CN106395846A - Spherical non-acidic molecular sieve, and preparation method and application thereof - Google Patents
Spherical non-acidic molecular sieve, and preparation method and application thereof Download PDFInfo
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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
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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
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/24—Type Y
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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
- C01B39/38—Type ZSM-5
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C—CHEMISTRY; METALLURGY
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/21—Attrition-index or crushing strength of granulates
Abstract
The invention discloses a spherical non-acidic molecular sieve, and a preparation method and application thereof. The preparation method of the molecular sieve comprises the following steps: mixing and stirring aluminum hydroxide powder, water and an acid aqueous solution to obtain sol; then adding the non-acidic molecular sieve into the sol and stirring to obtain slurry; dropping into a system composed of an aqueous solution with oil on the upper layer, aging liquid on the lower layer and a surfactant between two phases to form, drying and roasting. Through the method, cations which are lost in the peptizing process of the non-acidic molecular sieve can be immediately supplemented, and no washing is required after a forming carrier is aged, so that the operating process is simplified. Meanwhile, after an introduced small molecular additive is roasted, the mechanical strength of the forming carrier is improved. The spherical non-acidic molecular sieve prepared by the preparation method is smooth in surface, uniform in particle size and higher in strength and can be widely used as an absorbing agent, a catalyst, a catalyst carrier and the like.
Description
Technical field
The present invention relates to a kind of spherical non-acidic molecular sieve and preparation method and application.
Background technology
The oil ammonia column method of forming is to prepare a kind of common method of the beads such as aluminum oxide, silica, sial.It is by hydroxide
Aluminium powder acid is carried out after peptization, instill upper strata be oil, lower floor be Ageing solution, two alternate molten for, in the device of surfactant, making
Micelle balling-up in oil phase, gel in aging phase.The bead surface prepared in this way is smooth, uniform in size, mill
Damage low, intensity is high, is widely used as fixed bed and movable bed catalyst, catalyst carrier and adsorbent etc..
Boehmite or boehmite are dissolved in deionized water by US4542113, are mixing uniformly to form solid and contain
Measure the aluminum hydroxide suspension for 20～40 mass %, add dilute nitric acid solution to carry out peptization, then system is molded by oil ammonia column
Standby alumina balls.This patent is using addition nonionic surfactant (Alfol 610-4.5EO, Sasol North in colloidal sol
America Inc.) reducing oil water interfacial tension.Anion surfactant is replaced using nonionic surfactant, though energy
Reduce follow-up washing, calcination stepses, but when using nonionic surfactant water-soluble liquid, ball adhesion phenomenon usually occur,
Lead to balling-up yield extremely low.
CN1204964C describes a kind of oil ammonia column forming method of ball-aluminium oxide.Alumina sol is instilled by 0.1
Form spherical gel particles, so in the oil ammonia column of lower floor's electrolyte solution composition of the upper oil phase of～4.5mm and 10～300cm
After make gel particles aging 0.5～10h in electrolyte solution, re-dry, roasting.In the method, oil phase does not contain surface-active
Agent, but because oil reservoir is too thin, in large-scale industrial production oil cannot be carried out circulate, relatively costly it is difficult to realize industrialization.
Therefore choose suitable oil phase particularly critical with the volume ratio of aging phase.
Content of the invention
It is an object of the invention to provide a kind of spherical non-acidic molecular sieve and preparation method and application.
The method preparing spherical non-acidic molecular sieve that the present invention provides, comprises the steps：
1) by aluminium hydrate powder, water and sour mix and blend, obtain colloidal sol；
2) to step 1) add non-acidic molecular sieve in gained colloidal sol and stir, obtain slurries；
3) by step 2) gained slurries instill by upper strata be oil, lower floor is Ageing solution, is surfactant in the middle of two-phase
It is molded in the system of aqueous solution composition, dry for gained orbicule, roasting obtains described spherical non-acidic molecular sieve.
The step 1 of said method) in, the mesh number of described aluminium hydrate powder is 100～200 mesh；
The mass ratio of described aluminium hydrate powder and water is 1:2.5～1:10, preferably 1:2.5～1:5；
Described aluminium hydrate powder weightless ratio at 100 DEG C is 25%；
Described acid is nitric acid, hydrochloric acid, formic acid or acetic acid；
The mass percentage concentration of described acid is 5～20%, concretely 5%, 8%, 15% or 20%；
Described acid is 1ml with the amount ratio of aluminium hydrate powder：0.5-3g, specially 1ml：0.9g、1ml：1.2g、1ml：
1.7g、1ml：1.8g、1ml：2.7g or 1ml：2.9g；
In described whipping step, temperature is 60～90 DEG C, and the time is 1～6h, preferably 2～4h.
Described step 2) in, described non-acidic molecular sieve is Na-ZSM-5, NaY or KL molecular sieve；
Described non-acidic molecular sieve is 1 with the mass ratio of described aluminium hydrate powder:0.5-3, concretely 1:0.75、1:
0.9、1:1.2、1:1.5 or 1:2.9；
Mass fraction in shaping carrier for the non-acidic molecular sieve is 30%～80%；
In described whipping step, temperature is 60～90 DEG C, and the time is 0.5h～2h, preferably 0.5～1h.
Described step 3) in, described grease separation is from hexane, heptane, octane, nonane, toluene, gasoline, diesel oil, kerosene, petroleum ether
With at least one in atoleine；
Described Ageing solution is water-soluble selected from sodium hydrate aqueous solution, aqueous sodium carbonate, sodium bicarbonate aqueous solution, sodium metaaluminate
At least one in liquid, potassium hydroxide aqueous solution, wet chemical, potassium bicarbonate aqueous solution and the potassium metaaluminate aqueous solution；
The concentration of described Ageing solution is 0.5-2mol/L, specially 1mol/L；
Described surfactant is selected from α-sodium olefin sulfonate (AOS), lauryl both sexes sodium acetate (LAD-30), alcohol ether neighbour's benzene
Dioctyl phthalate monoesters sodium (PAES), lauryl sulfosuccinic acid monoester disodium (DLS), Coconut Fatty Acid Monoethanolamide sulfosuccinic acid list
Ester disodium (DMSS), Monododecylphosphate potassium (MAPK), laurel alcohol ether phosphate potassium (MAEPK), fatty acid potassium soap
(SFP), at least one in phenolic ether phosphate kalium salt (NP-10PK) and N- acyl glutamic acid potassium；
In the aqueous solution of described surfactant, surfactant is 1 with the volume ratio of water：4-8, concretely 1:5；
The volume ratio of described oil, Ageing solution and surfactant is 5～60：20～80：1, preferably 5～40：40～60：
1, can be more specifically 10:40:1、5:50:1、30:60:1、40:40:1、25:55:1 or 15:45:1.
Using the upper strata that the present invention provides be oil, lower floor be Ageing solution, in the middle of two-phase for the aqueous solution of surfactant
System is molded, and ensure that step 2) orbicule that is molded in this system of gained slurries has stable chondritic.
In described drying steps, baking temperature is 60～120 DEG C, preferably 60～90 DEG C, and drying time 12～48h is excellent
Elect 24～48h as；
In described calcination stepses, sintering temperature is 400～800 DEG C, preferably 400～600 DEG C, roasting time 3～10h,
It is preferably 3～6h.
Described roasting condition is：In the air is warming up to 400～800 DEG C of roastings 3～10 hours, and heating rate is 1 DEG C/min.
Methods described also comprises the steps：
In described step 1) after, described step 2) before whipping step, add micromolecule additive in system.
Described micromolecule additive be selected from sucrose, fructose, lactose, glucose, ethylene glycol, propane diols, glycerine, cellulose,
At least one of methylcellulose or carboxymethylcellulose calcium；
The consumption of described micromolecule additive is the 5%～20% of described aluminium hydrate powder quality, preferably 5%～
10%.
The present invention provide method prepare spherical non-acidic molecular sieve, from traditional oil ammonia column be molded unlike, system
In Ageing solution used be the solution containing cation with surfactant, the sun in described Ageing solution and surfactant solution
Ion is consistent with the cation in non-acidic molecular sieve.
In addition, the spherical non-acidic molecular sieve preparing according to the method described above and this spherical non-acidic molecular sieve are as load
Application in catalytic reaction for the body, falls within protection scope of the present invention.
Specifically, the particle diameter of described spherical non-acidic molecular sieve can be 1-5mm；The crushing of described spherical non-acidic molecular sieve
Intensity is more than 36N；Described spherical non-acidic molecular sieve for 0.5～1.2g/ml.
Described catalytic reaction can be alkane aromatization reaction, toluene chlorination, selective oxidation reaction or alkane
Aromatization.
In the aromatization of described alkane, the total number of carbon atoms of alkane can be 6-9, concretely 7；
The reaction condition of the aromatization of described alkane is concretely：The mass space velocity of described alkane is 1～3h-1；Hydrogen is 0.2～6.0 with the mol ratio of described alkane：1；Reaction pressure is 0.1～2MPa, such as 1.1MPa；Reaction temperature
For 300～600 DEG C, such as 500 DEG C.
The good sphericity that the global molecular sieve that the present invention provides has contributes to catalyst in moving bed catalytic reaction
During relative motion, can be effectively improved catalytic efficiency under moving bed catalytic condition for the catalyst, improve making of catalyst
Use the life-span.
The present invention using aluminum oxide as binding agent, using Ageing solution and the surfactant of cation, by powder
Non-acidic molecular sieve is made spherical, and gained particle has the advantages that smooth surface, epigranular, and Ageing solution can be mended in time simultaneously
Fill the cation that non-acidic molecular sieve loses in peptization course, do not change its original property.Meanwhile, introduce small molecule to add
Agent can improve the mechanical strength of shaping carrier.The method be obtained spherical non-acidic molecular sieve carrier, can be used as fixed bed and
Movable bed catalyst, catalyst carrier and adsorbent etc..This spherical non-acidic molecular sieve of the present invention is used for C6-C9 chain
During alkane aromatization reaction, up to 70～80%, aromatics yield is up to 40～50% for its liquid yield.
Brief description
Fig. 1 is the photo of embodiment 7 gained molecular sieve.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Institute
Method of stating is conventional method if no special instructions.Described raw material all can be either commercially available from open if no special instructions.
Used by following embodiments, KL molecular sieve is to be obtained as follows：
(1) 186.3g potassium hydroxide is dissolved in 1250g deionized water, after all dissolving, adds 45.14g aluminium hydrate powder
End, 96 DEG C of heating stirrings are clarified to solution, obtained solution A.
(2) solution A is dropped to room temperature, pour 667.7g Ludox into (containing 30%SiO in stirring with 300g water simultaneously2)
In, after continuing stirring 1h, load in enclosed high pressure kettle, in 175 DEG C of hydrothermal crystallizing 24h, after gained gel filtration, deionized water
By Washing of Filter Cake to filtrate pH value close to neutral, dry through 110 DEG C, roasting 6h at 500 DEG C, obtain degree of crystallinity close to 90%
KL molecular sieve.
Embodiment 1,
1) take the 67.6g aluminium hydrate powder (Sasol company produces, and alumina content is 76.7%) that mesh number is 100 mesh,
It is added to stirring 0.5h in 270g water under 60 DEG C of water bath condition, be subsequently adding the nitric acid aqueous solution that 25ml mass percentage concentration is 20%
Solution, stirs 2h, obtains colloidal sol；
2) to step 1) add in gained colloidal sol 55gNaY molecular sieve to stir 0.5h with 3.5g micromolecule additive ethylene glycol
Prepared slurries；
3) by step 2) gained slurries instill upper strata be diesel oil, lower floor be concentration for 0.5mol/L aqueous sodium carbonate,
In the middle of two-phase, for lauryl both sexes sodium acetate aqueous solution, (lauryl both sexes sodium acetate is 1 with the volume ratio of water：4) become in system
Type, the volume ratio of upper, middle and lower layer is 10:40:1, drip ball after take out rapidly, obtain orbicule, then 24h be dried at 80 DEG C, with 1 DEG C/
The heating rate of min is warming up to 500 DEG C of roasting 6h, obtains the spherical non-acidic molecular sieve of present invention offer.This is spherical nonacid
The physical property of molecular sieve is shown in Table 1.
Embodiment 2
1) take the 33g aluminium hydrate powder (Sasol company produces, and alumina content is 76.7%) that mesh number is 100 mesh, 80
DEG C stirring in water bath under the conditions of be added in the 100g aqueous solution stirring 1h, be subsequently adding the nitre that 18ml mass percentage concentration is 20%
Aqueous acid, stirs 4h, obtains colloidal sol；
2) to step 1) add in gained colloidal sol 35gNa-ZSM-5 molecular sieve stirring 1h that slurries are obtained；
3) by step 2) gained slurries instill upper strata be kerosene, lower floor be concentration for 1mol/L the sodium metaaluminate aqueous solution,
For the lauryl sulfosuccinic acid monoester two sodium water solution (volume ratio of lauryl sulfosuccinic acid monoester disodium and water in the middle of two-phase
For 1:4) it is molded in system, the volume ratio of upper, middle and lower layer is 5:50:1, take out rapidly after dripping ball, obtain orbicule, then 60
DEG C 24h is dried, 550 DEG C of roasting 4h are warming up to the heating rate of 1 DEG C/min, the spherical nonacid molecule of present invention offer is provided
Sieve.The physical property of this spherical non-acidic molecular sieve is shown in Table 1.
Embodiment 3
1) take the 11.73g aluminium hydrate powder (Sasol company produces, and alumina content is 76.7%) that mesh number is 100 mesh,
It is added to stirring 0.5h in the 55g aqueous solution under the conditions of 70 DEG C of stirring in water bath, being subsequently adding 10ml mass percentage concentration is 5%
Aqueous solution of nitric acid, stir 2.5h, obtain colloidal sol；
2) to step 1) add in gained colloidal sol 21gKL molecular sieve to stir 0.5h system with 1.1g micromolecule additive cellulose
Obtain slurries；
3) by step 2) gained slurries instill upper strata be diesel oil, lower floor be concentration for 0.5mol/L wet chemical,
The two alternate aqueous solution (laurel alcohol ether phosphate potassium, the fatty acid potassium soaps mixing with fatty acid potassium soap for laurel alcohol ether phosphate potassium
It is 1 with water volume ratio：1：4) it is molded in system, the volume ratio of upper, middle and lower layer is 30:60:1, take out rapidly after dripping ball, obtain
Orbicule, then 18h is dried at 60 DEG C, 500 DEG C of roasting 4h are warming up to the heating rate of 1 DEG C/min, present invention offer is provided
Spherical non-acidic molecular sieve.The physical property of this spherical non-acidic molecular sieve is shown in Table 1.
Embodiment 4
1) take the 94.6g aluminium hydrate powder (Sasol company produces, and alumina content is 76.7%) that mesh number is 200 mesh,
It is added to stirring 0.5h in the 300g aqueous solution, being subsequently adding 33ml mass percentage concentration is 15% under the conditions of 70 DEG C of stirring in water bath
Aqueous solution of nitric acid, stir 3.5h, obtain colloidal sol；
2) to step 1) add in gained colloidal sol 33gNa-ZSM-5 molecular sieve stirring 0.5h that slurries are obtained；
3) by step 2) to instill upper strata be atoleine to gained slurries, lower floor is total concentration is the sodium carbonate of 1mol/L and carbon
Sour hydrogen sodium equimolar is mixed with Nonyl pheno base ether for laurel alcohol ether phosphate potassium than in the middle of the aqueous solution of mixing, two-phase
The aqueous solution (volume ratio of laurel alcohol ether phosphate potassium, Nonyl pheno base ether and water be 1：1：5) it is molded in system,
The volume ratio of upper, middle and lower layer is 40:40:1, take out rapidly after dripping ball, obtain orbicule, then 36h is dried at 80 DEG C, with 1 DEG C/min
Heating rate be warming up to 500 DEG C of roasting 4h, obtain the present invention offer spherical non-acidic molecular sieve.This spherical nonacid molecule
The physical property of sieve is shown in Table 1.
Embodiment 5
1) take the 26.4g aluminium hydrate powder (Sasol company produces, and alumina content is 76.7%) that mesh number is 200 mesh,
It is added under the conditions of 70 DEG C of stirring in water bath in the 130g aqueous solution, stirs 1h, being subsequently adding 22ml mass percentage concentration is 15%
Aqueous solution of nitric acid, stir 2h, obtain colloidal sol；
2) to step 1) add in gained colloidal sol 38gKL molecular sieve stirring 1h that slurries are obtained；
3) by step 2) to instill upper strata be hexane and heptane miscella to gained slurries, lower floor is the hydrogen for 1mol/L for the total concentration
Potassium oxide with potassium carbonate equimolar than the aqueous solution mixing, two alternate for Monododecylphosphate potassium and laurel alcohol ether phosphate
(volume ratio of Monododecylphosphate potassium, laurel alcohol ether phosphate potassium and water is 1 to the aqueous solution of potassium mixing:1:5) system
Middle shaping, the volume ratio of upper, middle and lower layer is 25:55:1, take out rapidly after dripping ball, obtain orbicule, then 30h is dried at 70 DEG C, with
The heating rate of 1 DEG C/min is warming up to 500 DEG C of roasting 4h, obtains the spherical non-acidic molecular sieve of present invention offer.This is spherical non-
The physical property of acidic molecular sieve is shown in Table 1.
Embodiment 6
1) take the 37.4g aluminium hydrate powder (Sasol company produces, and alumina content is 76.7%) that mesh number is 200 mesh,
It is added under the conditions of 90 DEG C of stirring in water bath in 105g deionized water solution, stir 0.5h, be subsequently adding 42ml percent mass dense
Spend for, in 8% aqueous solution of nitric acid, stirring 3h, obtaining colloidal sol；
2) to step 1) add in gained colloidal sol 25gKL molecular sieve stirring 1h that slurries are obtained；
3) by step 2) gained slurries instill upper strata be diesel oil, lower floor be concentration for 2mol/L potassium hydroxide aqueous solution,
The two alternate aqueous solution (Monododecylphosphate potassium, the phenol mixing with phenolic ether phosphate kalium salt for Monododecylphosphate potassium
The volume ratio of ether phosphate sylvite and water is 1:1:5) it is molded in system, the volume ratio of upper, middle and lower layer is 15:45:1, after dripping ball
Rapid taking-up, obtains orbicule, then 48h is dried at 60 DEG C, be warming up to 500 DEG C of roasting 4h with the heating rate of 1 DEG C/min, obtain
The spherical non-acidic molecular sieve that the present invention provides.The physical property of this spherical non-acidic molecular sieve is shown in Table 1.
Embodiment 7
In embodiment 5 step 2) add 3.0g micromolecule additive glucose before stirring, other steps are identical, obtain this
The spherical non-acidic molecular sieve that invention provides.
The granule-morphology of this spherical non-acidic molecular sieve of embodiment gained is shown in Fig. 1, and particle diameter is 2～3mm.Its physical property is such as
Shown in table 1.
Will be molten in tetraammineplatinum chloride to this embodiment resulting vehicle particle or embodiment 5 resulting vehicle particle incipient impregnation
In liquid, stand 1～48h, filter, after 100～150 DEG C of drying 2～24h, roasting 4～8h, is born at 300～510 DEG C
Load type Pt catalyst, and have rated the normal heptane aromatization performance of gained catalyst, appreciation condition is：Reaction temperature 500,
DEG C pressure 1.1MPa, mass space velocity 1.0h-1, hydrogen hydrocarbon atomic ratio is 6.0, and evaluation cycle is 250h.Aromatization products liquid is received and is
73.4%, and aromatics yield is 50.9%.
The property of resulting vehicle in table 1, embodiment
As seen from table, the spherical non-acidic molecular sieve of present invention preparation, its crushing strength is 36.4～70.8N, heap density
For 0.61～1.19g/ml, substantially conform to the requirement to carrier of fixed bed and moving bed.Comparative example 5 is understood with embodiment 7,
The meeting that adds of micromolecule additive increases the intensity of carrier further.
Claims (10)
1. a kind of method preparing spherical non-acidic molecular sieve, comprises the steps：
1) by aluminium hydrate powder, water and sour mix and blend, obtain colloidal sol；
2) to step 1) add non-acidic molecular sieve in gained colloidal sol and stir, obtain slurries；
3) by step 2) gained slurries instill by upper strata be oil, lower floor be Ageing solution, in the middle of two-phase water-soluble for surfactant
It is molded in the system of liquid composition, dry for gained orbicule, roasting obtains described spherical non-acidic molecular sieve.
2. method according to claim 1 it is characterised in that：Described step 1) in, the mesh number of described aluminium hydrate powder is
100～200 mesh；
The mass ratio of described aluminium hydrate powder and water is 1：2.5～10；
Described acid is nitric acid, hydrochloric acid, formic acid or acetic acid；
The mass percentage concentration of described acid is 5～20%；
Described acid is 1ml with the amount ratio of aluminium hydrate powder：0.5-3g；
In described whipping step, temperature is 60～90 DEG C；Time is 1～6h.
3. method according to claim 1 and 2 it is characterised in that：Described step 2) in, described non-acidic molecular sieve is
Na-ZSM-5, NaY or KL molecular sieve；
Described non-acidic molecular sieve is 1 with the mass ratio of described aluminium hydrate powder:0.5-3；
In described whipping step, temperature is 60～90 DEG C；Time is 0.5h～2h.
4. according to described method arbitrary in claim 1-3 it is characterised in that：Described step 3) in, described grease separation from hexane,
At least one in heptane, octane, nonane, toluene, gasoline, diesel oil, kerosene, petroleum ether and atoleine；
Described Ageing solution be selected from sodium hydrate aqueous solution, aqueous sodium carbonate, sodium bicarbonate aqueous solution, the sodium metaaluminate aqueous solution,
At least one in potassium hydroxide aqueous solution, wet chemical, potassium bicarbonate aqueous solution and the potassium metaaluminate aqueous solution；
The concentration of described Ageing solution is 0.5-2mol/L；
Described surfactant is selected from α-sodium olefin sulfonate, lauryl both sexes sodium acetate, alcohol ether phthalic monoester sodium, bay
Base sulfosuccinic acid monoester disodium, Coconut Fatty Acid Monoethanolamide sulfosuccinic acid monoesters disodium, Monododecylphosphate potassium, the moon
At least one in cinnamic alcohol ether phosphate potassium, fatty acid potassium soap, phenolic ether phosphate kalium salt and N- acyl glutamic acid potassium；
In the aqueous solution of described surfactant, surfactant is 1 with the volume ratio of water：4-8；
The volume ratio of described oil, Ageing solution and surfactant is 5～60：20～80：1.
5. according to described method arbitrary in claim 1-4 it is characterised in that：Described step 3) in drying steps, temperature is
60～120 DEG C or 60～90 DEG C, time 12～48h or 24～48h；
In described calcination stepses, sintering temperature is 400～800 DEG C or 400～600 DEG C；Roasting time is 3～10h or 3～6h.
Described roasting condition is：In the air is warming up to 400～800 DEG C of roastings 3～10 hours；Heating rate is 1 DEG C/min.
6. according to described method arbitrary in claim 1-5 it is characterised in that：Methods described also comprises the steps：
In described step 1) after, described step 2) before whipping step, add micromolecule additive in system.
7. method according to claim 6 it is characterised in that：Described micromolecule additive be selected from sucrose, fructose, lactose,
At least one of glucose, ethylene glycol, propane diols, glycerine, cellulose, methylcellulose or carboxymethylcellulose calcium；
The consumption of described micromolecule additive is the 5%～20% of described aluminium hydrate powder quality.
8. the spherical non-acidic molecular sieve that the arbitrary methods described of claim 1-7 prepares.
9. the application in catalytic reaction as carrier of spherical non-acidic molecular sieve described in claim 8.
10. according to claim 9 application it is characterised in that：Described catalytic reaction is alkane aromatization reaction, toluene chlorine
Change the aromatization of reaction, selective oxidation reaction or alkane；
In the aromatization of described alkane, the total number of carbon atoms of alkane is specially 6-9 or 7；
The reaction condition of the aromatization of described alkane is specially：The mass space velocity of described alkane is 1～3h-1；Hydrogen
Mol ratio with described alkane is 0.2～6.0：1；Reaction pressure is 0.1～2MPa or 1.1MPa；Reaction temperature be 300～
600 DEG C or 500 DEG C.
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|---|---|---|---|---|
| CN112429755A (en) * | 2020-11-18 | 2021-03-02 | 山东物华新材料科技有限公司 | Preparation method of water treatment active alumina ball |
| CN115872424A (en) * | 2022-12-30 | 2023-03-31 | 黄河三角洲京博化工研究院有限公司 | High-strength spherical alumina and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112429755A (en) * | 2020-11-18 | 2021-03-02 | 山东物华新材料科技有限公司 | Preparation method of water treatment active alumina ball |
| CN115872424A (en) * | 2022-12-30 | 2023-03-31 | 黄河三角洲京博化工研究院有限公司 | High-strength spherical alumina and preparation method thereof |
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