CN110124611A - A kind of -11 molecular sieve preparation method of binderless ZSM-5 and its application in oil product absorption desulfurization - Google Patents
A kind of -11 molecular sieve preparation method of binderless ZSM-5 and its application in oil product absorption desulfurization Download PDFInfo
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- CN110124611A CN110124611A CN201910445051.8A CN201910445051A CN110124611A CN 110124611 A CN110124611 A CN 110124611A CN 201910445051 A CN201910445051 A CN 201910445051A CN 110124611 A CN110124611 A CN 110124611A
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- 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
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/365—Type ZSM-8; Type ZSM-11; ZSM 5/11 intermediate
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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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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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
- 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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- 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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Abstract
The invention discloses a kind of -11 molecular sieve preparation method of binderless ZSM-5 and its applications in oil product absorption desulfurization, molecular sieve preparation method is the following steps are included: molded ZSM-11 molecular screen primary powder, amorphous silica binder, template and water are mixed, addition sodium silicate aqueous solution；Adjust pH to 11-14；Mixture is placed in after stirred in water bath and is transferred to hydrothermal crystallizing kettle, hydrothermal crystallizing；Washing, drying, grinding, screening, roasting obtain -11 molecular sieve of binderless ZSM-5.The adsorbent of molecular sieve is compared to molecular screen primary powder, by wherein most Al2O3Binder is converted into molecular sieve structure by in-situ crystallization reaction, solves in molded molecular sieve containing a large amount of Al2O3Cause to adsorb the lower problem of desulfurization degree.Obtained -11 molecular sieve of binderless ZSM-5 can be used for the adsorbing and removing of the thiophene sulfides in oil product, and adsorption capacity has biggish promotion, improves desulfuration efficiency.
Description
Technical field
The invention belongs to adsorption cleanings, desulfurizing oil field, and in particular to a kind of -11 system with molecular sieve for preparing of binderless ZSM-5 is standby
Method and its application in oil product absorption desulfurization.
Background technique
Organic sulfur compound in fuel oil be cause environmental pollution, refining equipment corrosion and catalyst poisoning it is important because
Element.Therefore, it is current oil refining row that the organic sulfur compound in fuel oil, which is greatly reduced, to meet increasingly strict environmental requirement
The urgent task that industry is faced.Currently, oil product desulfurization method mainly include catalytic desulfurhydrogenation, oxidation sweetening, biological desulphurization and
Adsorb desulfurization etc..Catalytic desulfurhydrogenation not only consumes valuable H2Resource, while also consuming unsaturated olefin in oil product；Oxidation is de-
Though sulphur research achieves fine progress, the problems such as desulfurization degree is low and selectivity is low is still had；Biological desulphurization is in development phase, micro-
The problems such as biological respinse is not easy to control, and sweetening process fuel consumption is big still has to be solved.Traditional hydrodesulfurization is in fuel oil
Irreplaceable role is played in process, its very effective removing mercaptan of energy and thioether class sulfide, but for thiophene
The removal effect of pheno class sulfide is undesirable.Therefore, people invest sight the research of non-hydrodesulfurization.
Selective absorption desulfurization can carry out under room temperature, normal pressure, simple with process, selective high, removing precision height,
The features such as adsorbent is renewable, be particularly suitable for vapour, in diesel oil sulfide ultra-deep removing.High-performance adsorbent material is oil product
The core of middle sulfide removing research, but lack adsorbent is efficiently removed in depth at present.Common adsorbent include activated carbon,
Metallic framework compound (MOF), microporous coordination polymer, Metal Supported SiO2With NaY molecular sieve etc..Molecular sieve has abundant
Cellular structure, higher specific surface area and large hole are held, and being easy to introduce metal ion improves desulfurization effect, become research in recent years
Hot spot.But when the molecular sieves such as non-modified NaY, ZSM-5, MCM-41 are removed for sulfur compounds adsorption, there is purification precision not
High, the problems such as adsorption capacity is low, processing is modified to improve clean-up effect needs.
Doctor treatment is adsorbed because having mild condition, simple process invests the advantages such as low with operating cost, becomes state in recent years
The hot spot of inside and outside research.
What reason equalization has studied using kaolin and diatomite mixed clay as research object, using in-situ crystallization technology with
Duct control technology has synthesized the ZSM-5 molecular sieve with multistage pore canal.Zeolite crystal distribution is uniform, and shape is neat, tool
There are higher thermal stability, biggish specific surface area and aperture.
Liu Chunying etc. synthesizes ZSM-5 molecular sieve using diatomite as raw material, using in-situ crystallization method, has investigated crystallization time,
Water silicon ratio, the factors such as template dosage are to synthesis of molecular sieve relative crystallinity, the influence of grain morphology and size etc..
Tomaz Fakin is using dry silicate gel particle as raw material, and waterglass is as pseudo- binder, using hydro-thermal
Crystallisation is prepared for ZSM-5 zeolite particle, has studied crystallization temperature in hydrothermal treatment process, crystallization time, silica alumina ratio is to crystallization
The influence of process, so that synthetic product yield is significantly increased.
Do not find directly use so far ZSM-11 molecular screen primary powder and alumina binder particle after molding as
Crystal seed carries out hydrothermal crystallizing reaction, after convert aluminium oxide therein to the report of molecular sieve.
Summary of the invention
It is an object of the present invention to contain a large amount of Al afterwards for molecular sieve molded at present2O3Binder leads to adsorption capacity
The problems such as low, proposes a kind of -11 molecular sieve preparation method of binderless ZSM-5, sieves compared to original molecule, and the present invention prepares soap-free emulsion polymeization
The adsorption capacity and desulfurization degree of agent ZSM-11 molecular sieve improved for sulfide in oil product.
To achieve the above object, the technical solution adopted by the present invention is that: a kind of standby side of -11 system with molecular sieve for preparing of binderless ZSM-5
Method, comprising the following steps:
Step 1: by molded ZSM-11 molecular screen primary powder, template, amorphous silica binder and water according to such as
Sodium silicate aqueous solution is added into mixture, makes to mix by lower ratio mixing 1-5 (g): 5-25 (g): 5-15 (g): 100-300 (ml)
Closing silica alumina ratio in object is 50-90；The preferred molded ZSM-11 molecular screen primary powder, template, amorphous silica are viscous
Tie agent and water in ratio be 2-4 (g): 10-20 (g): 5-15 (g): 150-250 (ml)；
Step 2: adjusting the pH to 11-14 of mixture using NaOH solution；
Step 3: mixture is placed in 70-90 DEG C of water-bath, with 300-2000 revs/min of stirring 0.5-2h；
Step 4: mixture is transferred to hydrothermal crystallizing kettle, hydrothermal crystallizing reacts 18-32h under the conditions of 90-180 DEG C；
Step 5: taking out washing to neutrality, dries, grind, screening, 550-650 DEG C of roasting 2-8h obtains binder free
ZSM-11 molecular sieve.
Further, the partial size of molded ZSM-11 molecular screen primary powder described in step 1 is 150-425 μm.
Further, template described in step 1 be 4-propyl bromide (TPAB), tetrapropylammonium hydroxide (TPOH) or
One of cetyl trimethylammonium bromide (CTAB) or a variety of mixing.
Further, silica is selected from silica solution, waterglass or its mixing in silica binder described in step 1
Object, SiO2Weight percentage be 10-50%.
Further, the sodium silicate aqueous solution group becomes Na2O=6-8wt%, SiO2=26-28wt%, surplus are water.
Further, step 5 roasting heating rate is 5-30 DEG C/min, and heating rate of temperature fall can not be too fast, prevents molecule
It sieves black.After adsorbent is fired/is cooled to room temperature, it is stand-by to be transferred to hermetically drying device as early as possible, so as not to adsorbent by
Tide influences it and adsorbs desulfurization effect, or is handled using preceding by online high-temperature activation in -11 molecular sieve of binderless ZSM-5.
Further, maturing temperature described in step 5 is 550-650 DEG C, calcining time 2-8h.
Further, it is 0.25-0.425 μm that particle diameter is filtered out described in step 5.
Further, the preparation step of the molded ZSM-11 molecular screen primary powder is as follows: by molecular screen primary powder, Al2O3With
Sesbania powder is mixed in 1:0.25-2:0.03-0.07 ratio, and every gram molecule sieve original powder is corresponding to be added 1-20%wt acidic aqueous solution
0.5-2ml, after mediating uniformly, extruded moulding；Dry 2-8h, crosses standard screen in 60-160 DEG C of baking oven after grinding, is made and has become
Type ZSM-11 molecular screen primary powder.
Further, the acid solution is one of dust technology, citric acid and aluminum nitrate or a variety of mixing, and acidity is molten
Liquid concentration is 1-20wt%.
Another object of the present invention also discloses a kind of -11 molecular sieve of binderless ZSM-5, using above-mentioned preparation method system
It is standby to form.
Further, -11 molecular sieve of binderless ZSM-5 includes the following component of weight proportion: 90-99 parts of SiO2,
1-10 parts of Al2O3。
It is a further object to provide a kind of -11 molecular sieve of binderless ZSM-5 answering in desulfurizing oil
With and oil product desulfurization method.
Application of -11 molecular sieve of binderless ZSM-5 in desulfurizing oil: -11 molecular sieve of binderless ZSM-5 is used
It is in contact with sour product, desulfurizing oil is realized using static adsorptive method.The condition that wherein oil product is contacted with adsorbent is: pressure
For normal pressure 101.325kPa, temperature is 20-80 DEG C of constant temperature.
- 11 molecular sieve of binderless ZSM-5 of the present invention can be used for desulfurizing oil process.One specific unit operation is as follows:
Taking particle diameter is that 0.25-0.425 μm 0 of -11 molecular sieve of binderless ZSM-5 is put into container, and sour product configuration is added not
With finish ratio, the isothermal vibration set time in shaking bath, microsyringe sampling uses Agilent GC7890B gas phase color
Spectrum measurement sulfur content.
Oil product described in oil product desulfurization method provided by the invention is that the benzothiophene concentration of normal octane configuration contained is
The analog gasoline of 10-500ppmw concentration, liquid air speed 0.2-10h-1。
- 11 molecular sieve preparation method of adhesive ZSM-5 of the present invention compared with prior art, has the advantage that
Pure ZSM-11 molecular screen primary powder, which is difficult to form, when binder free carries out Dynamic Adsorption experiment, but binder molding is added
Contain a large amount of aluminium oxide in molecular sieve afterwards, so that molecular sieve absorption desulphurizing ability weakens.In-situ crystallization method prepares binder free
Composite molecular screen solves this problem.While improving effective molecular sieve content in prepared molecular sieve, adsorbent can control
Granule size increases the surface area and duct volume of molecular sieve, significantly improves the desulfurization degree and absorption Sulfur capacity of adsorbent.40
DEG C, silica alumina ratio 60, finish ratio is 20, when adsorption time is 4h, -11 adsorbent of molecular sieve of binderless ZSM-5 of the present invention
The 172.7% of adsorbent when desulfurization degree is containing binder.
Specific embodiment
The present invention is further described with reference to embodiments, but the contents of the present invention are not only in this.
Embodiment 1
Molded ZSM-11 molecular screen primary powder is prepared by following method: by ZSM-11 molecular screen primary powder, with Al2O3,
Sesbania powder is mixed in 1:1:0.05 ratio, and every gram molecule sieve original powder is corresponding to be added 10%wt diluted nitric acid aqueous solution 1.5mL, is mediated
After uniformly, extruded moulding.Dry 4h, crosses standard screen in 80 DEG C of baking ovens after grinding, and it is 150-425 μm that particle diameter, which is made,
Molded ZSM-11 molecular screen primary powder.
It is 250-425 μm of molded ZSM-11 molecular screen primary powder (molecular screen primary powder containing binder) 1g that sieve, which takes particle diameter,
150mLH is added in amorphous silica binder 5g2O, 5g TPAB, 33g sodium silicate aqueous solution (Si/Al=60), mixing
It uniformly, is 11.2,80 DEG C of heating water bath 1h by the way that NaOH aqueous solution is added to adjust solution ph, it is strong to stir, it is transferred to hydro-thermal
In crystallizing kettle, 180 DEG C of reactions are taken out afterwards for 24 hours in an oven, are washed, dry, and grinding, 550 DEG C of roastings obtain binderless ZSM-5-
11 molecular sieves.
The analog gasoline for being 50ppmw with normal octane configuration benzothiophene concentration.0.5g Adhesive-free Molecular Sieve is added simultaneously
It is compared with 0.5g molecular screen primary powder, 5mL analog gasoline is added, finish is than 10.The Static Adsorption 4h in 20 DEG C of constant-temperature tables,
Oil sample after absorption is taken to measure sulfur content in gas-chromatography.
Embodiment 2:
The analog gasoline for being 50ppmw with normal octane configuration benzothiophene concentration.0.5g Adhesive-free Molecular Sieve is added simultaneously
It is compared with 0.5g molecular screen primary powder, 10mL analog gasoline is added, finish is than 20.The Static Adsorption in 20 DEG C of constant-temperature tables
4h takes oil sample after absorption to measure sulfur content in gas-chromatography.
Embodiment 3:
The analog gasoline for being 50ppmw with normal octane configuration benzothiophene concentration.0.5g Adhesive-free Molecular Sieve is added simultaneously
It is compared with 0.5g molecular screen primary powder, 15mL analog gasoline is added, finish is than 30.The Static Adsorption in 20 DEG C of constant-temperature tables
4h takes oil sample after absorption to measure sulfur content in gas-chromatography.
Embodiment 4:
The analog gasoline for being 50ppmw with normal octane configuration benzothiophene concentration.0.5g Adhesive-free Molecular Sieve is added simultaneously
It is compared with 0.5g molecular screen primary powder, 20mL analog gasoline is added, finish is than 40.The Static Adsorption in 20 DEG C of constant-temperature tables
4h takes oil sample after absorption to measure sulfur content in gas-chromatography.
Embodiment 5:
The analog gasoline for being 50ppmw with normal octane configuration benzothiophene concentration.0.5g Adhesive-free Molecular Sieve is added simultaneously
It is compared with 0.5g molecular screen primary powder, 10mL analog gasoline is added, finish is than 20.The Static Adsorption in 40 DEG C of constant-temperature tables
2h takes oil sample after absorption to measure sulfur content in gas-chromatography.
Embodiment 6:
The analog gasoline for being 50ppmw with normal octane configuration benzothiophene concentration.0.5g Adhesive-free Molecular Sieve is added simultaneously
It is compared with 0.5g molecular screen primary powder, 10mL analog gasoline is added, finish is than 20.The Static Adsorption in 40 DEG C of constant-temperature tables
4h takes oil sample after absorption to measure sulfur content in gas-chromatography.
Embodiment 7:
The analog gasoline for being 50ppmw with normal octane configuration benzothiophene concentration.0.5g Adhesive-free Molecular Sieve is added simultaneously
It is compared with 0.5g molecular screen primary powder, 10mL analog gasoline is added, finish is than 20.The Static Adsorption in 40 DEG C of constant-temperature tables
6h takes oil sample after absorption to measure sulfur content in gas-chromatography.
Embodiment 8:
The analog gasoline for being 50ppmw with normal octane configuration benzothiophene concentration.0.5g Adhesive-free Molecular Sieve is added simultaneously
It is compared with 0.5g molecular screen primary powder, 10mL analog gasoline is added, finish is than 20.The Static Adsorption in 40 DEG C of constant-temperature tables
8h takes oil sample after absorption to measure sulfur content in gas-chromatography.
Embodiment 9:
The analog gasoline for being 50ppmw with normal octane configuration benzothiophene concentration.0.5g Adhesive-free Molecular Sieve is added simultaneously
It is compared with 0.5g molecular screen primary powder, 10mL analog gasoline is added, finish is than 20.The Static Adsorption in 30 DEG C of constant-temperature tables
4h takes oil sample after absorption to measure sulfur content in gas-chromatography.
Embodiment 10:
The analog gasoline for being 50ppmw with normal octane configuration benzothiophene concentration.0.5g Adhesive-free Molecular Sieve is added simultaneously
It is compared with 0.5g molecular screen primary powder, 10mL analog gasoline is added, finish is than 20.The Static Adsorption in 40 DEG C of constant-temperature tables
4h takes oil sample after absorption to measure sulfur content in gas-chromatography.
Embodiment 11:
The analog gasoline for being 50ppmw with normal octane configuration benzothiophene concentration.0.5g Adhesive-free Molecular Sieve is added simultaneously
It is compared with 0.5g molecular screen primary powder, 10mL analog gasoline is added, finish is than 20.The Static Adsorption in 50 DEG C of constant-temperature tables
4h takes oil sample after absorption to measure sulfur content in gas-chromatography.
Oil product adsorbs desulfurization effect under 1 molecular sieve containing binder of table, binder free composite molecular screen different condition
It is noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；Although ginseng
According to foregoing embodiments, invention is explained in detail, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments, or some or all of the technical features are carried out etc.
With replacement；And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution
Range.
Claims (10)
1. a kind of -11 molecular sieve preparation method of binderless ZSM-5, which comprises the following steps:
Step 1: by molded ZSM-11 molecular screen primary powder, template, amorphous silica binder and water according to following ratio
Example mixing 1-5:5-25:5-15:100-300, sodium silicate aqueous solution is added into mixture, makes silica alumina ratio 50- in mixture
90；
Step 2: adjusting the pH to 11-14 of mixture using NaOH solution；
Step 3: mixture is placed in 70-90 DEG C of water-bath, 0.5-2h is stirred；
Step 4: mixture is transferred to hydrothermal crystallizing kettle, hydrothermal crystallizing reacts 18-32h under the conditions of 90-180 DEG C；
Step 5: taking out washing to neutrality, dries, grind, screening, 550-650 DEG C of roasting 2-8h obtains binderless ZSM-5-11
Molecular sieve.
2. -11 molecular sieve preparation method of binderless ZSM-5 according to claim 1, which is characterized in that had become described in step 1
The partial size of type ZSM-11 molecular screen primary powder is 150-425 μm.
3. -11 molecular sieve preparation method of binderless ZSM-5 according to claim 1, which is characterized in that template described in step 1
Agent is one of 4-propyl bromide, tetrapropylammonium hydroxide or cetyl trimethylammonium bromide or a variety of mixing.
4. -11 molecular sieve preparation method of binderless ZSM-5 according to claim 1, which is characterized in that the silica is viscous
It ties agent and is selected from or mixtures thereof silica solution, waterglass, wherein SiO2Weight percentage be 10-50%.
5. -11 molecular sieve preparation method of binderless ZSM-5 according to claim 1, which is characterized in that the sodium metasilicate is water-soluble
Liquid group becomes Na2O=6-8wt%, SiO2=26-28wt%.
6. -11 molecular sieve preparation method of binderless ZSM-5 according to claim 1, which is characterized in that screened described in step 5
Particle diameter out is 0.25-0.425 μm.
7. -11 molecular sieve preparation method of binderless ZSM-5 according to claim 1, which is characterized in that the molded ZSM-
The preparation step of 11 molecular screen primary powders is as follows: by ZSM-11 molecular screen primary powder, Al2O31:0.25-2:0.03- is pressed with sesbania powder
The mixing of 0.07 ratio, every gram of ZSM-11 molecular screen primary powder is corresponding to be added 1-20%wt acidic aqueous solution 0.5-2ml, mediates uniform
Afterwards, extruded moulding；Dry 2-8h, crosses standard screen, molded ZSM-11 molecular screen primary powder is made in 80 DEG C of baking ovens after grinding.
8. a kind of -11 molecular sieve of binderless ZSM-5, which is characterized in that using preparation method described in claim 1-7 any one
It is prepared.
9. application of -11 molecular sieve of binderless ZSM-5 in desulfurizing oil described in a kind of claim 8, multiple using binder free
It closes molecular sieve to be in contact with sour product, realizes desulfurizing oil using static adsorptive method.
10. application of -11 molecular sieve of binderless ZSM-5 in desulfurizing oil according to claim 8, which is characterized in that oil
The condition that product are contacted with adsorbent is: pressure is normal pressure 101.325kPa, and temperature is 20-80 DEG C of constant temperature.
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| CN115701829A (en) * | 2022-10-17 | 2023-02-14 | 大连理工大学 | Preparation method of small pore molecular sieve forming adsorbent and application of adsorbent in preparation of electronic grade laughing gas by adsorbing unsaturated hydrocarbon |
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