CN114538464A - Method for preparing 4A molecular sieve by recycling alkali mud - Google Patents
Method for preparing 4A molecular sieve by recycling alkali mud Download PDFInfo
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- 239000003513 alkali Substances 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 52
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 41
- 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 41
- 238000004064 recycling Methods 0.000 title claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000002425 crystallisation Methods 0.000 claims abstract description 25
- 230000008025 crystallization Effects 0.000 claims abstract description 25
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 20
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 239000002910 solid waste Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 51
- 238000001035 drying Methods 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 abstract description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 26
- 229910052710 silicon Inorganic materials 0.000 description 26
- 239000010703 silicon Substances 0.000 description 26
- 230000008569 process Effects 0.000 description 13
- 239000012535 impurity Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 239000010802 sludge Substances 0.000 description 10
- 239000000499 gel Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 238000005188 flotation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal aluminosilicate Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000010447 natron Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
- C01B39/14—Type A
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention relates to a method for preparing a 4A molecular sieve by recycling alkali mud. 1) Mixing alkali mud, aluminum hydroxide and sodium hydroxide to obtain a mixture, wherein the alkali mud is solid waste discharged by liquid sodium silicate through precipitation or filter pressing after the sodium silicate is prepared by a dry method or a wet method; 2) roasting the mixture, dissolving a product obtained by roasting in water, and aging to obtain a gel product; 3) and carrying out crystallization reaction on the gel product to obtain a crystallized product after the crystallization reaction, wherein the solid crystallized product obtained after filtering the crystallized product contains the 4A molecular sieve. Realizes the resource utilization of the alkali mud without a complex separation process. The problem of solid waste disposal of sodium silicate enterprises is solved.
Description
Technical Field
The invention belongs to the technical field of alkali mud waste recycling, and particularly relates to a method for preparing a 4A molecular sieve by recycling alkali mud.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The alkali mud is a silicon-rich solid waste resource generated in the production process of sodium silicate enterprises. The insoluble substance is discharged by precipitation or filter pressing operation in the filtering process of liquid sodium silicate, and the pH value is controlled within 10 when the insoluble substance is discharged, so that the insoluble substance belongs to common solid waste. The powder is an off-white mud in a water-containing state and a light-white powder in a dry state. In the sodium silicate production enterprises, the production amount of the solid waste accounts for about 2 percent of the product yield. According to the calculation, the wet alkali mud discharged in China is about 20 ten thousand tons every year at present, so that the difficulty is brought to the solid waste disposal work of enterprises, and the disposal cost is increased. The chemical components of the alkali mud are complex and exist in the form of solid mixture, and the common method is difficult to separate and recover various components. At present, the industry generally entrusts a third party to dispose and pays a certain entrusted disposing fee.
In the prior reports, the alkali mud is tried to be recycled. However, the existing method has certain disadvantages such as: silicon and other elements in the alkali mud are often in a symbiotic state, and selective separation is difficult to realize.
In the prior art, the impurity separator is used for solving the problems existing in the production enterprises of silica gel and sodium silicate for a long time, namely the problems of environmental pollution and resource waste caused by a large amount of discharged waste silicon slag, and the method for producing sodium silicate by using the waste silicon slag for recycling is provided. However, the content of impurities in the alkali mud is too much, and the alkali mud cannot be effectively separated.
The prior art proposes a method for producing white carbon black by using silicon sludge, but the method adopts a complicated method to separate silicon and other elements, and has higher treatment cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for preparing a 4A molecular sieve by recycling alkali mud. Filling the technical blank of preparing the 4A molecular sieve from the alkali mud, and realizing the resource treatment of the alkali mud.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for preparing a 4A molecular sieve by recycling alkali mud,
1) mixing alkali mud, aluminum hydroxide and sodium hydroxide to obtain a mixture, wherein the alkali mud is solid waste discharged by liquid sodium silicate through precipitation or filter pressing after the sodium silicate is prepared by a dry method or a wet method;
2) roasting the mixture, dissolving the product obtained by roasting in water, and aging to obtain a gel product;
3) and carrying out crystallization reaction on the gel product to obtain a crystallized product after the crystallization reaction, wherein the solid crystallized product obtained after filtering the crystallized product contains the 4A molecular sieve.
The method for preparing the 4A molecular sieve by recycling the alkali mud realizes the zero discharge of solid wastes of the sodium silicate.
The dry base sludge contains about 30% quartz sand, about 15% sodium silicate, about 4% perlite, and about 1% other impurities. Wherein, the content of silicon dioxide is as high as 70 percent to 90 percent, and the silicon dioxide also contains a certain amount of compounds such as sodium, aluminum, calcium, iron, magnesium and the like.
The 4A molecular sieve is an alkali metal aluminosilicate and contains sodium element, aluminum element and silicon element.
The invention prepares the 4A molecular sieve by a one-pot method, the silicon source, the aluminum source and the caustic soda are roasted and pretreated together, and the gelling process and the crystallization process can be finished in the same reactor. Seed crystals are not required to be added in the crystallization process.
The silicon source and the aluminum source are synchronously extracted in the roasting process, and initial reaction products are synchronously formed. And (3) adding the roasted material into softened water to enable the silicon source and the aluminum source to be dissociated and to be structurally rearranged to form a gel product, and fully aging. Then the gel is crystallized to generate the 4A molecular sieve.
After crystallization, the impurities of soluble iron compounds can be transferred into the filtrate as much as possible without cooling treatment and diameter filtration treatment, so that the purity and whiteness of the product are improved, and the separation of part of the impurities from the 4A molecular sieve is realized. The rest impurity elements are formed in the interior of the 4A molecular sieve to form the interior of the 4A molecular sieve product. Solves the problem that the prior alkali mud recycling method needs a complex impurity treatment process. The 4A molecular sieve is composed of three elements of silicon, aluminum and oxygen. The raw material alkali mud mainly contains silicon, other impurity elements can be removed in the form of insoluble impurities in the treatment after calcination, and the insoluble impurities are removed by thermal filtration after the synthesis reaction, so that the silicon is retained to the maximum extent, and other impurity elements are removed.
In some embodiments of the present invention, the alkali mud before being mixed with the aluminum hydroxide and the sodium hydroxide in step 1) is a powdery raw material obtained by drying and crushing wet alkali mud. Further, the drying temperature is 80-130 ℃. So that the final moisture content is below 10%. The crushing treatment process is that the caking formed by the materials in the wet alkali mud drying process is restored to the original powder state through simple crushing operations such as extrusion, collision and the like, the dry alkali mud is not required to be ground into a product with smaller granularity, the alkali mud pretreatment cost can be effectively reduced, and the generation of dust can be reduced.
In some embodiments of the invention, the mass ratio of the alkali mud, the aluminum hydroxide and the sodium hydroxide is 1.0:1.0-2: 1.8-2.8; further 1.0:1.05-1.77: 1.83-2.58. Mixing the three solid raw materials, and stirring for 20-70 min; further 30-60 min.
In some embodiments of the invention, the temperature of calcination is 500-; further, the temperature of the calcination was 550 ℃ and 735 ℃.
In some embodiments of the invention, the calcined product is added to water in a ratio of 1:12-25 by mass of the alkali mud to the water; further, the mass ratio of the alkali mud to the water is 1: 13.4-22.7; further, the temperature of the water is 30-65 ℃; further, the standing and aging time is 1-3 h.
In some embodiments of the invention, the temperature of the crystallization reaction is 90-110 ℃ and the reaction time is 2-12 h; furthermore, the reaction temperature is 93.8-105.6 ℃, and the reaction time is 2.5-10.5 h.
In some embodiments of the invention, after the crystallization reaction, the crystallized product is directly subjected to a filtration treatment to remove the filtrate. There is no cooling or chilling process.
In some embodiments of the invention, the filtered solid product is washed with water and then dried. The pH value is washed to be less than 11, and the filtrate is colorless. Finally obtaining a white powder product.
One or more technical schemes of the invention have the following beneficial effects:
the invention relates to a method for preparing a 4A molecular sieve by recycling alkali mud, which is used for preparing a fine chemical product with high added value, solves the problem of solid waste disposal of sodium silicate enterprises, improves the profitability of the sodium silicate enterprises, and realizes good environmental benefit, economic benefit and social benefit.
The invention utilizes a new technology of preparing the 4A molecular sieve by a one-pot method, namely, a silicon source, an aluminum source and caustic soda are roasted together for pretreatment, and the gelling process and the crystallization process are finished in the same reactor, so that the 4A molecular sieve product with regular appearance is prepared.
The method of the invention synthesizes the gel firstly, and actually firstly stores the crystal seeds in the crystallization process of the gel, and then grows into a large crystal.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description, serve to explain the invention and not to limit the invention.
FIG. 1 is a flow chart of preparation of a 4A molecular sieve by recycling alkali mud;
FIG. 2 is a scan of a 4A molecular sieve product prepared in example 1;
FIG. 3 is a scan of a 4A molecular sieve product prepared in example 2;
figure 4 is a scan of the 4A molecular sieve product prepared in example 3.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The alkali mud used in the invention can also be called as silicon mud, alkali silicon mud, water glass solid waste, sodium silicate waste and the like, which all accord with the names of the sources.
In the existing alkali mud regeneration method, the existing alkali mud is recycled after mechanical separation, chemical combination reaction-flotation machine separation, precipitation and filter pressing, and metal ions or compounds in slurry form compounds dissolved in water through chemical combination reaction to complete chemical combination separation in liquid. In the method, the available effective component silicon dioxide in the silicon sludge is separated and recovered, but silicon and other elements in the alkali sludge are always in a symbiotic state, so that the selective separation is difficult to realize.
In the existing method, waste silicon slag is used for producing sodium silicate, but the sodium silicate is too rich in impurities and cannot be effectively separated, so that after the liquid sodium silicate is obtained, the product has obvious green color and the purity of the product does not reach the standard. On the other hand, a large amount of waste water is generated while solid waste is treated, so that a new environmental problem is brought.
In the prior method, silicon sludge is utilized to produce white carbon black, silicon sludge slurry is stirred and beaten uniformly, solid-liquid separation is carried out, solid waste residues are automatically separated and removed, the separated silicon sludge solution is pumped into special flotation equipment to extract carbon powder, the silicon sludge solution is circulated in a flotation tank for a period of time under the action of a circulating pump and then is kept stand for a period of time, then a suspending agent is added, a drain valve of a transparent pipe on the top surface of the flotation tank is opened, sewage in the transparent pipe above the drain valve is discharged, and a proper amount of water is added after each discharge is finished, and the procedures are repeated in a circulating manner until no black fine particles exist in the silicon sludge solution in the transparent pipe on the flotation tank; and the pickling process is to pump the floated silicon sludge solution into an acid tank, add hydrogen carbonate and stir the solution uniformly. And then the uniform granular white carbon black is formed by precipitation, washing, filter pressing, pulping again and spray drying. However, silicon and other elements in the alkali mud are often in a symbiotic state, selective separation is difficult to realize, the effective treatment amount of the alkali mud is not high, the obtained product amount is low, and the actual treatment cost is too high due to the addition of a complex treatment process and raw material investment.
The invention will be further illustrated by the following examples
Example 1
The 4A molecular sieve product is successfully prepared by adopting the technical scheme of the invention by taking alkali mud of a certain natron manufacturing enterprise in Shandong as a raw material. The preparation method of the product comprises the following steps:
(1) putting the wet alkali mud in an environment of 110 ℃ for fully drying for 6h, wherein the final water content is 6.1%;
(2) crushing the caking adhered together in the drying process to recover the powder with the original granularity;
(3) and (3) placing 30 parts of alkaline mud, 30 parts of aluminum hydroxide and 64 parts of sodium hydroxide in a closed mixing device, and stirring and mixing for 40min to ensure that the mixture composition is uniform.
(4) The mixed materials are conveyed to a roasting furnace, roasted for 3 hours at 685 ℃, and then cooled to 60 ℃.
(5) And (3) putting the roasted product into a crystallization kettle containing 550 parts of softened water, controlling the temperature in the kettle at 50 ℃, stirring at a low speed for 2 hours, and standing and aging for 2 hours to obtain gel.
(6) The temperature of the crystallization kettle is increased to 98 ℃, and the reaction lasts for 5.5 hours.
(7) After the crystallization reaction is finished, immediately filtering the product to remove filtrate;
(8) after the filtration was complete, the solid product was washed continuously with demineralized water until its pH was 10.5 and the filtrate was observed to be colorless. And drying the washed product to obtain a white powder product.
As shown in the attached figure 2, the 4A molecular sieve product with regular morphology is obtained by the scheme, and the crystal grain size is about 2 um.
Example 2
The technical scheme of the invention is adopted to successfully prepare the 4A molecular sieve product by taking the alkali mud of a metasilicate manufacturing enterprise in Shandong as a raw material. The preparation method of the product comprises the following steps:
(1) putting the wet alkali mud in an environment at 118 ℃ for fully drying for 4h, wherein the final water content is 6%;
(2) crushing the caking blocks adhered together in the drying process to recover the caking blocks into powder with the original granularity;
(3) and (3) putting 30 parts of alkaline mud, 34 parts of aluminum hydroxide and 58 parts of sodium hydroxide into a closed mixing device, and stirring and mixing for 30min to enable the mixture composition to be uniform.
(4) The mixed materials are conveyed to a roasting furnace, roasted for 3.5 hours at 635 ℃, and then cooled to 60 ℃.
(5) And (3) putting the roasted product into a crystallization kettle containing 485 parts of softened water, controlling the temperature in the kettle at 40 ℃, stirring at a low speed for 2 hours, and standing and aging for 1 hour to obtain the gel.
(6) The temperature of the crystallization kettle is increased to 96 ℃, and the reaction is carried out for 6 hours.
(7) After the crystallization reaction is finished, immediately filtering the product to remove the filtrate;
(8) after the end of the filtration, the solid product is washed continuously with demineralized water until its pH reaches 10.5, and the filtrate is observed to be colourless. And drying the washed product to obtain a white powder product.
As shown in the attached figure 3, the 4A molecular sieve product with regular morphology is obtained by the scheme, and the crystal grain size is about 1.2 um.
Example 3
The technical scheme of the invention is adopted to successfully prepare the 4A molecular sieve product by taking the alkali mud of certain silicate manufacturing enterprises in Shandong as the raw material. The preparation method of the product comprises the following steps:
(1) putting the wet alkali mud in an environment of 95 ℃ for fully drying for 10h, wherein the final water content is 7.2%;
(2) crushing the caking adhered together in the drying process to recover the powder with the original granularity;
(3) and (3) placing 30 parts of alkaline mud, 26 parts of aluminum hydroxide and 47 parts of sodium hydroxide in a closed mixing device, and stirring and mixing for 40min to ensure that the mixture composition is uniform.
(4) The mixed materials are conveyed to a roasting furnace, roasted for 5 hours at the temperature of 600 ℃, and then cooled to 60 ℃.
(5) And (3) putting the roasted product into a crystallization kettle containing 400 parts of softened water, controlling the temperature in the kettle at 55 ℃, stirring at a low speed for 3 hours, and standing and aging for 2 hours to obtain the gel.
(6) The temperature of the crystallization kettle is increased to 102.5 ℃ and the reaction lasts for 6 hours.
(7) After the crystallization reaction is finished, immediately filtering the product to remove the filtrate;
(8) after the filtration was complete, the solid product was washed continuously with demineralized water until its pH was 10.5 and the filtrate was observed to be colorless. And drying the washed product to obtain a white powder product.
As shown in the attached figure 4, the 4A molecular sieve product with regular morphology is obtained by the scheme, and the crystal grain size is about 1.2 um.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a 4A molecular sieve by recycling alkali mud is characterized by comprising the following steps: 1) mixing alkali mud, aluminum hydroxide and sodium hydroxide to obtain a mixture, wherein the alkali mud is solid waste discharged by liquid sodium silicate through precipitation or filter pressing after the sodium silicate is prepared by a dry method or a wet method;
2) roasting the mixture, dissolving the product obtained by roasting in water, and aging to obtain a gel product;
3) and carrying out crystallization reaction on the gel product to obtain a crystallized product after the crystallization reaction, wherein the solid crystallized product obtained after filtering the crystallized product contains the 4A molecular sieve.
2. The method for preparing the 4A molecular sieve by recycling the alkali mud as claimed in claim 1, which is characterized in that: the alkali mud before being mixed with the aluminum hydroxide and the sodium hydroxide in the step 1) is a powdery raw material obtained by drying and crushing wet alkali mud.
3. The method for preparing the 4A molecular sieve by recycling the alkali mud as claimed in claim 2, wherein the method comprises the following steps: the drying temperature is 80-130 ℃.
4. The method for preparing the 4A molecular sieve by recycling the alkali mud as claimed in claim 1, which is characterized in that: the mass ratio of the alkali mud to the aluminum hydroxide to the sodium hydroxide is 1.0:1.0-2: 1.8-2.8; further 1.0:1.05-1.77: 1.83-2.58.
5. The method for preparing the 4A molecular sieve by recycling the alkali mud as claimed in claim 1, which is characterized in that: the roasting temperature is 500-750 ℃; further, the temperature of the calcination was 550-.
6. The method for preparing the 4A molecular sieve by recycling the alkali mud as claimed in claim 1, which is characterized in that: adding the roasted product into water according to the mass ratio of the alkali mud to the water of 1: 12-25.
7. The method for preparing the 4A molecular sieve by recycling the alkali mud as claimed in claim 6, wherein the method comprises the following steps: the mass ratio of the alkali mud to the water is 1: 13.4-22.7;
or, the temperature of the water is 30-65 ℃;
or standing and aging for 1-3 h.
8. The method for preparing the 4A molecular sieve by recycling the alkali mud as claimed in claim 1, wherein the method comprises the following steps: the temperature of the crystallization reaction is 90-110 ℃, and the reaction time is 2-12 h; furthermore, the reaction temperature is 93.8-105.6 ℃, and the reaction time is 2.5-10.5 h.
9. The method for preparing the 4A molecular sieve by recycling the alkali mud as claimed in claim 1, which is characterized in that: after the crystallization reaction, directly filtering the crystallization product to remove the filtrate.
10. The method for preparing the 4A molecular sieve by recycling the alkali mud as claimed in claim 1, which is characterized in that: the solid product after filtration was washed with water and then dried.
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| CN103482644A (en) * | 2013-07-17 | 2014-01-01 | 内蒙古工业大学 | Method used for preparing 4A molecular sieve by coal gangue alkaline leaching one-step method |
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| CN109354036A (en) * | 2018-10-30 | 2019-02-19 | 中国神华能源股份有限公司 | A kind of preparation method of 4A molecular sieve |
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