CN114408940A - 4A molecular sieve ingredient and 4A molecular sieve manufacturing method - Google Patents
4A molecular sieve ingredient and 4A molecular sieve manufacturing method Download PDFInfo
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- CN114408940A CN114408940A CN202210038953.1A CN202210038953A CN114408940A CN 114408940 A CN114408940 A CN 114408940A CN 202210038953 A CN202210038953 A CN 202210038953A CN 114408940 A CN114408940 A CN 114408940A
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- 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 126
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 114
- 239000004615 ingredient Substances 0.000 title claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 73
- 238000010304 firing Methods 0.000 claims abstract description 66
- 239000011230 binding agent Substances 0.000 claims abstract description 36
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000004088 foaming agent Substances 0.000 claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 239000003607 modifier Substances 0.000 claims abstract description 25
- 239000000314 lubricant Substances 0.000 claims abstract description 22
- 238000003825 pressing Methods 0.000 claims abstract description 19
- 238000000465 moulding Methods 0.000 claims abstract description 10
- 238000001125 extrusion Methods 0.000 claims abstract description 8
- 238000005507 spraying Methods 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- 238000007599 discharging Methods 0.000 claims description 18
- 239000003292 glue Substances 0.000 claims description 15
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000009966 trimming Methods 0.000 claims description 10
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 9
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229920000881 Modified starch Polymers 0.000 claims description 4
- 239000004368 Modified starch Substances 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 235000019426 modified starch Nutrition 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 2
- 239000008158 vegetable oil Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 39
- 238000009826 distribution Methods 0.000 abstract description 12
- 238000001179 sorption measurement Methods 0.000 abstract description 8
- 238000004891 communication Methods 0.000 abstract description 5
- 238000010137 moulding (plastic) Methods 0.000 abstract description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract description 4
- 238000005096 rolling process Methods 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 239000011800 void material Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 23
- 239000007921 spray Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- 235000019484 Rapeseed oil Nutrition 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 5
- 235000012424 soybean oil Nutrition 0.000 description 4
- 239000003549 soybean oil Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 241001133794 Acoelorraphe wrightii Species 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 ethylene, propylene, methane Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
-
- 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
- C01B39/14—Type A
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0006—Honeycomb structures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Structural Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a 4A molecular sieve ingredient which comprises the following components in percentage by mass: 85% -96% of amorphous silica-alumina main material; 0-10% of a forming binder; 0.5-3% of pore-forming agent; 1-4% of a forming lubricant; 0.1-0.5% of a modifier; 0.05-0.1% of molecular sieve framework foaming agent. Also discloses a method for preparing the 4A molecular sieve by adopting the ingredients, which obtains the uniform pore distribution and the full open pore structure of the molecular sieve framework and improves the adsorption performance of the molecular sieve. The addition amount of the adhesive is reduced by adopting a mixed formula of amorphous silicon oxide and aluminum hydroxide. The dry pressing molding of the invention adopts a plastic molding bracket to obtain the mutual communication among the pores of the 4A molecular sieve. The void fraction is increased. And adding a modifier to reduce the firing temperature by 150-250 ℃. The manufacturing process of the invention is more environment-friendly. The honeycomb structure can be manufactured by (1) extrusion molding respectively; (2) dry pressing to form flat plate or anisotropic structure; (3) the ball rolling machine is used for manufacturing a spherical structure.
Description
Technical Field
The invention relates to a 4A molecular sieve ingredient, in particular to a molecular sieve for adsorbing environmental VOC, which can be used for the environmental protection field of adsorption treatment of VOC gases such as water, methanol, ethanol, hydrogen sulfide, hydrogen fluoride, sulfur dioxide, carbon dioxide, ethylene, propylene, methane, ether, acetylene and the like. The invention also relates to a manufacturing method of the molecular sieve.
Background
Molecular sieve adsorption is a polluted gas separation technology with great application value and is widely applied to many VOC emission fields. As an advantageous adsorption material, the molecular sieve material has the characteristics of medium corrosion resistance, good mechanical property, long service life and the like. Compared with the traditional combustion process, the molecular sieve has long service life, low energy consumption and good treatment effect, and can solve the problem of treating the unorganized waste gas. Meanwhile, the adsorption and desorption process is automatically controlled, waste gas can be conveniently and automatically collected and enriched, and the automatic and efficient implementation of VOC treatment in industrial production is realized.
The 4A molecular sieve has higher specific adsorption surface area at the same volume with high packing density. However, the production and processing of 4A molecular sieves face the following problems:
firstly, the pore distribution of the molecular sieve framework is not uniform, and the adsorption efficiency is low;
secondly, the internal pore structure of the molecular sieve seals the excessive proportion of pores;
thirdly, the regeneration temperature of the common molecular sieve is too high, the nano structure collapses when the regeneration process exceeds 650 ℃, and the structural stability of the molecular sieve is poor;
and fourthly, the addition amount of the organic matters is large, the burning process needs advanced treatment on waste gas generated by the organic matters, and the production process of the molecular sieve is not beneficial to environmental protection.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a 4A molecular sieve ingredient, the 4A molecular sieve prepared by the 4A molecular sieve ingredient has uniform pore distribution and high open pore occupation ratio, and the preparation process is relatively environment-friendly.
The invention also provides a preparation method of the 4A molecular sieve by using the 4A molecular sieve ingredient.
The invention also provides a preparation method of the 4A molecular sieve.
The 4A molecular sieve ingredient adopts the following technical scheme:
A4A molecular sieve ingredient comprises the following components in percentage by mass:
the invention can further adopt the following improvement measures to solve the problems:
preferably, the amorphous silica-alumina main material comprises at least one of amorphous silica and aluminum hydroxide.
Preferably, in the amorphous silica-alumina main material, the mass ratio of amorphous silica to aluminum hydroxide is 9: 1-6: 4. better forming performance and sintering characteristic can be obtained through the coordination and the proportion of the amorphous silicon oxide and the aluminum hydroxide.
Preferably, the particle size of the amorphous silica-alumina main material is not more than 10 microns, and a proper particle size range is selected according to the requirement of designing the pore diameter of an airflow channel of the molecular sieve. More preferably, when the aperture of the designed molecular sieve airflow channel is 0.1 micron, the amorphous silica-alumina main material with the particle size of 2-4 microns is selected; when the aperture of the designed molecular sieve airflow channel is 1 micron, the amorphous silica-alumina main material with the granularity of 5-8 microns is selected.
Preferably, the forming binder comprises at least one of polyvinyl alcohol (PVA), modified starch ether, carboxymethyl starch (CMS); the pore-forming agent comprises at least one of carbon black powder, graphite powder, expanded graphite powder and cellulose.
Preferably, the forming lubricant is a vegetable oil. More preferably the forming lubricant is rapeseed oil.
Preferably, the modifier comprises one or more of magnesium oxide, magnesium hydroxide, calcium oxide, kaolin, zinc oxide, vanadium pentoxide and zirconium oxide;
the molecular sieve skeleton foaming agent comprises one or more of silicon carbide, silicon nitride, aluminum nitride and boron nitride.
In order to obtain a better macroporosity molecular sieve framework, a trace amount of medium-high temperature foaming agent is selected and matched with a pore-forming agent, so that the open porosity of more than 55 percent can be obtained.
The technical scheme of the preparation method of the 4A molecular sieve by using the 4A molecular sieve ingredient is as follows:
the method comprises the following steps:
A. uniformly mixing the components in proportion to obtain a mixed material;
B. performing extrusion molding on the mixed material, specifically comprising the steps of performing ball milling, pugging, aging, extruding, drying, firing and trimming on the mixed material to obtain the 4A molecular sieve; or
C. And (3) dry-pressing and molding the mixed material, specifically comprising the steps of dry-pressing, firing and trimming the mixed material to obtain the 4A molecular sieve.
Preferably, in the step B, the aging time is 12-36 hours.
Preferably, in the step B, a step of removing glue is further included before the firing, wherein the glue removing temperature is 260-400 ℃, and the glue removing time is 2-8 hours; the firing temperature is 770-1050 ℃, and the firing time is 0.5-2 hours;
step C, a step of removing glue is further included before the firing, wherein the glue removing temperature is 260-400 ℃, and the glue removing time is 1-2 hours; the firing temperature is 770-1050 ℃, and the firing time is 0.5-2 hours;
preferably, in the steps B and C, the thickness of the sprayed film is 5-25 micrometers; the sintering temperature is 880-980 ℃, and the sintering time is 0.5-1.5 hours.
The technical scheme has the following technical effects:
1) according to the invention, the uniform pore distribution and the full pore structure of the molecular sieve framework are obtained by matching the pore-forming agent and the foaming agent, and the adsorption performance of the molecular sieve is improved by adding a proper modifier. The addition amount of the adhesive is reduced by adopting a mixed formula of amorphous silicon oxide and aluminum hydroxide.
2) The dry pressing molding of the invention adopts a plastic molding bracket to obtain the mutual communication among the pores of the 4A molecular sieve. The void fraction is increased.
3) The manufacturing process of the invention is more environment-friendly.
4) According to the invention, the pore-forming agent and the foaming agent are matched for use, so that uniform pore distribution and a full pore structure of the molecular sieve framework are obtained, and the appropriate modifier is added to reduce the sintering temperature by 150-250 ℃.
5) The 4A molecular sieve manufacturing method can respectively adopt (1) extrusion molding to manufacture a honeycomb structure; (2) dry pressing to form flat plate or anisotropic structure; (3) the ball rolling machine is used for manufacturing a spherical structure.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1:
A4A molecular sieve ingredient comprises an amorphous silica-alumina main material, a modifier, a pore-forming agent, a forming lubricant, a molecular sieve framework foaming agent and a forming binder. The weight percentage of each component is as follows: the amorphous silica-alumina main material is a mixture of amorphous silica and aluminum hydroxide, and the mixture of amorphous silica and aluminum hydroxide (the mixing ratio is 8: 2) is 85 percent; a forming binder, namely polyvinyl alcohol (PVA) 10%; pore-forming agent, namely carbon black powder, 0.5 percent; a forming lubricant, namely 4% of rapeseed oil; modifier, i.e. magnesia 0.45%; molecular sieve skeleton foaming agent, namely silicon carbide 0.05%.
The embodiment provides a method for preparing a 4A molecular sieve, which comprises the following steps:
A. uniformly mixing a modifier, a pore-forming agent, a forming lubricant and a molecular sieve framework foaming agent with a forming binder, and then adding an amorphous silica-alumina main material to mix to obtain a mixed material; the weight percentage of each component is as follows: 85% of a mixture of amorphous silica and aluminum hydroxide (the mixing ratio is 8: 2); 10% of polyvinyl alcohol (PVA); 0.5 percent of carbon black powder; 4% of rapeseed oil; 0.45 percent of magnesium oxide; 0.05 percent of silicon carbide.
Preferably, the particle size of the amorphous silica-alumina main material is not more than 10 microns, and a proper particle size range is selected according to the requirement of designing the pore diameter of an airflow channel of the molecular sieve. More preferably, when the aperture of the designed molecular sieve airflow channel is 0.1 micron, the amorphous silica-alumina main material with the particle size of 2-4 microns is selected; when the aperture of the designed molecular sieve airflow channel is 1 micron, the amorphous silica-alumina main material with the granularity of 5-8 microns is selected.
B. Performing extrusion molding on the mixed material, specifically comprising the steps of performing ball milling, pugging, aging, extruding, drying, firing and trimming on the mixed material to obtain the 4A molecular sieve;
in the step B, the ball milling time of the mixed materials is 5-10 hours, nine parts of mixed raw materials are added with one part of water to be kneaded to prepare mud, and the kneaded mud is aged for 12-36 hours and then is ready to be molded; the firing comprises the steps of sequentially discharging glue, spraying a film and firing, wherein the glue discharging temperature is 260-400 ℃, and the glue discharging time is 2-8 hours; the firing temperature is 770-1050 ℃, and the firing time is 0.5-2 hours; the thickness of the spray film is 5-25 microns, the spray film is carried out by conventional operation, the spray film temperature is 770-1050 ℃, equivalently, a layer of stabilizer is made on the surface of a molecular sieve product, and the main formula of the film material is the raw material powder particles with smaller particle size.
The pore distribution of the 4A molecular sieve prepared in the embodiment is uniform, and the porous structure pore ratio is 32-34% measured by a saturated water absorption method, namely, all pores account for 32-34% of the volume of the molecular sieve.
In this example, the step of discharging the paste and spraying the film during firing may be eliminated, or one of the steps of discharging the paste and spraying the film may be eliminated.
Example 2:
A4A molecular sieve ingredient comprises an amorphous silica-alumina main material, a modifier, a pore-forming agent, a forming lubricant, a molecular sieve framework foaming agent and a forming binder. The weight percentage of each component is as follows: the amorphous silica-alumina main material is a mixture of amorphous silica and aluminum hydroxide, and the mixture of amorphous silica and aluminum hydroxide (the mixing ratio is 6: 4) is 90%; 4.4 percent of forming binder, namely modified starch ether; pore-forming agent, namely 3% of graphite powder; a forming lubricant, i.e. soybean oil 2%; modifier, namely 0.5 percent of magnesium hydroxide; molecular sieve skeleton foaming agent, namely silicon nitride 0.1%.
The embodiment provides a method for preparing a 4A molecular sieve, which comprises the following steps:
A. uniformly mixing a modifier, a pore-forming agent, a forming lubricant and a molecular sieve framework foaming agent with a forming binder, and then adding an amorphous silica-alumina main material to mix to obtain a mixed material; the weight percentage of each component is as follows: 90 percent of mixture of amorphous silicon oxide and aluminum hydroxide (the mixing ratio is 6: 4); 4.4% of modified starch ether; 3% of graphite powder; 2% of soybean oil; 0.5 percent of magnesium hydroxide; 0.1% of silicon nitride.
The method for selecting the particle size of the amorphous silica-alumina main material is the same as that of example 1.
B. Performing extrusion molding on the mixed material, specifically comprising the steps of performing ball milling, pugging, aging, extruding, drying, firing and trimming on the mixed material to obtain the 4A molecular sieve;
in the step B, the ball milling time of the mixed materials is 5-10 hours, nine parts of mixed raw materials are added with one part of water to be kneaded to prepare mud, and the kneaded mud is aged for 12-36 hours and then is ready to be molded; the firing comprises the steps of binder removal, film spraying and firing, wherein the binder removal temperature is 260-400 ℃, and the binder removal time is 2-8 hours; the firing temperature is 770-1050 ℃, and the firing time is 0.5-2 hours; the thickness of the spray film is 5-25 microns, the spray film is carried out by conventional operation, the spray film temperature is 770-1050 ℃, and the main formula of the film material is the raw material powder particles with smaller particle size. The firing time may be selected from 0.5 to 1.5 hours.
In the embodiment, the pore distribution of the prepared 4A molecular sieve is uniform by adopting a saturated water absorption method, and the pore occupation ratio of the porous structure (namely the proportion of all pores in the volume of the molecular sieve) is 30-33%.
In this example, the step of discharging the paste and spraying the film during firing may be eliminated, or one of the steps of discharging the paste and spraying the film may be eliminated.
Example 3:
A4A molecular sieve ingredient comprises an amorphous silica-alumina main material, a modifier, a pore-forming agent, a forming lubricant, a molecular sieve framework foaming agent and a forming binder. The weight percentage of each component is as follows: the amorphous silica-alumina main material is a mixture of amorphous silica and aluminum hydroxide, and the mixture of amorphous silica and aluminum hydroxide (the mixing ratio is 5: 5) is 95 percent; a forming binder, namely 3% of polyvinyl alcohol (PVA); pore-forming agent, namely cellulose 1.8%; a forming lubricant, namely 1% of rapeseed oil; modifier, namely 0.1 percent of vanadium pentoxide; molecular sieve skeleton foaming agent, namely 0.1 percent of aluminum nitride.
The embodiment provides a method for preparing a 4A molecular sieve, which comprises the following steps:
A. uniformly mixing a modifier, a pore-forming agent, a forming lubricant and a molecular sieve framework foaming agent with a forming binder, and then adding an amorphous silica-alumina main material to mix to obtain a mixed material; the weight percentage of each component is as follows: 95% of a mixture of amorphous silica and aluminum hydroxide (mixing ratio: 5: 5); 3% of polyvinyl alcohol (PVA); 1.8% of cellulose; 1% of rapeseed oil; 0.1 percent of vanadium pentoxide; 0.1 percent of aluminum nitride.
The method for selecting the particle size of the amorphous silica-alumina main material is the same as that of example 1.
B. Performing extrusion molding on the mixed material, specifically comprising the steps of performing ball milling, pugging, aging, extruding, drying, firing and trimming on the mixed material to obtain the 4A molecular sieve;
in the step B, the ball milling time of the mixed materials is 5-10 hours, nine parts of mixed raw materials are added with one part of water to be kneaded to prepare mud, and the kneaded mud is aged for 12-36 hours and then is ready to be molded; the firing comprises the steps of binder removal, film spraying and firing, wherein the binder removal temperature is 260-400 ℃, and the binder removal time is 2-8 hours; the firing temperature is 770-1050 ℃, and the firing time is 0.5-2 hours; the thickness of the spray film is 5-25 microns, the spray film is carried out by conventional operation, the spray film temperature is 770-1050 ℃, equivalently, a layer of stabilizer is made on the surface of a molecular sieve product, and the main formula of the film material is the raw material powder particles with smaller particle size.
The pore distribution of the 4A molecular sieve prepared in the embodiment is uniform, and the porous structure pore occupation ratio (namely the proportion of all pores in the volume of the molecular sieve) measured by a saturated water absorption method is 30-32%.
In this example, the step of discharging the paste and spraying the film during firing may be eliminated, or one of the steps of discharging the paste and spraying the film may be eliminated.
Example 4:
A4A molecular sieve ingredient comprises an amorphous silica-alumina main material, a modifier, a pore-forming agent, a forming lubricant, a molecular sieve framework foaming agent and a forming binder. The weight percentage of each component is as follows: the amorphous silica-alumina main material is a mixture of amorphous silica and aluminum hydroxide, and the mixture of amorphous silica and aluminum hydroxide (the mixing ratio is 5: 5) is 96 percent; 0% of forming binder; pore-forming agent, namely cellulose 1.8%; a forming lubricant, namely 1% of rapeseed oil; modifier, namely 0.1 percent of vanadium pentoxide; molecular sieve skeleton foaming agent, namely 0.1 percent of aluminum nitride.
The embodiment provides a method for preparing a 4A molecular sieve, which comprises the following steps:
A. drying the modifier, the pore-forming agent, the forming lubricant, the molecular sieve skeleton foaming agent and the amorphous silica-alumina main material, and mixing for 5-10 hours to obtain a mixed material; the weight percentage of each component is as follows: 96% of a mixture of amorphous silica and aluminum hydroxide (mixing ratio: 5: 5); 2.8 percent of cellulose; 1% of rapeseed oil; 0.1 percent of vanadium pentoxide; 0.1 percent of aluminum nitride.
The method for selecting the particle size of the amorphous silica-alumina main material is the same as that of example 1.
C. Dry pressing and molding the mixed material, specifically comprising the steps of dry pressing, firing and trimming the mixed material to obtain the 4A molecular sieve;
in the step C, the firing comprises the steps of binder removal, film spraying and firing, wherein the binder removal step is carried out before firing, the binder removal temperature is 260-400 ℃, and the binder removal time is 1-2 hours; the firing temperature is 770-1050 ℃, and the firing time is 0.5-2 hours; the thickness of the spray film is 5-25 microns, the spray film is carried out by conventional operation, the spray film temperature is 770-1050 ℃, equivalently, a layer of stabilizer is made on the surface of a molecular sieve product, and the main formula of the film material is the raw material powder particles with smaller particle size. The firing temperature may be 880 to 980 ℃ and the firing time may be 0.5 to 1.5 hours.
And the dry pressing molding adopts a plastic molding bracket to obtain mutual communication among pores of the 4A molecular sieve.
The pore distribution of the 4A molecular sieve prepared in the embodiment is uniform, and the porous structure pore occupation ratio (namely the proportion of all pores in the volume of the molecular sieve) measured by a saturated water absorption method is 30-33%.
In this example, the step of discharging the paste and spraying the film during firing may be eliminated, or one of the steps of discharging the paste and spraying the film may be eliminated.
Example 5:
A4A molecular sieve ingredient comprises an amorphous silica-alumina main material, a modifier, a pore-forming agent, a forming lubricant, a molecular sieve framework foaming agent and a forming binder. The weight percentage of each component is as follows: the amorphous silica-alumina main material is a mixture of amorphous silica and aluminum hydroxide, and the mixture of amorphous silica and aluminum hydroxide (the mixing ratio is 6: 4) is 93 percent; 0% of forming binder; pore-forming agent, namely carbon black powder 2.5%; a forming lubricant, i.e. 4% soybean oil; modifier, namely magnesium hydroxide, 0.45 percent; molecular sieve skeleton foaming agent, namely silicon carbide 0.05%.
The embodiment provides a method for preparing a 4A molecular sieve, which comprises the following steps:
A. drying the modifier, the pore-forming agent, the forming lubricant, the molecular sieve skeleton foaming agent and the amorphous silica-alumina main material, and mixing for 5-10 hours to obtain a mixed material; the weight percentage of each component is as follows: 93% of a mixture of amorphous silica and aluminum hydroxide (mixing ratio of 6: 4); 2.5 percent of carbon black powder; 4% of soybean oil; 0.45 percent of magnesium hydroxide; 0.05 percent of silicon carbide.
The method for selecting the particle size of the amorphous silica-alumina main material is the same as that of example 1.
C. Dry pressing and molding the mixed material, specifically comprising the steps of dry pressing, firing and trimming the mixed material to obtain the 4A molecular sieve;
in the step C, the firing comprises the steps of binder removal, film spraying and firing, wherein the step of binder removal is carried out before firing, the binder removal temperature is 260-400 ℃, and the binder removal time is 1-2 hours; the firing temperature is 770-1050 ℃, and the firing time is 0.5-2 hours; the thickness of the spray film is 5-25 microns. The film spraying is carried out by conventional operation, the film spraying temperature is 770-1050 ℃, equivalently, a layer of stabilizer is made on the surface of a molecular sieve product, and the main formula of the film material is the raw material powder particles with smaller particle size. The firing temperature may be 880 to 980 ℃.
And the dry pressing molding adopts a plastic molding bracket to obtain mutual communication among pores of the 4A molecular sieve.
The pore distribution of the 4A molecular sieve prepared in the embodiment is uniform, and the porous structure pore occupation ratio (namely the proportion of all pores in the volume of the molecular sieve) measured by a saturated water absorption method is 31-35%.
In this example, the step of discharging the paste and spraying the film during firing may be eliminated, or one of the steps of discharging the paste and spraying the film may be eliminated.
Example 6:
A4A molecular sieve ingredient comprises an amorphous silica-alumina main material, a modifier, a pore-forming agent, a forming lubricant, a molecular sieve framework foaming agent and a forming binder. The weight percentage of each component is as follows: the amorphous silica-alumina main material is a mixture of amorphous silica and aluminum hydroxide, and the mixture of amorphous silica and aluminum hydroxide (the mixing ratio is 8: 2) is 95 percent; 0% of forming binder; pore-forming agent, namely graphite powder, 0.5 percent; a forming lubricant, i.e. palm oil 4%; modifier, i.e. calcium oxide 0.4%; molecular sieve skeleton foaming agent, namely silicon nitride 0.1%.
The embodiment provides a method for preparing a 4A molecular sieve, which comprises the following steps:
A. drying the modifier, the pore-forming agent, the forming lubricant, the molecular sieve skeleton foaming agent and the amorphous silica-alumina main material, and mixing for 5-10 hours to obtain a mixed material; the weight percentage of each component is as follows: 95% of a mixture of amorphous silica and aluminum hydroxide (the mixing ratio is 8: 2); 0.5 percent of graphite powder; 4% of palm oil; 0.4 percent of calcium oxide; 0.1% of silicon nitride.
The method for selecting the particle size of the amorphous silica-alumina main material is the same as that of example 1.
C. Dry pressing and molding the mixed material, specifically comprising the steps of dry pressing, firing and trimming the mixed material to obtain the 4A molecular sieve;
in the step C, the firing comprises the steps of binder removal, film spraying and firing, wherein the binder removal step is carried out before firing, the binder removal temperature is 260-400 ℃, and the binder removal time is 1-2 hours; the firing temperature is 770-1050 ℃, and the firing time is 0.5-2 hours; the thickness of the spray film is 5-25 microns. The film spraying is carried out by conventional operation, the film spraying temperature is 770-1050 ℃, equivalently, a layer of stabilizer is made on the surface of a molecular sieve product, and the main formula of the film material is the raw material powder particles with smaller particle size. The firing temperature may be 880 to 980 ℃. And the dry pressing molding adopts a plastic molding bracket to obtain mutual communication among pores of the 4A molecular sieve.
The pore distribution of the 4A molecular sieve prepared in the embodiment is uniform, and the porous structure pore occupation ratio (namely the proportion of all pores in the volume of the molecular sieve) measured by a saturated water absorption method is 30-33%.
In this example, the step of discharging the paste and spraying the film during firing may be eliminated, or one of the steps of discharging the paste and spraying the film may be eliminated.
Comparative example 1:
a 4A molecular sieve formulation, the components being the same as in example 1. The molecular sieve framework foaming agent is silicon nitride.
This comparative example provides a method for making a 4A molecular sieve, the specific steps being substantially the same as in example 1, except that: in the step A, the adopted molecular sieve skeleton foaming agent is silicon nitride.
In the comparative example, the molecular sieve framework foaming agent is silicon nitride, the sintering is carried out at the lower sintering temperature, and the porous structure pore ratio of the prepared 4A molecular sieve measured by a saturated water absorption method is 40-45%.
The 4A molecular sieve manufacturing method can respectively adopt (1) extrusion molding to manufacture a honeycomb structure; (2) dry pressing to form flat plate or anisotropic structure; (3) the ball rolling machine is used for manufacturing a spherical structure.
When the ingredient of the invention is used, the ingredients can be prepared by dry pressing and ball rolling machine forming processes.
According to the invention, the pore-forming agent and the foaming agent are matched for use, so that uniform pore distribution and a full pore structure of the molecular sieve framework are obtained, and the appropriate modifier is added to reduce the sintering temperature by 150-250 ℃.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A4A molecular sieve ingredient is characterized in that: comprises the following components in percentage by mass:
2. the 4A molecular sieve furnish of claim 1 characterized by: the amorphous silica-alumina main material comprises at least one of amorphous silica and aluminum hydroxide.
3. The 4A molecular sieve furnish of claim 1 characterized by: the amorphous silica-alumina main material comprises amorphous silica and aluminum hydroxide, wherein the mass ratio of the amorphous silica to the aluminum hydroxide is (9): 1-6: 4.
4. a 4A molecular sieve formulation according to claim 1, characterized by: the forming binder comprises at least one of polyvinyl alcohol, modified starch ether and carboxymethyl starch; the pore-forming agent comprises at least one of carbon black powder, graphite powder, expanded graphite powder and cellulose.
5. The 4A molecular sieve furnish of claim 1 characterized by: the forming lubricant is vegetable oil.
6. The 4A molecular sieve formulation of claim 1, wherein the modifier comprises one or more of magnesium oxide, magnesium hydroxide, calcium oxide, kaolin, zinc oxide, vanadium pentoxide, and zirconium oxide; the molecular sieve skeleton foaming agent comprises one or more of silicon carbide, silicon nitride, aluminum nitride and boron nitride.
7. A method for producing a 4A molecular sieve, characterized by using the 4A molecular sieve formulation according to any one of claims 1 to 6,
the method comprises the following steps:
A. uniformly mixing the components in proportion to obtain a mixed material;
B. performing extrusion molding on the mixed material, specifically comprising the steps of performing ball milling, pugging, aging, extruding, drying, firing and trimming on the mixed material to obtain the 4A molecular sieve;
or,
C. and (3) dry-pressing and molding the mixed material, specifically comprising the steps of dry-pressing, firing and trimming the mixed material to obtain the 4A molecular sieve.
8. The method for preparing the 4A molecular sieve of claim 7, wherein in the step B, the aging time is 12-36 hours.
9. The method for manufacturing the 4A molecular sieve according to claim 7, wherein in the step B, the firing comprises a firing step, and the method further comprises a glue discharging step before the firing, wherein the glue discharging temperature is 260-400 ℃, and the glue discharging time is 2-8 hours; the firing temperature is 770-1050 ℃, and the firing time is 0.5-2 hours;
in the step C, the firing comprises firing, and the step of removing glue is also included before firing, wherein the glue removing temperature is 260-400 ℃, and the glue removing time is 1-2 hours; the sintering temperature is 770-1050 ℃, and the sintering time is 0.5-2 hours.
10. The preparation method of the 4A molecular sieve of claim 7, wherein in the step B or C, the firing comprises a firing step, a film spraying step is provided before firing, and the thickness of the sprayed film is 5-25 microns; the sintering temperature is 770-1050 ℃, and the sintering time is 0.5-1.5 hours.
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| US20050058597A1 (en) * | 2003-09-16 | 2005-03-17 | Corbin David Richard | Process for the production of nan-sized zeolite A |
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| CN102502692A (en) * | 2011-11-21 | 2012-06-20 | 烟台大学 | High-intensity molecular sieve and preparation method thereof |
| CN112619604A (en) * | 2020-12-01 | 2021-04-09 | 上海雪峰分子筛有限公司 | 4A molecular sieve and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050058597A1 (en) * | 2003-09-16 | 2005-03-17 | Corbin David Richard | Process for the production of nan-sized zeolite A |
| CN101172618A (en) * | 2007-09-27 | 2008-05-07 | 中国铝业股份有限公司 | Method for synthesizing 4A zeolite for abluent with liveness soluble glass solution |
| CN102502692A (en) * | 2011-11-21 | 2012-06-20 | 烟台大学 | High-intensity molecular sieve and preparation method thereof |
| CN112619604A (en) * | 2020-12-01 | 2021-04-09 | 上海雪峰分子筛有限公司 | 4A molecular sieve and preparation method thereof |
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