107970977 A CN 107970977A CN 201610920674 A CN201610920674 A CN 201610920674A CN 107970977 A CN107970977 A CN 107970977A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to desulfurization of hydrocarbon oil field, the method for disclosing a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil.On the basis of the gross 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) aluminium oxide of 3~35 weight %；3) vanadium carbide of 5~40 weight %；4) molecular sieve with FAU and/or BEA structures 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 the desulphurizing activated of more preferable stability and higher, and more preferable abrasion resistance properties, service life is longer, while also has the advantage of obvious increase octane number.
Description
Technical field
The present invention relates to desulfurization of hydrocarbon oil field, and in particular, to a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof and hydrocarbon
The method of oily desulfurization.
Background technology
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 one of most important measure for improving air quality.Most of sulphur in China's gasoline products come 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 in China《Motor petrol》It is required that on December 31st, 2013,
Sulfur content must drop to 50 μ g/g in gasoline products.And following gasoline product quality standard will be stringenter.At this
In the case of kind, catalytically cracked gasoline has to pass through the requirement that deep desulfuration can just make gasoline products meet environmental protection.
At present, the process for deep desulphurization of oil product mainly selective two kinds of desulfurization of catalytic desulfurhydrogenation and catalytic hydrogenation absorption
Method.Catalytic hydrogenation absorption desulfurization is to realize under conditions of hydrogen to inhale in the sulfide in hydrocarbon ils in certain temperature, pressure and facing
Attached removing, it is not high which has the characteristics that hydrogen consumes low and to hydrogen purity requirement so that the technology is in terms of fuel desulfuration
Have broad application prospects.
CN1355727A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel
Thing, is made of zinc oxide, silica, oxidation al and ni, and for wherein nickel substantially to reduce valence state presence, its amount can be from de-
Sulphur is removed in the cracking gasoline or diesel fuel stream that are contacted under the conditions of sulphur with the nickeliferous adsorbent composition.Said composition is led to
Cross and be granulated to form particle by the compound particles that zinc oxide, silica and aluminium oxide are formed, nickel or nickeliferous chemical combination are used after dry, roasting
Thing impregnates, and re-dry, roasting, reduction obtain.
CN1382071A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel
Thing, is made of zinc oxide, silica, aluminium oxide and cobalt, and for wherein cobalt substantially to reduce valence state presence, its amount can be from de-
Sulphur is removed in the cracking gasoline or diesel fuel stream that are contacted under the conditions of sulphur with the adsorbent composition containing cobalt.
US6150300 disclose it is a kind of prepare the method for adsorbent, including prepare spheric granules：(a) silica will be contained
Composition, the composition containing scattered metal oxide in an aqueous medium and the composition containing zinc oxide mix shape
First mixture is not extruded into the first mixture and；(b) forming the first mixture globulate has diameter 10-
The particle of 1000mm.Wherein step (a) is further included mixes with metallic promoter agent.
CN1422177A discloses a kind of combination of adsorbents suitable for removing sulphur from cracking gasoline and diesel fuel
Thing, is made of zinc oxide, expanded perlite, aluminium oxide and promoter metals, wherein the promoter metals are substantially to reduce
Valence state and while contacting under desulfurization conditions amount that sulphur can be removed from cracking gasoline or diesel fuel stream exist.
CN1627988A discloses one kind and is suitable for removing elementary sulfur and vulcanization conjunction from cracking gasoline and diesel fuel
The adsorbent composition of thing, the adsorbent composition include：Zinc oxide, expanded perlite, aluminate and promoter metals, its
Described in promoter metals will cause from cracking when making cracking gasoline or diesel fuel stream contacts under desulfurization conditions with it
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, including：A) mixing liquid, zinc compound, containing two
Silica material, aluminium oxide and co-catalyst, to form its mixture；B) dry mixture, to be formed through dry mixing
Thing；C) this is calcined through dry mixture, to form the mixture through calcining；D) with appropriate reducing agent under suitable condition
The mixture through calcining is reduced, to produce the composition of the co-catalyst content in it with reduction valence state, and e)
Recycling reorganization compound.Co-catalyst contains selected from various metals such as nickel.
CN1871063A discloses a kind of method for producing composition, and this method includes：A) by liquid, zinc compound,
Mixed containing earth silicon material, aluminium oxide to form its mixture；B) mixture is dried into the mixing to form first
Through drying composite；C) described first is calcined to form first through calcining mixt through drying composite；D) by accelerating agent knot
Close described first through within calcining mixt or on to form promoted mixture；E) the promoted mixture and choosing are made
Contacted 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 drying with
Second is formed through drying composite；G) described second is calcined to form second through calcining mixt through drying composite；H) exist
Suitable reducing agent reduction described second is used wherein to promote through calcining mixt to produce containing reduction valence state under conditions of appropriate
Into the composition of agent content, 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 requirement is also constantly stringent.And abrasion easily occurs in use for such catalyst, it is necessary to be continuously replenished
Catalyst, improves operating cost.As can be seen here, it is necessary to which providing a kind of there is more high desulfurization activity and the new of abrasion resistance properties to urge
Agent.
The content 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 be poor the defects of, there is provided the method for a kind of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil.
To achieve these goals, 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) aluminium oxide of 3~35 weight %；3) vanadium carbide of 5~40 weight %；4) 1~20 weight %'s has
The molecular sieve of FAU and/or BEA structures；5) metallic promoter agent of 5~30 weight %, the metallic promoter agent are selected from cobalt, nickel, iron
At least one of with manganese.
Present invention also offers the method for the desulfurization of hydrocarbon oil catalyst for preparing the present invention, including：(1a) by vanadium carbide, oxidation
Al binder, water and acidic liquid contact to form slurries, by the slurries with FAU and/or BEA structures molecular sieve,
At least one metal oxide selected from IIB, VB and group vib element is mixed to get carrier pulp；Or (1b) glues aluminium oxide
Knot agent, water and acidic liquid contact to form slurries, by the slurries and the molecular sieve with FAU and/or BEA structures, at least one
Metal oxide, vanadium carbide of the kind selected from IIB, VB and group vib element are mixed to get carrier pulp；(2) by the carrier pulp
Be molded, first drying, first roasting, obtain carrier；(3) precursor of metallic promoter agent is introduced in the carrier, then
The second drying and the second roasting are carried out, obtains catalyst precarsor；(4) catalyst precarsor is reduced in a hydrogen atmosphere, obtained
To desulfurization of hydrocarbon oil catalyst.
Present invention also offers desulfurization of hydrocarbon oil catalyst made from the method for the present invention.
Present invention also offers a kind of method of desulfurization of hydrocarbon oil, including：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 under 350~500 DEG C, 0.5~4MPa.
The vanadium carbide (VC) stablized in the composition of desulfurization of hydrocarbon oil catalyst provided by the invention containing chemical property, reduces
With the dependent interaction of the metal oxide such as zinc oxide, avoid such as the formation of silicic acid zinc material, such as the embodiment 1 that Fig. 1 is shown
The characteristic peak of zinc silicate is not present in XRD spectra after the hydrothermal aging of the desulfurization of hydrocarbon oil catalyst A1 of acquisition.The present invention provides
Desulfurization of hydrocarbon oil catalyst there is the desulphurizing activated of more preferable stability and higher, can be during desulfurization of hydrocarbon oil more effectively
Sulphur in hydrocarbon ils is adsorbed onto on desulfurization of hydrocarbon oil catalyst, obtains the lower hydrocarbon ils of sulfur content.And hydrocarbon ils provided by the invention
Desulphurization catalyst has a more preferable abrasion resistance properties, and catalyst attrition is lower in sweetening process, and service life is longer.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description of the drawings
Attached drawing is for providing a further understanding of the present invention, and a part for constitution instruction, 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 spectrums of the obtained desulfurization of hydrocarbon oil catalyst A1 of embodiment 1 before and after hydrothermal aging；
Fig. 2 is XRD spectrums of the obtained desulfurization of hydrocarbon oil catalyst B1 of comparative example 1 before and after hydrothermal aging.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of desulfurization of hydrocarbon oil catalyst, on the basis of the gross 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 aluminium oxide of~35 weight %；3) vanadium carbide of 5~40 weight %；4) 1~20 weight %'s has FAU and/or BEA structures
Molecular sieve；5) metallic promoter agent of 5~30 weight %, the metallic promoter agent are selected from least one of cobalt, nickel, iron and manganese.
Preferably, on the basis of the gross weight of the desulfurization of hydrocarbon oil catalyst, using the gross weight of the desulfurization of hydrocarbon oil catalyst as
Benchmark, the desulfurization of hydrocarbon oil catalyst contain the metal oxide of 25~70 weight %, the aluminium oxide of 6~25 weight %, and 10
The vanadium carbide of~30 weight %, the molecular sieve with FAU and/or BEA structures of 2~15 weight %, 8~25 weight %'s
The metallic promoter agent.
It is highly preferred that on the basis of the gross weight of the desulfurization of hydrocarbon oil catalyst, with the gross weight of the desulfurization of hydrocarbon oil catalyst
On the basis of, which contains the metal oxide of 40~60 weight %, the aluminium oxide of 8~15 weight %,
The vanadium carbide of 12~25 weight %, the molecular sieve with FAU and/or BEA structures of 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 37.3 °, 43.36 °
With 63.10 ° at there are vanadium carbide crystalline phase peak.
Contain the vanadium carbide with face-centered cubic crystal structure in desulfurization of hydrocarbon oil catalyst provided by the invention as structure
Constituent element, since the structure vanadium carbide has very high hydrothermal stability, can be effectively prevented from during desulfurization of hydrocarbon oil is carried out
Such as silicic acid zinc material is formed in the composition of the catalyst, ensures that the catalyst has more preferable desulphurizing activated and stability.Preferably,
Do not have in XRD spectra of the desulfurization of hydrocarbon oil catalyst after hydrothermal aging at 2 θ is 22.0 °, 25.54 °, 48.9 ° and 59.4 °
Occur the characteristic peak of zinc silicate.The condition of the hydrothermal aging includes：Temperature is 500~700 DEG C, steam partial pressure be 10~
30kPa, processing time are 10~24h.
According to the present invention, the FAU structure molecular screens are faujasite-type molecular sieve, and the type molecular sieve has three-dimensional ten
Two membered ring channels, aperture areThe FAU structure molecular screens are mainly the molecular sieve of X-type and Y types.X-type and Y
The skeleton structure of 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 structures further includes the modified molecular sieve with FAU structures.
Method of modifying can 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 be combined with chemical treatment.Modified obtained molecular sieve includes but 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 structures
The SiO of son sieve2：Al2O3Molar ratio be (1~4)：1；Preferably, the SiO of the molecular sieve with FAU structures2：Al2O3's
Molar ratio is (1.5~3)：1.
According to the present invention, the BEA structure molecular screens are mainly beta-molecular sieve, its structural formula is (Nan[AlnSi64-nO128],
n<7), it is the mixed crystal that is formed by two structures are different but are closely related polymorph A and B, both with 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 parameter
β=114.5 °.Twelve-ring pore size is in BEA structure molecular screens<100 directions>With <001 direction>.The SiO of the molecular sieve with BEA structures2：Al2O3Molar ratio be (5~10)：1；Preferably,
The SiO of the molecular sieve with BEA structures2：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 structures is X-type molecular sieve, Y types
At least one of molecular sieve and beta-molecular sieve；It is preferably selected from USY, REUSY, REHY, REY, PUSY, PREHY, PREY and beta molecule
At least one of sieve.
According to the present invention, at least one metal oxide selected from IIB, VB and group vib element can be 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；Can further preferably described metallic promoter agent be nickel.
In the case of, according to the invention it is preferred to, the aluminium oxide is to be provided in the desulfurization of hydrocarbon oil catalyst between each component
Cementation.Wherein, the aluminium oxide is at least one of gama-alumina, η-aluminium oxide, θ-aluminium oxide and χ-aluminium oxide；
Preferably, the aluminium oxide is gama-alumina.
In the present invention, the desulfurization of hydrocarbon oil catalyst can also contain other components, as desulphurization catalyst can contain
Component, such as laminated clay column, clay, alkali metal oxide etc..Wherein the content of laminated clay column can be 1~10 weight %, glue
The content of soil can be 1~10 weight %, and the content of alkali metal oxide is 0.1~5 weight %.
In the present invention, the laminated clay column is interstratified minerals crystal, is by two kinds of individual layer mineral clay component rule alternatings
Rearrange, its bottom surface spacing is not less than 1.7nm.It is preferred that the example of the laminated clay column includes but not limited to rectorite, Yun Meng
At least one of stone, bentonite, montmorillonite and smectite.
In the present invention, the clay can be selected from raw clay well-known to those skilled in the art, common clay kind
Class may be incorporated for the present invention, and preferably described clay can be selected from kaolin, halloysite, montmorillonite, diatomite, Ai Luo
One or more in stone, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.
In the present invention, the alkali metal oxide can be sodium oxide molybdena and/or potassium oxide.
Present invention also offers a kind of method for the desulfurization of hydrocarbon oil catalyst for preparing the present invention, including：(1a) by vanadium carbide,
Alumina binder, water and acidic liquid contact to form slurries, by the slurries and the molecule with FAU and/or BEA structures
Sieve, at least one metal oxide selected from IIB, VB and group vib element are mixed to get carrier pulp；Or (1b) by aluminium oxide
Binding agent, water and acidic liquid contact to form slurries, by the slurries and the molecular sieve, at least with FAU and/or BEA structures
A kind of metal oxide, vanadium carbide selected from IIB, VB and group vib element are mixed to get carrier pulp；(2) carrier is starched
Liquid is molded, first dries, the first roasting, obtains carrier；(3) precursor of metallic promoter agent is introduced in the carrier, so
The second drying and the second roasting are carried out afterwards, obtain catalyst precarsor；(4) catalyst precarsor is reduced in a hydrogen atmosphere,
Obtain desulfurization of hydrocarbon oil catalyst.
According to the present invention, the vanadium carbide used selects specific structure to provide desulfurization of hydrocarbon oil catalyst with preferably resistance to
Grind performance and desulphurizing activated.Under preferable case, vanadium carbide has face-centered cubic crystal structure, in the form of sheets or column structure.It is preferred that
Ground, the grain diameter of vanadium carbide is 2~30 μm, is preferably 3~15 μm.Preferably, the specific surface area of vanadium carbide is 10m2/ g~
50m2/g；Preferably 20m2/ g~35m2/g。
In the preparation method of the present invention, adding for the metal oxide can be with the powder shape of the metal oxide
Formula adds, and the metal oxide can also add water be mixed into after slurries and add in form of slurry again.
According to the present invention, at least one metal oxide selected from IIB, VB and group vib element can be 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.
According to the present invention, the FAU structure molecular screens are faujasite-type molecular sieve, and the type molecular sieve has three-dimensional ten
Two membered ring channels, aperture areThe FAU structure molecular screens are mainly the molecular sieve of X-type and Y types.X-type and Y
The skeleton structure of 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 structures further includes the modified molecular sieve with FAU structures.
Method of modifying can 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 be combined with chemical treatment.Modified obtained molecular sieve includes but 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 structures
The SiO of son sieve2：Al2O3Molar ratio be (1~4)：1；Preferably, the SiO of the molecular sieve with FAU structures2：Al2O3's
Molar ratio is (1.5~3)：1.
According to the present invention, the BEA structure molecular screens are mainly beta-molecular sieve, its structural formula is (Nan[AlnSi64-nO128],
n<7), it is the mixed crystal that is formed by two structures are different but are closely related polymorph A and B, both with 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 screens<100 directions>With <001 direction>.The SiO of the molecular sieve with BEA structures2：Al2O3Molar ratio be (5~10)：1；Preferably,
The SiO of the molecular sieve with BEA structures2：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 structures is X-type molecular sieve, Y types
At least one of molecular sieve and beta-molecular sieve；It is preferably selected from USY, REUSY, REHY, REY, PUSY, PREHY, PREY and beta molecule
At least one of sieve.
In the case of, according to the invention it is preferred to, the alumina binder can be aluminium oxide or be roasted described first
Under conditions of be changed into γ-Al2O3Material.Under preferable case, the alumina binder can be selected from SB powder, aqua oxidation
Aluminium, Aluminum sol, boehmite (boehmite), false boehmite (boehmite), hibbsite and amorphous
At least one of aluminium hydroxide；Preferably, the alumina binder be SB powder, boehmite and Aluminum sol at least
It is a kind of.
According to the present invention, the acidic liquid can be the aqueous solution of acid or acid, and the acid can be selected from water-soluble
Inorganic acid and/or organic acid, 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 of the carrier pulp be 1~5, excellent
Elect 1.5~4 as.
In the present invention, step (1a) and (1b) middle amount for adding water can be not specially limited, as long as can obtain described
Carrier pulp.Such as the weight ratio for the amount and the alumina binder for adding water is 5：1~10：1；Or add water
Amount is 5 with the weight ratio of the alumina binder and the weight summation of vanadium carbide：1~10：1.
In the present invention, other components for preparing desulphurization catalyst, such as layer column can also be added in step (1a) and (1b)
Clay, clay, the precursor etc. of alkali metal oxide.Laminated clay column, clay are as it was previously stated, repeat no more.Alkali metal oxide
Precursor can be to be changed into the material of alkali metal oxide, such as alkali metal oxygen under the first roasting condition of step (2)
Compound, the nitric acid of alkali metal, alkali metal sulfates, alkali metal phosphate, for example, can be selected from sodium oxide molybdena, potassium oxide, sodium nitrate,
At least one of potassium nitrate, potassium sulfate, sodium sulphate, potassium phosphate and sodium phosphate.
In the present invention, the obtained carrier pulp can be the forms such as pastel or slurries.Can be by the carrier pulp
Dry reshaping after thickening.More preferably the carrier pulp is slurry form, and granularity can be formed by spray drying as 20~200
μm microballoon, reach molding purpose.For the ease of spray drying, it is dry before the carrier pulp solid content can be 10~
50 weight %, are preferably 20~50 weight %.It can also include adding water during the carrier pulp is obtained, water adds
Entering amount, there is no particular limitation, 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 temperature of first drying can be room temperature~400
DEG C, it is preferably 100~350 DEG C；The time of first drying is more than 0.5h, is 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, is 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, step (3) is used to add metallic promoter agent, and the metallic promoter agent is as previously shown.The metal
The precursor of accelerating agent is the material for the oxide that can be changed into 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 precipitation.
The dipping can be the solution or suspension impregnation carrier with the precursor of metallic promoter agent；The precipitation can be to promote metal
Solution or suspension into the precursor of agent are mixed with carrier, then add ammonium hydroxide by the precursor precipitation of metallic promoter agent in carrier
On.
In the case of, according to the invention it is preferred to, the temperature of second drying is 50~300 DEG C, is preferably 100~250 DEG C；
The time of second drying is 0.5~8h, is preferably 1~5h.
Preferably, the temperature of second roasting is 300~800 DEG C, is preferably 450~750 DEG C；Second roasting
Time is more than 0.5h, is 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
Simple substance, the catalyst precarsor can be reduced, metallic promoter agent is substantially deposited with reduction-state under hydrogen atmosphere
Obtaining the catalyst of the present 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, be preferably 400~500 DEG C；The time of the reduction is 0.5~6h, is 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
Carried out before use (before being adsorbed for desulfurization).Since metallic promoter agent easily aoxidizes, and the metal in catalyst precarsor promotees
Exist in the form of an oxide into agent, therefore catalyst precarsor is reduced and is carrying out desulfurization absorption for ease of transport, 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, obtain the present invention's
Desulphurization catalyst.
In the case of, according to the invention it is preferred to, the alumina binder, vanadium carbide, the metal oxide, described have
The desulfurization of hydrocarbon oil catalyst that the addition of the molecular sieve of FAU and/or BEA structures and the precursor of the metallic promoter agent causes
In, on the basis of the gross weight of the desulfurization of hydrocarbon oil catalyst, the desulfurization of hydrocarbon oil catalyst contains the institute of 10~80 weight %
Metal oxide is stated, preferably comprises 25~70 weight %, further preferably 40~60 weight %；Oxygen containing 3~35 weight %
Change aluminium, preferably comprise 6~25 weight %, further preferably 8~15 weight %；Vanadium carbide containing 5~40 weight %, preferably contains
There are 10~30 weight %, further preferably 12~25 weight %；Containing described in 1~20 weight % there is FAU and/or BEA to tie
The molecular sieve of structure, preferably comprises 2~15 weight %, further preferably 2~10 weight %；The gold containing 5~30 weight %
Belong to accelerating agent, preferably comprise 8~25 weight %, further preferably 12~20 weight %.
The dosage of other components can be added in method provided by the invention, the desulfurization of hydrocarbon oil catalysis that can cause
In agent, the laminated clay column containing 1~10 weight %, the clay of 1~10 weight %, the alkali metal oxide of 0.1~5 weight %.
Present invention also offers desulfurization of hydrocarbon oil catalyst made from the method for the present invention.
Present invention also offers a kind of method of desulfurization of hydrocarbon oil, this method includes：In a hydrogen atmosphere, by hydrocarbon oil containing surphur with
Desulfurization of hydrocarbon oil catalyst provided by the invention carries out desulphurization reaction under 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, so as 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：Regenerated pressure is normal pressure, and regenerated temperature is 400~700 DEG C, is preferably 500~600 DEG C.
In the present invention, the catalyst after regeneration is before desulfurization of hydrocarbon oil is re-started, it is also necessary to reduced under hydrogen atmosphere,
The reducing condition of catalyst after regeneration includes：Temperature is 350~500 DEG C, is preferably 400~450 DEG C；Pressure for 0.2~
2MPa, is preferably 0.2~1.5MPa.
In the present invention, it is gauge pressure to be related to pressure.
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 larger hydrocarbon molecule be cracked into heat or catalytic process compared with small molecule DEG C to 210 DEG C of hydrocarbon or its any cut
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 not limited to fluid catalystic cracking and heavy oil catalytic cracking etc. and combinations thereof.Therefore, it is applicable
Catalytically cracked gasoline include but 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 as hydrocarbon-containifluids fluids when can be incited somebody to action before desulfurization
The cracking gasoline fractionation and/or hydrotreating." diesel fuel " means that the hydrocarbon that boiling range is 170 DEG C to 450 DEG C mixes
The liquid of thing or its any fractional composition.Such hydrocarbon-containifluids fluids include but not limited to light cycle oil, kerosene, straight-run diesel oil and hydrogenation
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 not limited to carbonyl sulfide (COS), two
Nitric sulfid (CS2), mercaptan or other thiophenes etc. and combinations thereof, especially including thiophene, benzothiophene, alkylthrophene,
The thiophene-based chemical combination for the molecular weight bigger being commonly present in alkyl benzothiophenes and methyldibenzothiophene, and diesel fuel
Thing.
Contain vanadium carbide component in the composition of desulfurization of hydrocarbon oil catalyst provided by the invention, the component is in the multiple of catalyst
Reaction and regenerative process in be not easy with the zinc oxide component effect of reacting, will not produce silicic acid zinc material urges the desulfurization of hydrocarbon oil
Agent reduces desulphurizing activated because losing zinc oxide.Catalyst of the present invention has very high desulphurizing activated, while also has obvious
Increase catalyst abrasion strength resistance property, be applicable to the reaction repeatedly and regeneration of catalytically cracked gasoline or diesel fuel
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 obtain uses X-ray diffractometer (Siemens companies D5005 types)
XRD spectra is obtained, carries out structure determination, Cu targets, K α radiation, solid probe, tube voltage 40kV, tube current 40mA；
The vanadium carbide used in embodiment is vanadium carbide -1, vanadium carbide -2 and vanadium carbide -3, is had by Sinopec catalyst
Nanjing branch company of limit company provides, and specific structural features are shown in Table 1,
Table 1
* 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 the desulfurization of hydrocarbon oil catalyst of the present invention.
(1) carrier is prepared.By Zinc oxide powder (Headhorse companies, 99.7 weight % of purity), the 0.88kg of 4.43kg
Beta-molecular sieve (catalyst asphalt in Shenli Refinery, 0.70kg containing butt, SiO2：Al2O3Molar ratio be 8：1) and 6.57kg go from
Sub- water mixing, the mixed serum of zinc oxide and beta-molecular sieve is obtained after stirring 30min；
Boehmite 1.33kg (catalyst Nanjing branch company, containing butt 1.36kg) and the vanadium carbide -1 of 2.06kg is taken to stir
Mixing is mixed, then addition deionized water 4.6kg is uniformly mixed (chemical after slurries, to add the hydrochloric acid of the 30 weight % of 360ml
Pure, Beijing Chemical Plant produces) make slurries pH=2.1,80 DEG C of aging 2h are warming up to after stirring acidifying 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 TowerTMIt is dry that the spray dryer of model carries out spraying
Dry, spray drying pressure is 8.5 to 9.5MPa, and below 500 DEG C of inlet temperature, outlet temperature is about 150 DEG C.By being spray-dried
The first 1h dry at 180 DEG C of 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 thing is after 180 DEG C of dry 4h, in sky
635 DEG C of roasting 1h of gas atmosphere, are made catalyst precarsor；
(3) reduce.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 is：Zinc oxide content is 44.3 weight %, and carbonization content of vanadium is 20.6 weight %, beta-molecular sieve
Content 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 the desulfurization of hydrocarbon oil catalyst of the present invention.
Boehmite 1.56kg (catalyst Nanjing branch company, containing butt 1.17kg) and the vanadium carbide -2 of 1.50kg are stirred
Mixing is mixed, then adding deionized water 8.2kg and being uniformly mixed makes slurry after slurries, to add the hydrochloric acid of the 30 weight % of 260ml
80 DEG C of aging 2h are warming up to after liquid pH=1.9, stirring acidifying 1h.After temperature reduction after add 5.52kg Zinc oxide powder and
REUSY molecular sieves (catalyst asphalt in Shenli Refinery, 0.3kg containing butt, the SiO of 0.38kg2：Al2O3Molar ratio be 2：1), and stir
Mix 1h and obtain carrier pulp.
Method with reference 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 is：Zinc oxide content is 55.2 weight %, and carbonization content of vanadium is 15.0 weight %, REUSY point
Son 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 the desulfurization of hydrocarbon oil catalyst of the present invention.
By the Zinc oxide powder of 4.93kg, 0.63kg USY molecular sieve (catalyst asphalt in Shenli Refinery, 0.50kg containing butt,
SiO2：Al2O3Molar ratio be 3：1), the deionized water of the vanadium carbide -3 of 2.1kg and 8.8kg mix, and are obtained after stirring 30min
The mixed serum of zinc oxide, USY molecular sieve and vanadium carbide；
Boehmite 1.80kg (Shandong Aluminum Plant produces, containing butt 1.36kg) and deionized water 4.6kg is taken to be uniformly mixed
After slurries, adding the hydrochloric acid (chemistry is pure, and Beijing Chemical Plant produces) of the 30 weight % of 300ml 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 vanadium carbide
Somaplasm liquid.
The spray drying forming of carrier pulp is carried out with reference to the method for embodiment 1.
Catalyst precarsor and catalyst are prepared with reference 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 is：Zinc oxide content is 49.3 weight %, and carbonization content of vanadium is 16.0 weight %, USY molecules
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 the desulfurization of hydrocarbon oil catalyst of the present invention.
By USY molecular sieve (the catalyst asphalt in Shenli Refinery, containing butt of the Zinc oxide powder of 4.93kg, 0.66kg
0.50kg), the deionized water of the vanadium carbide -1 of 2.1kg and 8.8kg mix, and zinc oxide, USY molecular sieve are obtained after stirring 30min
With the mixed serum of vanadium carbide；
Boehmite 1.80kg (Shandong Aluminum Plant produces, containing butt 1.36kg) and deionized water 4.6kg is taken to be uniformly mixed
After slurries, adding the hydrochloric acid of the 30 weight % of 300ml makes slurries pH=2.5, and 80 DEG C of aging 2h are warming up to after stirring acidifying 1h.
Stirring 1h obtains carrier pulp after adding the mixed serum of zinc oxide, USY molecular sieve and vanadium carbide.
Method with reference 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 is：Zinc oxide content is 49.3 weight %, and carbonization content of vanadium is 16.0 weight %, USY molecules
Sieve content is 5.0 weight %, and alumina content is 13.5 weight %, and nickel content is 16.2 weight %.
Comparative example 1
The deionized water of the Zinc oxide powder of 4.43kg and 6.57kg are mixed, zinc oxide slurries are obtained after stirring 30min；
Take the expanded perlite of boehmite 1.81kg (catalyst Nanjing branch company, containing butt 1.36kg) and 2.46kg
(catalyst Nanjing branch company, containing butt 2.40kg) is stirred, and then adds deionized water 4.6kg 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 acidifying 1h, adds zinc oxide
Stirring 1h obtains carrier pulp after slurries mixing.
Method with reference 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 is：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, containing butt 1.17kg) and the diatomite of 1.85kg is taken (to contain butt
1.80kg) it is stirred, then adds deionized water 8.2kg and be uniformly mixed, adding the hydrochloric acid of the 30 weight % of 260ml makes slurry
80 DEG C of aging 2h are warming up to after liquid pH=1.9, stirring acidifying 1h.The Zinc oxide powder of 5.52kg is added after temperature reduction simultaneously
Stirring 1h obtains carrier pulp.
Method with reference 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 is：Zinc oxide content is 55.2 weight %, and diatomite content is 18.0 weight %, and aluminium oxide contains
It is 15.1 weight % to measure as 11.7 weight %, nickel content.
Comparative example 3
The deionized water of the Zinc oxide powder of 4.93kg and 5.57kg are mixed, zinc oxide slurries are obtained after stirring 30min；
Take diatomite (world's ore deposit of boehmite 1.80kg (Shandong Aluminum Plant produces, containing butt 1.35kg) and 2.16kg
Industry company, containing butt 2.10kg) it is stirred, then add deionized water 4.6kg and be uniformly mixed, add 30 weights of 300ml
The hydrochloric acid of amount % makes slurries pH=2.5, and 80 DEG C of aging 2h are warming up to after stirring acidifying 1h.Stirred after adding the mixing of zinc oxide slurries
Mix 1h and obtain carrier pulp.
Method with reference to embodiment 3 carries out the spray drying forming of carrier pulp and introduces active component nickel and cobalt, reduces
After obtain desulfurization of hydrocarbon oil catalyst B3.
The chemical composition of B3 is：Zinc oxide content is 49.3 weight %, and diatomite content is 21.0 weight %, and aluminium oxide contains
It is 8.1 weight % to measure as 13.5 weight %, nickel content, 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, zinc oxide slurries are obtained after stirring 30min；
Take kaolin (the Suzhou height of boehmite 1.80kg (Shandong Aluminum Plant produces, containing butt 1.35kg) and 2.84kg
Ling Tu factories, containing butt 2.10kg) it is stirred, then add deionized water 3.6kg and be uniformly mixed, add 30 weights of 300ml
The hydrochloric acid of amount % makes slurries pH=2.5, and 80 DEG C of aging 2h are warming up to after stirring acidifying 1h.Stirred after adding the mixing of zinc oxide slurries
Mix 1h and obtain carrier pulp.
Method with reference to embodiment 1 carries out the spray drying forming of mixing taste and introduces active component nickel, is obtained after reduction
Desulfurization of hydrocarbon oil catalyst B4.
The chemical composition of B4 is：Zinc oxide content is 49.3 weight %, and kaolin content is 21.0 weight %, and aluminium oxide contains
It is 16.2 weight % to measure as 13.5 weight %, nickel content.
Comparative example 5
According to the method for embodiment 1, the difference is that, it is prepared according to embodiment in CN101774593A 2 ordered porous
Carbonitride of silicium material, with vanadium carbide -1 of the ordered porous carbonitride of silicium material substitution 2.40kg of 2.40kg, obtains hydrocarbon ils and takes off
Sulfur catalyst B5.
The chemical composition of B5 is：Zinc oxide content is 44.3 weight %, and ordered porous carbonitride of silicium material content is 24.0
Weight %, alumina content are 13.6 weight %, and nickel content is 18.1 weight %.
Embodiment 5
(1) abrasion strength resistance is evaluated.Abrasion strength resistance test is carried out to desulfurization of hydrocarbon oil catalyst A1-A4 and B1-B5.Using
Straight tube wears method, method reference《Petrochemical Engineering Analysis method (RIPP) experimental method》Middle RIPP 29-90, the results are shown in Table 2.Survey
The numerical value for trying to obtain is smaller, shows that abrasion strength resistance is higher.It is thin when wearing under certain condition that abrasion index is corresponding in table 2
The percentage of powder generation.
(2) desulfurization performance is evaluated.To desulfurization of hydrocarbon oil catalyst A1-A4 and B1-B5 using the micro- anti-experimental provision of fixed bed into
Row HDS evaluation is tested, by the desulfurization of hydrocarbon oil Catalyst packing of 16g 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, and reaction pressure 1.38MPa, hydrogen flowing quantity is
6.3L/h, gasoline flow 80mL/h, reaction temperature are 410 DEG C, and the weight space velocity of raw material hydrocarbon ils is 4h-1, carry out hydrocarbon oil containing surphur
Desulphurization reaction.
Weighed with sulfur content in product gasoline desulphurizing activated.Sulfur content is by offline chromatogram analysis method in product gasoline,
It is measured using the GC6890-SCD instruments of An Jielun companies.
In order to which accurate characterization goes out activity of the desulfurization of hydrocarbon oil catalyst in industrial actual motion, after the completion of HDS evaluation experiment
Catalyst regeneration treatment is carried out under 550 DEG C of air atmosphere.Desulfurization of hydrocarbon oil catalyst is subjected to HDS evaluation experiment, regeneration
Its activity settles out substantially after 6 circulations, represents to urge with the sulfur content in the product gasoline after the 6th stable circulation of catalyst
The activity of agent, sulfur content and product liquid are received as shown in table 2 in product gasoline after stablizing.
The working sulfur capacity that desulfurization of hydrocarbon oil is carried out to desulfurization of hydrocarbon oil catalyst A1-A4 and B1-B5 calculates, and the results are shown in Table 4.Its
In, penetrating in working sulfur capacity refers to：Fresh desulfurization of hydrocarbon oil catalyst is taken off under above-mentioned desulfurization performance appreciation condition
Reaction of Salmon-Saxl, is more than 10 μ g/g until reacting sulfur content in the product hydrocarbon oil obtained, that is, defines desulfurization of hydrocarbon oil catalyst and penetrated.
Working sulfur capacity refers to：The content of the sulphur of absorption is accumulated on the desulfurization of hydrocarbon oil catalyst penetrated (with the total of desulfurization of hydrocarbon oil catalyst
On the basis of weight).
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 relation to octane number are the variable quantities of the octane number compared to feed gasoline in table."-" represent compared to
The octane number of feed gasoline reduces.
1st, the sulfur content of feed gasoline is 780ppm, RON 93.0, MON 82.7.
2nd, △ MON represent the value added of product MON；
3rd, △ RON represent the value added of product RON；
4th, △ (RON+MON)/2 is the difference of product anti-knock index and raw material anti-knock index.
It can be seen that from the result data of table 2 and contain vanadium carbide component, hydrocarbon in desulfurization of hydrocarbon oil catalyst provided by the invention
The sulfur content for reducing gasoline still can be well realized after carrying out multiple circulation desulfurization in oily desulphurization catalyst, illustrates the catalyst
With more preferable desulphurizing activated and activity stability.And the abrasion index of the desulfurization of hydrocarbon oil catalyst is lower, illustrate have more
Good 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
Catalyst contains ordered porous carbonitride of silicium material, does not contain the vanadium carbide of the application, therefore abrasion index is far above embodiment
The abrasion index of obtained catalyst, illustrates that desulfurization of hydrocarbon oil catalyst provided by the invention can have more preferable wear-resisting property.
Embodiment 6
Aging is carried out to desulfurization of hydrocarbon oil catalyst A1-A4 and B1-B5, condition is：Catalyst is positioned over 600 DEG C, water steaming
Qi leel pressure is to handle 16h under the atmosphere of 20kPa.
XRD spectra analysis is carried out to the A1 before and after aging and B1, wherein, XRD spectra such as Fig. 1 institutes before and after A1 hydrothermal agings
Show, fresh dose there are the crystalline phase peak of vanadium carbide at 2 θ=37.3 °, 43.36 ° and 63.10 ° with aging agent；B1 hydrothermal agings
Front and rear XRD spectra is as shown in Figure 2.
In Fig. 1, do not occur in the XRD spectra after A1 hydrothermal agings zinc silicate 2 θ=22.0 °, 25.54 °, 48.9 °
With 59.4 ° of characteristic peak；In fig. 2, there is the features described above peak of zinc silicate in the XRD spectra after B1 hydrothermal agings.Using
Silicic acid Zn content in the XRD spectra of crystal content quantitative analysis B1-B5, the results are shown in Table 3.
With the A1-A4 and the desulfurization performance of B1-B5 after evaluation method evaluation aging same as Example 5, the results are shown in Table
3。
The working sulfur capacity that desulfurization of hydrocarbon oil is carried out to desulfurization of hydrocarbon oil the catalyst A1-A4 and B1-B5 after aging calculates, the result is shown in
Table 4.
Table 3
Note：The data in relation to octane number are the variable quantities of the octane number compared to feed gasoline in table."-" represent compared to
The octane number of feed gasoline reduces.
1st, the sulfur content of feed gasoline is 780ppm, RON 93.0, MON 82.7.
2nd, △ MON represent the value added of product MON；
3rd, △ RON represent the value added of product RON；
4th, △ (RON+MON)/2 is the difference of product anti-knock index and raw material anti-knock index.
Table 4
From the results shown in Table 3, after ageing process, do 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, so that catalyst
Desulphurizing activated reduction.
The data of product gasoline can also be seen that method provided by the invention can still obtain high product from table 2 and 3
Yield of gasoline, while also there is the advantage of obvious increase octane number.
From table 4, it can be seen that before aging, desulfurization of hydrocarbon oil catalyst using the present invention carries out the working sulfur capacity of desulfurization of hydrocarbon oil
It is close with the working sulfur capacity of the desulfurization of hydrocarbon oil catalyst using comparative example；After ageing process, since the hydrocarbon ils that embodiment obtains takes off
Without generation zinc silicate in sulfur catalyst, and the catalyst in comparative example 1-4, zinc oxide can generate silicon with the material of silicon oxide-containing
Sour zinc, so that the working sulfur capacity of catalyst is decreased obviously, therefore desulphurizing activated is significantly reduced.
Claims (15)
1. a kind of desulfurization of hydrocarbon oil catalyst, on the basis of the gross weight of the desulfurization of hydrocarbon oil catalyst, which contains
Have：
1) at least one metal oxide selected from IIB, VB and group vib element of 10~80 weight %；
2) aluminium oxide of 3~35 weight %；
3) vanadium carbide of 5~40 weight %；
4) molecular sieve with FAU and/or BEA structures 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.
2. desulfurization of hydrocarbon oil catalyst according to claim 1, wherein, using the gross weight of the desulfurization of hydrocarbon oil catalyst as base
Standard, the desulfurization of hydrocarbon oil catalyst contain the metal oxide of 40~60 weight %, the aluminium oxide of 8~15 weight %, 12~
The vanadium carbide of 25 weight %, the molecular sieve with FAU and/or BEA structures of 2~10 weight %, 12~20 weight %'s
The metallic promoter agent.
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 37.3 °, 43.36 ° and 63.10 ° at there are vanadium carbide crystalline phase peak.
4. desulfurization of hydrocarbon oil catalyst according to claim 1 or 2, wherein, the metal oxide is zinc oxide, molybdenum oxide
At least one of with vanadium oxide；It is preferred that the metal oxide is zinc oxide.
5. desulfurization of hydrocarbon oil catalyst according to claim 1 or 2, wherein, the molecule with FAU and/or BEA structures
Sieve as at least one of X-type molecular sieve, Y type molecular sieve and beta-molecular sieve；Be preferably selected from USY, REUSY, REHY, REY, PUSY,
At least one of PREHY, PREY and beta-molecular sieve.
6. a kind of method for preparing the desulfurization of hydrocarbon oil catalyst in claim 1-5 described in any one, including：
Vanadium carbide, alumina binder, water and acidic liquid are contacted to form slurries by (1a), by the slurries and have FAU
And/or molecular sieve, at least one metal oxide selected from IIB, VB and group vib element of BEA structures are mixed to get carrier slurry
Liquid；Or
Alumina binder, water and acidic liquid are contacted to form slurries by (1b), by the slurries with being tied with FAU and/or BEA
The molecular sieve of structure, at least one metal oxide, vanadium carbide selected from IIB, VB and group vib element are mixed to get carrier pulp；
(2) carrier pulp is molded, first drying, first roasting, obtain carrier；
(3) precursor of metallic promoter agent is introduced in the carrier, the second drying and the second roasting is then carried out, obtains catalyst
Precursor；
(4) catalyst precarsor is reduced in a hydrogen atmosphere, obtains desulfurization of hydrocarbon oil catalyst.
7. according to the method described in claim 6, wherein, vanadium carbide has face-centered cubic crystal structure, in the form of sheets or column knot
Structure.
8. the method according to claim 6 or 7, wherein, the grain diameter of vanadium carbide is 2~30 μm, is preferably 3~15 μ
m；The specific surface area of vanadium carbide is 10m2/ g~50m2/g；Preferably 20m2/ g~35m2/g。
9. according to the method described in claim 6, wherein, the molecular sieve with FAU and/or BEA structures is X-type molecule
At least one of sieve, Y type molecular sieve and beta-molecular sieve；It is preferably selected from USY, REUSY, REHY, REY, PUSY, PREHY, PREY
At least one of with beta-molecular sieve.
10. according to the method described in claim 6, wherein, it is molten that the alumina binder is selected from SB powder, hydrated alumina, aluminium
At least one of glue, boehmite, false boehmite, hibbsite and amorphous hydroted alumina.
11. according to the method described in claim 6, 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 6, wherein, the dosage of the acidic liquid makes the pH value of the carrier pulp be 1
~5；The acidic liquid is selected from water-soluble inorganic acid and/or organic acid for acid or the aqueous solution of acid, the acid.
13. according to the method described in claim 6, wherein, the temperature of first drying is room temperature~400 DEG C, described first
The dry time is 0.5~8h；It is described first roasting temperature be 400~700 DEG C, it is described first roasting time for 0.5h with
On；The temperature of second drying is 50~300 DEG C, and the time of second drying is 0.5~8h；The temperature of second roasting
Spend for 300~800 DEG C, the time of second roasting is 0.5~4h；The temperature of the reduction is 300~600 DEG C, described to go back
The former time is 0.5~6h, and hydrogen content is 10~60 volume % in the hydrogen atmosphere.
14. desulfurization of hydrocarbon oil catalyst made from the method in claim 6-13 described in any one.
15. a kind of method of desulfurization of hydrocarbon oil, including：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 under 350~500 DEG C, 0.5~4MPa.
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