CN110465325A - Support type oxidation-desulfurizing catalyst molecular sieve and its preparation method and application - Google Patents
Support type oxidation-desulfurizing catalyst molecular sieve and its preparation method and application Download PDFInfo
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- CN110465325A CN110465325A CN201810439173.1A CN201810439173A CN110465325A CN 110465325 A CN110465325 A CN 110465325A CN 201810439173 A CN201810439173 A CN 201810439173A CN 110465325 A CN110465325 A CN 110465325A
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- molecular sieve
- niobium
- support type
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- type oxidation
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 49
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000002425 crystallisation Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 29
- 230000008025 crystallization Effects 0.000 claims abstract description 26
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000010955 niobium Substances 0.000 claims abstract description 14
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 13
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 12
- 230000023556 desulfurization Effects 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000000295 fuel oil Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 5
- 239000004698 Polyethylene Substances 0.000 claims abstract description 5
- 239000004743 Polypropylene Substances 0.000 claims abstract description 5
- 239000000470 constituent Substances 0.000 claims abstract description 5
- -1 polyethylene Polymers 0.000 claims abstract description 5
- 229920000573 polyethylene Polymers 0.000 claims abstract description 5
- 229920001155 polypropylene Polymers 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 238000007598 dipping method Methods 0.000 claims description 9
- 150000002822 niobium compounds Chemical class 0.000 claims description 9
- 238000002803 maceration Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004115 Sodium Silicate Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 abstract description 7
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000004088 simulation Methods 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 229910004328 HNbO3 Inorganic materials 0.000 description 3
- 229940126678 chinese medicines Drugs 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
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
- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to oxidative desulfurization of fuel oils fields, disclose a kind of support type oxidation-desulfurizing catalyst molecular sieve and its preparation method and application, the preparation method of support type oxidation-desulfurizing catalyst molecular sieve of the invention is the following steps are included: the step of (1) in the presence of water, silicon-containing material, inorganic acid and template are mixed；(2) the step of product that step (1) obtains successively being subjected to crystallization, separation of solid and liquid, drying and the first roasting, obtaining mesopore molecular sieve；(3) the carried metal active constituent niobium on the mesopore molecular sieve the step of, wherein the template is polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.The support type oxidation-desulfurizing catalyst molecular sieve being prepared according to the method for the present invention especially also has preferable removal effect with preferable desulfurization effect to dibenzothiophenes.
Description
Technical field
The present invention relates to oxidative desulfurization of fuel oils fields, and in particular to a kind of support type oxidation-desulfurizing catalyst molecular sieve and
Preparation method and application.
Background technique
Industrial common desulfurization technology has hydrodesulfurization and oxidation sweetening.Although traditional hydrodesulfurization technology is able to satisfy
The low-sulfur requirement of fuel oil, but big, operating cost height is invested, operating condition is harsher.And oxidative desulfurization techniques are because of its reaction
Mild condition, simple process, non-hydrogen operation, and dibenzothiophenes (DBT) the class compound for being difficult to remove to hydrodesulfurization has
Good removal effect.In oxidative desulfurization techniques, common oxidant is H2O2, catalyst HCOOH, CH3COOH, heteropoly acid,
Ionic liquid etc..These homogeneous catalyst separations and recycling are difficult, therefore limit its extensive use.
Therefore, seeking new heterogeneous catalyst is one of the effective way for improving oxidation sweetening efficiency.
Summary of the invention
The purpose of the invention is to overcome the above problem of the existing technology, it is de- to provide a kind of new support type oxidation
Sulfur catalyst molecular sieve and its preparation method and application, the support type oxidation-desulfurizing catalyst molecular sieve have dibenzothiophenes
Preferable removal effect.
To achieve the goals above, one aspect of the present invention provides a kind of preparation of support type oxidation-desulfurizing catalyst molecular sieve
Method, wherein method includes the following steps:
(1) in the presence of water, the step of silicon-containing material, inorganic acid and template being mixed；
(2) product that step (1) obtains successively is subjected to crystallization, filtering, drying and the first roasting, obtains mesopore molecular sieve
The step of；
(3) the carried metal active constituent niobium on the mesopore molecular sieve the step of,
Wherein, the template is polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.
Second aspect of the present invention provides the support type oxidation-desulfurizing catalyst molecular sieve that the above method is prepared.
Third aspect present invention provides support type oxidation-desulfurizing catalyst molecular sieve of the invention in oxidative desulfurization of fuel oils
In application.
The support type oxidation-desulfurizing catalyst molecular sieve being prepared according to the method for the present invention, with preferable desulfurization
Effect especially also has preferable removal effect to dibenzothiophenes.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of preparation method of support type oxidation-desulfurizing catalyst molecular sieve, wherein this method
The following steps are included:
(1) in the presence of water, the step of silicon-containing material, inorganic acid and template being mixed；
(2) product that step (1) obtains successively is subjected to crystallization, filtering, drying and the first roasting, obtains mesopore molecular sieve
The step of；
(3) the carried metal active constituent niobium on the mesopore molecular sieve the step of,
Wherein, the template is polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.
According to the present invention, in step (1), for the silicon-containing material, there is no particular limitation, can for it is existing can
It is used to prepare the various silicon-containing compounds of mesopore molecular sieve, preferably one of tetraethyl orthosilicate, sodium metasilicate and silica solution
Or it is a variety of；More preferably tetraethyl orthosilicate.
According to the present invention, in step (1), the inorganic acid is preferably one of hydrochloric acid, sulfuric acid and phosphoric acid or a variety of；More
Preferably hydrochloric acid.
According to the present invention, in step (1), the dosage of silicon-containing material and inorganic acid, template and water can be in biggish model
Enclose interior variation, it is preferable that the molar ratio of silicon-containing material and inorganic acid, template and water is 1:1-10:0.001-1:100-200,
Preferably 1:4-6:0.01-0.05:130-170, more preferably 1:5-6:0.01-0.02:135-160.
In the present invention, the mode that silicon-containing material, inorganic acid and template are mixed is not limited particularly
It is fixed, they can directly be mixed, can also be mixed again with remaining fractions after first mixing portion ingredient.It is preferred that
Ground first mixes template with water, and inorganic acid solution then is added and silicon-containing material is mixed.
In the present invention, the water is preferably deionized water.
According to invention, after the mixing step for completing step (1), the product that step (1) is obtained carries out Crystallizing treatment, institute
Stating crystallization can carry out in crystallization tank commonly used in the art.The condition of the crystallization includes: that temperature is 80-150 DEG C, when
Between be 12-48 hours；Preferably, it is 80-110 DEG C that the condition for stating crystallization, which includes: temperature, and the time is 10-20 hours.
After completing above-mentioned Crystallizing treatment, the product that crystallization is obtained is filtered and dries.It is described to be separated by solid-liquid separation and do
It is dry to be carried out using condition well known in the art.For example, the separation of solid and liquid can be carried out using filtering etc.；The drying can
With 12-48 hours dry at 80-150 DEG C.
Preferably, before dry after the product for obtaining crystallization is filtered, the solid being obtained by filtration is washed
It washs, the washing can be washed with water (preferably deionized water).
According to the present invention, desciccate is subjected to the first roasting after the drying and obtains the mesopore molecular sieve.The roasting
It can carry out, such as can be carried out in Muffle furnace in equipment commonly used in the art.The condition packet of first roasting
Include: temperature is 400-600 DEG C, and the time is 4-8 hours；Preferably, it is 450-550 DEG C that the condition of the roasting, which includes: temperature, when
Between be 5-7 hours.
According to the present invention, in step (2), it is preferable that the BET specific surface area of the mesopore molecular sieve is 500-700m2/ g,
Total pore volume is 0.5-2cm3/g；It is highly preferred that the BET specific surface area of the mesopore molecular sieve is 550-600m2/ g, total hole body
Product is 0.7-1cm3/g。
In accordance with the present invention it is preferred that including: to pass through in the step of carried metal active constituent niobium on the mesopore molecular sieve
The mesopore molecular sieve is impregnated in the product after being impregnated in the maceration extract containing niobium compound, and by the product after dipping
Carry out the second roasting.
Preferably, the niobium compound is niobic acid and/or niobium pentaoxide.
There is no particular limitation for content of the above-mentioned niobium compound in maceration extract, as long as can obtain meeting following load capacity
Support type oxidation-desulfurizing catalyst molecular sieve.Preferably, the niobium compound in terms of niobium element is in maceration extract
Content is 5-30 mass %, preferably 10-20 mass %.In addition, the maceration extract is preferably aqueous solution.
In addition, the maceration extract can also contain organic acid, it is preferable that the organic acid is in oxalic acid, formic acid and propionic acid
It is one or more.The content of organic acid can be 4-8 mass %, preferably 5-6.5 mass % in the maceration extract.
Additionally, it is preferred that the dosage of the niobium compound makes the load capacity of the metal active ingredient niobium in terms of niobium element be 5-
The dosage of 30 mass %, the more preferable niobium compound make the load capacity of the metal active ingredient niobium in terms of niobium element be 10-
20 mass %.
According to the present invention, for the impregnation method, there is no particular limitation, as long as the oxygen of above-mentioned load capacity can be obtained
Change desulphurization catalyst.It can be incipient impregnation, excessive dipping, repeatedly the methods of dipping, it is preferred to use incipient impregnation.
In addition, the condition of dipping can be the normal condition of this field.Such as the temperature of dipping can be 40-120 DEG C, it is excellent
It is selected as 50-100 DEG C, the time of dipping can be 2h or more, preferably 2-6h.
In accordance with the present invention it is preferred that the product after dipping is carried out before being roasted the product after the dipping
It is dry.The drying can carry out at 50-120 DEG C of temperature.
According to the present invention, it is 200-600 DEG C that the condition of second roasting, which includes: temperature, and the time is 2-8 hours；It is preferred that
Ground, it is 250-400 DEG C that the condition of second roasting, which includes: temperature, and the time is 4-8 hours.
The present invention also provides methods of the invention, and support type oxidation-desulfurizing catalyst molecular sieve is prepared.
The present invention also provides support type oxidation-desulfurizing catalyst molecular sieve answering in oxidative desulfurization of fuel oils of the invention
With.
Embodiment
The present invention will be described in detail by way of examples below, but the present invention is not limited in following embodiments.
In following embodiment, BET specific surface area and total pore volume are automatic by U.S.'s Micromeritics ASAP-2400 type
Adsorption instrument is made, test condition are as follows: N2Make adsorbate, adsorption temp is -196.15 DEG C (liquid nitrogen temperature), and sample exists before measuring
Vacuum activating 16h under 383K.
In following embodiment, template uses polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer
(being purchased from Mobil company, the U.S., molecular weight 5800).
Embodiment 1
Template is add to deionized water, after stirring 100 minutes at 25 DEG C, concentrated hydrochloric acid is added, and (concentration is 35 matter
Measure %) and tetraethyl orthosilicate, 16h is then stirred at 25 DEG C is beaten.Then slurry is fitted into crystallization tank and carries out water
Thermal crystallisation；After hydrothermal crystallizing, crystallization product is filtered, and (the dosage of deionized water is washed with deionized in solid
It is 3 times of the deionized water of crystallization system investment), 12h is dried after washing at 80 DEG C, then carries out roasting in Muffle furnace
To mesopore molecular sieve A1 (BET specific surface area 550m2/ g, total pore volume 0.78cm3/g).Wherein, tetraethyl orthosilicate and nothing
The molar ratio of machine acid, template and water is 1:5:0.01:135；The temperature of crystallization is 80 DEG C, and the time of crystallization is 12 hours；Roasting
The temperature of burning is 450 DEG C, and the time of roasting is 5 hours.
Using infusion process, weigh with HNbO3It is calculated as the HNbO of 0.3g3(n 2-4 is purchased from Shenyang Chinese medicines group to nH2O
Learn reagent Co., Ltd) and 5g oxalic acid be put into 100mL beaker, with 80mL deionized water in 50 DEG C dissolve, then be added 2g be situated between
Solvent is evaporated after impregnating 3 hours at 50 DEG C at 70 DEG C by porous molecular sieve, and 12 hours dry with 100 DEG C in an oven, so
It is finally roasted 4 hours in Muffle furnace in 320 DEG C afterwards, obtains the support type oxygen that Nb load capacity (in terms of niobium element) is 15 mass %
Change desulphurization catalyst molecular sieve S1.
Embodiment 2
Template is add to deionized water, after stirring 120 minutes at 25 DEG C, concentrated hydrochloric acid is added, and (concentration is 36 matter
Measure %) and tetraethyl orthosilicate, it then stirs at 25 DEG C and is beaten for 24 hours.Then slurry is fitted into crystallization tank and carries out water
Thermal crystallisation；After hydrothermal crystallizing, crystallization product is filtered, and (the dosage of deionized water is washed with deionized in solid
It is 3.5 times of the deionized water of crystallization system investment), 15h is dried after washing at 90 DEG C, is then roasted in Muffle furnace
Obtain mesopore molecular sieve A2 (BET specific surface area 590m2/ g, total pore volume 0.90cm3/g).Wherein, tetraethyl orthosilicate with
The molar ratio of inorganic acid, template and water is 1:5.5:0.012:140；The temperature of crystallization is 95 DEG C, and the time of crystallization is 16 small
When；The temperature of roasting is 480 DEG C, and the time of roasting is 5.5 hours.
Using infusion process, weigh with HNbO3It is calculated as the HNbO of 0.2g3(n 2-4 is purchased from Shenyang Chinese medicines group to nH2O
Learn reagent Co., Ltd) and 6g oxalic acid be put into 100mL beaker, with 80mL deionized water in 55 DEG C dissolve, then be added 2g be situated between
Solvent is evaporated after impregnating 4 hours at 55 DEG C at 70 DEG C by porous molecular sieve A2, and 12 hours dry with 100 DEG C in an oven,
Then it is finally roasted 4.5 hours in Muffle furnace in 350 DEG C, obtains the load that Nb load capacity (in terms of niobium element) is 10 mass %
Type oxidation-desulfurizing catalyst molecular sieve S2.
Embodiment 3
Template is add to deionized water, after stirring 150 minutes at 25 DEG C, concentrated hydrochloric acid is added, and (concentration is 37 matter
Measure %) and tetraethyl orthosilicate, 32h is then stirred at 25 DEG C is beaten.Then slurry is fitted into crystallization tank and carries out water
Thermal crystallisation；After hydrothermal crystallizing, crystallization product is filtered, and (the dosage of deionized water is washed with deionized in solid
It is 4 times of the deionized water of crystallization system investment), drying for 24 hours, is then roasted in Muffle furnace at 100 DEG C after washing
Obtain mesopore molecular sieve A3 (BET specific surface area 580m2/ g, total pore volume 0.88cm3/g).Wherein, tetraethyl orthosilicate with
The molar ratio of inorganic acid, template and water is 1:6:0.02:160；The temperature of crystallization is 110 DEG C, and the time of crystallization is 20 hours；
The temperature of roasting is 500 DEG C, and the time of roasting is 6 hours.
Using infusion process, weigh with HNbO3It is calculated as the HNbO of 0.4g3(n 2-4 is purchased from Shenyang Chinese medicines group to nH2O
Learn reagent Co., Ltd) and 4g oxalic acid be put into 100mL beaker, with 60mL deionized water in 60 DEG C dissolve, then be added 2g be situated between
Solvent is evaporated after impregnating 6 hours at 58 DEG C at 70 DEG C by porous molecular sieve A3, and 12 hours dry with 100 DEG C in an oven,
Then it is finally roasted 5 hours in Muffle furnace in 300 DEG C, obtains the support type that Nb load capacity (in terms of niobium element) is 20 mass %
Oxidation-desulfurizing catalyst molecular sieve S3.
Embodiment 4
It is carried out according to the method for embodiment 3, unlike, tetraethyl orthosilicate is replaced with into sodium metasilicate, is obtained in the same manner
Nb load capacity is the support type oxidation-desulfurizing catalyst molecular sieve S4 of 15 mass %.
Comparative example 1
It is carried out according to the method for embodiment 3, unlike, carrier is replaced with into silica, obtains Nb load in the same manner
Amount is the support type oxidation-desulfurizing catalyst molecular sieve D1 of 15 mass %.
Test case 1
Using the isooctane solution for the dibenzothiophenes that sulfur content is 150 μ g/g as simulation oil.Take catalyst (respectively using upper
Support type oxidation-desulfurizing catalyst the molecular sieve S1-S4 and D1 stated, dosage be simulation oil 5 mass %), 10ml simulation oil
Product, 10ml solvent (distilled water/extractant NMP=1) and oxidant H2O2It is added in closed steel bomb and is aoxidized together
Experiment.Reaction temperature is set as 50 DEG C, after reacting 2h, cooling is carried out, washes, the simulation oil after taking oxidation surveys its sulfur content, and
Desulfurization degree is measured by the following method, and result is shown in Table 1 below.
Using WK-2B type Microcoulomb instrument to sample carry out analysis of sulfur content, WK-2B type Microcoulomb instrument be micro-amounts of liquids into
Sample, gasification section temperature are 650 DEG C, and burning zone temperature is 850 DEG C, and stable section temperature is 750 DEG C, and the measurement result is as sulfur content
Quantitative data.
Simulation oil desulfurization degree is calculated with following formula: x=(wo-wt)/wo × 100%.In formula, x is the removing of dibenzothiophenes
Rate, wo, wt are respectively the mass fraction for reacting sulphur in the simulation oil of front and back.
Table 1
| Molecular sieve number | Remove dibenzothiophenes effect |
| S1 | 93.50% |
| S2 | 95.25% |
| S3 | 93.23% |
| S4 | 58.53% |
| D1 | 52.50% |
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of preparation method of support type oxidation-desulfurizing catalyst molecular sieve, which is characterized in that method includes the following steps:
(1) in the presence of water, the step of silicon-containing material, inorganic acid and template being mixed；
(2) product that step (1) obtains successively is subjected to crystallization, separation of solid and liquid, drying and the first roasting, obtains mesopore molecular sieve
The step of；
(3) the carried metal active constituent niobium on the mesopore molecular sieve the step of,
Wherein, the template is polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.
2. according to the method described in claim 1, wherein, the silicon-containing material is tetraethyl orthosilicate, sodium metasilicate and silica solution
One of or it is a variety of；
The inorganic acid is one of hydrochloric acid, sulfuric acid and phosphoric acid or a variety of.
3. according to the method described in claim 1, wherein, in step (1), silicon-containing material rubs with inorganic acid, template and water
You are than being 1:1-10:0.001-1:100-200, preferably 1:4-6:0.01-0.05:130-170.
4. method described in any one of -3 according to claim 1, wherein the condition of the crystallization includes: that temperature is 80-
150 DEG C, the time is 12-48 hours.
5. method described in any one of -3 according to claim 1, wherein the condition of first roasting includes: that temperature is
400-600 DEG C, the time is 4-8 hours.
6. method described in any one of -3 according to claim 1, wherein the carried metal activity on the mesopore molecular sieve
The step of ingredient niobium includes: by after being impregnated in the mesopore molecular sieve and being impregnated in the maceration extract containing niobium compound
Product, and the product after dipping is subjected to the second roasting；
Preferably, the niobium compound is niobic acid and/or niobium pentaoxide.
7. according to the method described in claim 6, wherein, the dosage of the niobium compound makes the metal active in terms of niobium element
The load capacity of ingredient niobium is 5-30 mass %.
8. method described in any one of -3 according to claim 1, wherein the BET specific surface area of the mesopore molecular sieve is
500-700m2/ g, total pore volume 0.5-2cm3/g。
9. the support type oxidation-desulfurizing catalyst molecular sieve that method described in any one of claim 1-8 is prepared.
10. application of the support type oxidation-desulfurizing catalyst molecular sieve as claimed in claim 9 in oxidative desulfurization of fuel oils.
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