CN108479858A - A kind of binder free spray forming technique improving molecular sieve catalyst intensity - Google Patents
A kind of binder free spray forming technique improving molecular sieve catalyst intensity Download PDFInfo
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- CN108479858A CN108479858A CN201810390995.5A CN201810390995A CN108479858A CN 108479858 A CN108479858 A CN 108479858A CN 201810390995 A CN201810390995 A CN 201810390995A CN 108479858 A CN108479858 A CN 108479858A
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- molecular sieve
- sieve catalyst
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- forming technique
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention belongs to catalyst technical fields, and in particular to a kind of binder free spray forming technique improving molecular sieve catalyst intensity includes the following steps：（1）Dispersant is added in deionized water, dispersant solution is formed, then molecular sieve catalyst is added in dispersant solution, forms the slurry that solid content is 35 50%；（2）Agate ball, 2 6h of ball milling are added into slurry, screening detaches agate ball, the constant temperature at 25 DEG C of the slurry after separation saves backup；（3）By step（2）Obtained slurry carries out spray drying forming；（4）By step（3）Product it is dry under 100 150 DEG C of air atmosphere, then roast.Moulding process provided by the invention improves the wear-resistant strength of catalyst, in the case where not adding binder, still can keep higher wear-resistant strength.
Description
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of binder free spray improving molecular sieve catalyst intensity
Mist moulding process.
Background technology
Molding refers to that all kinds of powders, particle, solution or fused raw material are assembled mutually under certain outer force effect, and being made has
The unit process of the solid particle of definite shape, size and intensity.Though solid catalyst with which kind of method prepare, finally with
The particle of different shape and size uses in catalytic reactor, and molding is the important procedure in catalyst preparation.
Spray shaping is, using the drying equipment of similar milk powder producing, suspension or cream to be pasted using spray drying principle
The forming method of micro-spherical catalyst is made in shape material.Solution is separated into misty liquid droplets, the mesh of atomization by generally use atomizer
Be slurries are dispersed into the fine mist of average diameter (20~60) μm, when droplet and hot wind contact, droplet gasifies rapidly,
It is dried to powder or granular product.
Currently, spray forming technique has been obtained for being widely applied in the preparation of fluid catalyst, still, existing
In some catalyst spray moulding process, it is required for addition binder, with the mechanical strength for improving preformed catalyst and wear-resisting journey
Degree.And the addition of binder, the activity of catalyst can be influenced, certain influence is also brought along to the post-processing of catalysis.
Invention content
In view of the drawbacks of the prior art, the present invention provides a kind of binder free spray shaping method of molecular sieve catalyst,
The intensity of molecular sieve of preparation is high, and wearability is good.
A kind of binder free spray forming technique improving molecular sieve catalyst intensity, includes the following steps：
（1）Dispersant is added in deionized water, dispersant solution is formed, dispersant solution then is added in molecular sieve catalyst
In, form the slurry that solid content is 35-50%；
（2）Agate ball is added into slurry so that ratio of grinding media to material is（3-5）：1, ball milling 2-6h, screening, agate ball is detached, and is detached
The constant temperature at 25 DEG C of slurry afterwards saves backup；
（3）By step（2）Obtained slurry carries out spray drying forming, and spray drying forming technique is：Charging rate 70mL/
Min, 220-230 DEG C of intake air temperature, 100-105 DEG C of air outlet temperature, nebulizer pressure -40~-65Pa, atomizer frequency
50-90Hz；
（4）By step（3）Product under 100-150 DEG C of air atmosphere dry 3-7h, then with the heating of 50-100 DEG C/h
Speed is warming up to 500-700 DEG C, roasts 5-7h.
Preferably, the mass concentration of the dispersant solution is 0.4-0.6%.
Preferably, the dispersant is polyvinyl alcohol.
Preferably, it is 1 that the agate ball, which is mass ratio,：The mixture of the agate ball of 2 diameter 10mm and diameter 6mm.
Preferably, the frequency of ball mill is 60-120Hz when the ball milling.
Heretofore described molecular sieve catalyst is in the prior art using molecular sieve as carrier, and active component is loaded
Catalyst on molecular sieve carrier, be using prior art preparation at molecular sieve catalyst.
Step of the present invention（1）Middle meaning solid content is the weight percent of catalyst in slurry.
Ratio of grinding media to material of the present invention refers to the mass ratio of agate ball and slurry.
Advantages of the present invention：
Molecular sieve catalyst can improve the homogeneity of particle diameter distribution after ball milling, in spray shaping, between catalyst granules
Uniform hole support construction can be formed, in drying and roasting, the inside and outside uniform shrinkage of catalyst granules increases
The wear-resistant strength of the compactness of catalyst granules, final catalyst improves.In the case where not adding binder, still can keep
Higher wear-resistant strength.
Specific implementation mode
Spray drying forming device therefor is the special spray dryer of high technology ceramics（Model C SD-20, Changzhou guide are dry
Dry equipment Co., Ltd）.
Embodiment 1
Raw material：HZSM-5 molecular sieve catalysts are the HZSM-5 molecular sieves of the active molybdenum Mo of load in the prior art,
The SiO of middle molecular sieve2∕Al2O3=30, specific surface area is >=320m2The loading of/g, molybdenum element are 2%.
A kind of binder free spray forming technique improving molecular sieve catalyst intensity, includes the following steps：
（1）Polyethylene of dispersing agent alcohol is added in deionized water, the poly-vinyl alcohol solution that mass concentration is 0.4% is formed, then will
HZSM-5 molecular sieve catalysts are added in poly-vinyl alcohol solution, form the slurry that solid content is 35%；
（2）Agate ball is added into slurry so that ratio of grinding media to material 3：1, ball milling 2h, the frequency of ball mill is 60Hz, sieve when ball milling
Point, agate ball is detached, the constant temperature at 25 DEG C of the slurry after separation saves backup；Wherein, it is 1 that the agate ball, which is mass ratio,：2
Diameter 10mm and diameter 6mm agate ball mixture；
（3）By step（2）Obtained slurry carries out spray drying forming, and spray drying forming technique is：Charging rate 70mL/
Min, 220 DEG C of intake air temperature, 100 DEG C, nebulizer pressure -40Pa of air outlet temperature, atomizer frequency 50Hz；
（4）By step（3）Product under 100 DEG C of air atmosphere dry 7h, be then warming up to the heating rate of 50 DEG C/h
500 DEG C, roast 7h.
Embodiment 2
Raw material：Molecular sieve catalyst is the same as embodiment 1.
A kind of binder free spray forming technique improving molecular sieve catalyst intensity, includes the following steps：
（1）Polyethylene of dispersing agent alcohol is added in deionized water, the poly-vinyl alcohol solution that mass concentration is 0.6% is formed, then will
HZSM-5 molecular sieve catalysts are added in poly-vinyl alcohol solution, form the slurry that solid content is 50%；
（2）Agate ball is added into slurry so that ratio of grinding media to material 5：1, ball milling 6h, the frequency of ball mill is 70Hz when ball milling, so
After sieve, agate ball is detached, the constant temperature at 25 DEG C of the slurry after separation saves backup；Wherein, the agate ball is mass ratio
It is 1：The mixture of the agate ball of 2 diameter 10mm and diameter 6mm；
（3）By step（2）Obtained slurry carries out spray drying forming, and spray drying forming technique is：Charging rate 70mL/
Min, 230 DEG C of intake air temperature, 105 DEG C, nebulizer pressure -65Pa of air outlet temperature, atomizer frequency 90Hz；
（4）By step（3）Product under 150 DEG C of air atmosphere dry 3h, be then warming up to the heating rate of 100 DEG C/h
700 DEG C, roast 5h.
Embodiment 3
Raw material：Molecular sieve catalyst is the same as embodiment 1.
A kind of binder free spray forming technique improving molecular sieve catalyst intensity, includes the following steps：
（1）Polyethylene of dispersing agent alcohol is added in deionized water, the poly-vinyl alcohol solution that mass concentration is 0.5% is formed, then will
HZSM-5 molecular sieve catalysts are added in poly-vinyl alcohol solution, form the slurry that solid content is 40%；
（2）Agate ball is added into slurry so that ratio of grinding media to material 4：1, ball milling 4h, the frequency of ball mill is 120Hz when ball milling, so
After sieve, agate ball is detached, the constant temperature at 25 DEG C of the slurry after separation saves backup；Wherein, the agate ball is mass ratio
It is 1：The mixture of the agate ball of 2 diameter 10mm and diameter 6mm；
（3）By step（2）Obtained slurry carries out spray drying forming, and spray drying forming technique is：Charging rate 70mL/
Min, 225 DEG C of intake air temperature, 102 DEG C, nebulizer pressure -50Pa of air outlet temperature, atomizer frequency 70Hz；
（4）By step（3）Product under 130 DEG C of air atmosphere dry 5h, be then warming up to the heating rate of 100 DEG C/h
600 DEG C, roast 6h.
Embodiment 4
Raw material：HZSM-5 molecular sieve catalysts are the HZSM-5 molecular sieves of the active molybdenum Mo of load in the prior art,
The SiO of middle molecular sieve2∕Al2O3=45, specific surface area is >=340m2The loading of/g, molybdenum element are 6%.
A kind of binder free spray forming technique improving molecular sieve catalyst intensity, includes the following steps：
（1）Polyethylene of dispersing agent alcohol is added in deionized water, the poly-vinyl alcohol solution that mass concentration is 0.5% is formed, then will
Molecular sieve catalyst is added in poly-vinyl alcohol solution, forms the slurry that solid content is 40%；
（2）Agate ball is added into slurry so that ratio of grinding media to material 4：1, ball milling 4h, rotating speed when ball milling are 70 Hz, are sieved, will
Agate ball detaches, and the constant temperature at 25 DEG C of the slurry after separation saves backup；Wherein, it is 1 that the agate ball, which is mass ratio,：2 it is straight
The mixture of the agate ball of diameter 10mm and diameter 6mm；
（3）By step（2）Obtained slurry carries out spray drying forming, and spray drying forming technique is：Charging rate 70mL/
Min, 225 DEG C of intake air temperature, 102 DEG C, pressure -50Pa of air outlet temperature, atomizer frequency 70Hz；
（4）By step（3）Product under 130 DEG C of air atmosphere dry 5h, be then warming up to the heating rate of 100 DEG C/h
600 DEG C, roast 6h.
Performance detection
The abrasion index that the catalyst that each embodiment is finally prepared is measured using abrasion index determinator, not have in each embodiment
It is blank control, the i.e. raw molecule of embodiment 1-3 by the raw molecule sieve catalyst that process provided by the invention is crossed
Sieve catalyst（The HZSM-5 molecular sieves of active elements Mo are loaded, the loading of Mo is 2%, the SiO of molecular sieve2∕Al2O3=30,
Specific surface area is >=320m2/g）For blank control 1；The raw molecule of embodiment 4 sieves（Load the HZSM-5 of active elements Mo
The loading of molecular sieve, Mo is 6%, the SiO of molecular sieve2∕Al2O3=45, specific surface area is >=340m2/g）For blank control 2, knot
Fruit is shown in Table 1.
1 abrasion index result of table
。
Claims (5)
1. a kind of binder free spray forming technique improving molecular sieve catalyst intensity, it is characterised in that：Include the following steps：
（1）Dispersant is added in deionized water, dispersant solution is formed, dispersant solution then is added in molecular sieve catalyst
In, form the slurry that solid content is 35-50%；
（2）Agate ball is added into slurry so that ratio of grinding media to material is（3-5）：1, ball milling 2-6h, screening, agate ball is detached, and is detached
The constant temperature at 25 DEG C of slurry afterwards saves backup；
（3）By step（2）Obtained slurry carries out spray drying forming, and spray drying forming technique is：Charging rate 70mL/
Min, 220-230 DEG C of intake air temperature, 100-105 DEG C of air outlet temperature, nebulizer pressure -40~-65Pa, atomizer frequency
50-90Hz；
（4）By step（3）Product under 100-150 DEG C of air atmosphere dry 3-7h, then with the heating of 50-100 DEG C/h
Speed is warming up to 500-700 DEG C, roasts 5-7h.
2. a kind of binder free spray forming technique improving molecular sieve catalyst intensity according to claim 1, special
Sign is：The mass concentration of the dispersant solution is 0.4-0.6%.
3. a kind of binder free spray forming technique improving molecular sieve catalyst intensity according to claim 1 or 2,
It is characterized in that：The dispersant is polyvinyl alcohol.
4. a kind of binder free spray forming technique improving molecular sieve catalyst intensity according to claim 1, special
Sign is：The agate ball is that mass ratio is 1：The mixture of the agate ball of 2 diameter 10mm and diameter 6mm.
5. a kind of binder free spray forming technique improving molecular sieve catalyst intensity according to claim 1, special
Sign is：The frequency of ball mill is 60-120Hz when the ball milling.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810390995.5A CN108479858A (en) | 2018-04-27 | 2018-04-27 | A kind of binder free spray forming technique improving molecular sieve catalyst intensity |
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| CN201810390995.5A CN108479858A (en) | 2018-04-27 | 2018-04-27 | A kind of binder free spray forming technique improving molecular sieve catalyst intensity |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112058302A (en) * | 2020-10-26 | 2020-12-11 | 陕西延长石油（集团）有限责任公司 | Preparation method and application of ZSM-5 molecular sieve catalyst |
| CN114044522A (en) * | 2021-11-24 | 2022-02-15 | 福州大学 | Functional active aluminosilicate and preparation method and application thereof |
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| CN102502692A (en) * | 2011-11-21 | 2012-06-20 | 烟台大学 | High-intensity molecular sieve and preparation method thereof |
| CN102527445A (en) * | 2011-12-21 | 2012-07-04 | 陕西煤化工技术工程中心有限公司 | Preparation method of low-abrasion fluidized bed microspherical catalyst |
| CN102631945A (en) * | 2011-10-24 | 2012-08-15 | 常云峰 | Preparing method of wearing-resistant catalyst |
| CN103623858A (en) * | 2012-08-21 | 2014-03-12 | 湖北赛因化工有限公司 | Catalytic cracking catalyst and preparation method |
| WO2015004230A1 (en) * | 2013-07-11 | 2015-01-15 | Basf Se | Application of binderless zeolite molecular sieves for the drying of carbonates used as eletrolytic solvents |
| CN104549551A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing microsphere FCC (fluid catalytic cracking) catalyst |
| US20160133992A1 (en) * | 2013-07-11 | 2016-05-12 | Basf Se | Drying of electrolyte mixtures containing acids with molecular sieves |
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2018
- 2018-04-27 CN CN201810390995.5A patent/CN108479858A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102006934A (en) * | 2008-04-18 | 2011-04-06 | 株式会社明电舍 | Catalyst and process for producing the same |
| CN102631945A (en) * | 2011-10-24 | 2012-08-15 | 常云峰 | Preparing method of wearing-resistant catalyst |
| CN102502692A (en) * | 2011-11-21 | 2012-06-20 | 烟台大学 | High-intensity molecular sieve and preparation method thereof |
| CN102527445A (en) * | 2011-12-21 | 2012-07-04 | 陕西煤化工技术工程中心有限公司 | Preparation method of low-abrasion fluidized bed microspherical catalyst |
| CN103623858A (en) * | 2012-08-21 | 2014-03-12 | 湖北赛因化工有限公司 | Catalytic cracking catalyst and preparation method |
| WO2015004230A1 (en) * | 2013-07-11 | 2015-01-15 | Basf Se | Application of binderless zeolite molecular sieves for the drying of carbonates used as eletrolytic solvents |
| US20160133992A1 (en) * | 2013-07-11 | 2016-05-12 | Basf Se | Drying of electrolyte mixtures containing acids with molecular sieves |
| CN104549551A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for preparing microsphere FCC (fluid catalytic cracking) catalyst |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112058302A (en) * | 2020-10-26 | 2020-12-11 | 陕西延长石油（集团）有限责任公司 | Preparation method and application of ZSM-5 molecular sieve catalyst |
| CN112058302B (en) * | 2020-10-26 | 2023-02-28 | 陕西延长石油（集团）有限责任公司 | Preparation method and application of ZSM-5 molecular sieve catalyst |
| CN114044522A (en) * | 2021-11-24 | 2022-02-15 | 福州大学 | Functional active aluminosilicate and preparation method and application thereof |
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Application publication date: 20180904 |