CN114538464B - Method for preparing 4A molecular sieve by alkali mud recycling - Google Patents
Method for preparing 4A molecular sieve by alkali mud recycling Download PDFInfo
- Publication number
- CN114538464B CN114538464B CN202210288709.0A CN202210288709A CN114538464B CN 114538464 B CN114538464 B CN 114538464B CN 202210288709 A CN202210288709 A CN 202210288709A CN 114538464 B CN114538464 B CN 114538464B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- alkali mud
- preparing
- recycling
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003513 alkali Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 46
- 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 46
- 238000004064 recycling Methods 0.000 title claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 238000002425 crystallisation Methods 0.000 claims abstract description 31
- 230000008025 crystallization Effects 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 21
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 21
- 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 53
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- 239000012535 impurity Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 5
- 238000005580 one pot reaction Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000000717 retained effect Effects 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 238000007781 pre-processing Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- 239000000843 powder Substances 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000000499 gel Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000002699 waste material Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000005188 flotation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000006229 carbon black Substances 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
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 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
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 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
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- -1 alkali metal aluminosilicate Chemical class 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 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
- 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
- 239000000284 extract Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000006872 improvement Effects 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
- 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
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011069 regeneration method Methods 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
- 239000002351 wastewater Substances 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
-
- 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
Landscapes
- 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 using alkali mud as a resource. 1) Mixing alkali mud, aluminum hydroxide and sodium hydroxide to obtain a mixture, wherein the alkali mud is solid waste discharged from a precipitation or press filtration process of liquid sodium silicate after 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 (3) carrying out crystallization reaction on the gel product, and obtaining a crystallized product after the crystallization reaction, wherein the solid crystallized product obtained after the crystallization product is filtered contains the 4A molecular sieve. Realizes the resource utilization of alkali mud without complex separation process. Solves the problem of solid waste disposal of sodium silicate enterprises.
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 using alkali mud as a resource.
Background
The disclosure of this background section is only intended to increase the 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 already known to those of ordinary skill in the art.
The alkali mud is a solid waste resource rich in silicon, which is generated in the production process of sodium silicate enterprises. The method is insoluble substances discharged through precipitation or filter pressing operation in the liquid sodium silicate filtering process, and the pH value is controlled within 10 during discharge, and belongs to common solid waste. The powder is in a gray mud state in a water-containing state and in a light gray powder state in a dry state. In the sodium silicate production enterprises, the solid waste production amount accounts for about 2% of the product yield. According to the calculation, the current annual discharge of wet alkali mud in China is about 20 ten thousand tons, which makes the solid waste disposal work of enterprises difficult and increases the disposal cost. The alkali mud has complex chemical components and exists in the form of a solid mixture, and various components of the alkali mud are difficult to separate and recycle by a common method. Currently, the industry commonly entrusts third party disposal and pays a certain entrustment fee.
In the prior art, there have been attempts to recycle alkaline mud. However, the existing method has certain disadvantages such as: the silicon and other elements in the alkaline 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 of environmental pollution and resource waste caused by a large amount of discharged waste silicon slag in the production enterprises of silica gel and sodium silicate for a long time, and the method for recycling sodium silicate produced by using the waste silicon slag is provided. However, the alkali mud has excessive impurity content and has the problem of incapability of effective separation.
In the prior art, a method for producing white carbon black by using silica mud is proposed, but a complex method is adopted to separate silicon from other elements, so that the treatment cost is high.
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. Fills the technical blank of preparing the 4A molecular sieve by the alkali mud, and realizes the recycling 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 from a precipitation or press filtration process of liquid sodium silicate after 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 (3) carrying out crystallization reaction on the gel product, and obtaining a crystallized product after the crystallization reaction, wherein the solid crystallized product obtained after the crystallization product is filtered contains the 4A molecular sieve.
According to the invention, the 4A molecular sieve is prepared by recycling alkali mud, so that zero emission of solid waste of sodium silicate is realized.
The dry alkali mud contains about 30% quartz sand, about 15% sodium silicate, about 4% perlite, and about 1% other impurities. Wherein, the silicon dioxide content is up to 70% -90%, and contains a certain amount of sodium, aluminum, calcium, iron, magnesium and other compounds.
The 4A molecular sieve is an alkali metal aluminosilicate and contains sodium element, aluminum element and silicon element.
In the invention, a one-pot method is used for preparing the 4A molecular sieve, a silicon source, an aluminum source and caustic soda are roasted together for pretreatment, and the gelling process and the crystallization process can be completed in the same reactor. Seed crystal is not needed in the crystallization process.
The roasting process synchronously extracts the silicon source and the aluminum source and synchronously forms initial reaction products. And adding the roasted material into softened water to enable a silicon source and an aluminum source to be free and to carry out structural rearrangement to form a gel product, and carrying out sufficient aging. The gel is then crystallized to yield the 4A molecular sieve.
After crystallization, the compound impurities of the soluble iron 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 partial impurities and the 4A molecular sieve is realized. The remainder of the impurity elements form within the interior of the 4A molecular sieve, forming the interior of the 4A molecular sieve product. Solves the problem that the prior alkali mud recycling method requires 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 an insoluble impurity form in the calcined treatment, and the impurity elements are removed through hot filtration after the synthesis reaction, so that the silicon is retained to the greatest extent, and the other impurity elements are removed.
In some embodiments of the present invention, the alkali mud before mixing with aluminum hydroxide and 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 water content is below 10%. The crushing treatment process is to recover the caking formed by the materials in the wet alkali mud drying process into the original powder state through crushing operations such as simple extrusion, collision and the like, and the dry alkali mud is not required to be ground into a product with smaller granularity, so that 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 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. Mixing the three solid raw materials, stirring uniformly for 20-70min; further for 30-60min.
In some embodiments of the invention, the firing temperature is 500-750 ℃; further, the roasting temperature is 550-735 ℃.
In some embodiments of the invention, the calcined product is added to water in a ratio of alkali mud to water of 1:12-25 by mass; 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 ageing time is 1-3h.
In some embodiments of the invention, the crystallization reaction is carried out at a temperature of 90-110 ℃ for a period of 2-12 hours; further, the reaction temperature is 93.8-105.6 ℃, and the reaction time is 2.5-10.5h.
In some embodiments of the invention, the crystallized product is directly subjected to filtration treatment after crystallization reaction to remove the filtrate. There is no cooling or cooling process.
In some embodiments of the invention, the filtered solid product is washed with water and then dried. Washing to pH value less than 11, and the filtrate is colorless. Finally, a white powder product is obtained.
One or more of the technical schemes of the invention has the following beneficial effects:
the invention relates to a method for preparing a 4A molecular sieve by alkali mud recycling, which prepares a fine chemical product with high added value, solves the problem of solid waste disposal of sodium silicate enterprises, improves the profitability 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, roasting pretreatment is carried out on a silicon source, an aluminum source and caustic soda together, and a gelling process and a crystallization process are completed in the same reactor, so that the 4A molecular sieve product with regular morphology is prepared.
The product of alkali mud, aluminium hydroxide and sodium hydroxide after roasting is dissolved in water to form gel product, and the crystallization process of the gel product can be implemented without adding seed crystal.
Drawings
The accompanying drawings, which 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.
FIG. 1 is a flow chart for the preparation of a 4A molecular sieve by alkali mud reclamation;
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;
fig. 4 is a scan of a 4A molecular sieve product prepared in example 3.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. 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 in accordance with the present application. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
The alkali mud used in the invention can also be called as silicon mud, alkali silicon mud, sodium silicate solid waste, sodium silicate waste and the like which meet the names of sources.
The existing alkali mud regeneration method is to recycle after mechanical separation, combination reaction-flotation machine separation, precipitation and filter pressing, and to form water-soluble compounds from metal ions or compounds in slurry through combination reaction, so as to complete the combination separation in liquid. The method is to separate and recycle the available active ingredient silicon dioxide in the silicon mud, but the silicon and other elements in the alkali mud are often in a symbiotic state, so that the selective separation is difficult to realize.
In the existing method, waste silica slag is utilized to produce sodium silicate, but the sodium silicate cannot be effectively separated due to excessive impurity content in alkali mud, so that after the liquid sodium silicate is obtained, the product is obviously green and the purity is not up to standard. On the other hand, a large amount of wastewater is generated while solid waste is treated, so that new environmental problems are brought.
In the existing method, silica mud is utilized to produce white carbon black, firstly, silica mud slurry is stirred and stirred uniformly, then solid-liquid separation is carried out, solid waste residues are automatically separated and removed, separated silica mud solution is pumped into special flotation equipment to extract carbon powder, the separated silica mud solution is circulated in a flotation cylinder for a period of time through the action of a circulating pump, then, the silica mud solution is left for a period of time, a suspending agent is added, a drain valve of a transparent pipe on the top surface of the flotation cylinder is opened, sewage in the transparent pipe above the drain valve is discharged, a proper amount of water is added after each discharge is completed, and the above procedures are repeated in a circulating mode until no black fine particles exist in the silica mud solution in the transparent pipe on the flotation cylinder; the pickling process is to pump the floated silicon mud solution into an acid tank, add bicarbonate and stir uniformly. And then precipitating, washing, press-filtering, pulping again, and spray-drying to form relatively uniform granular white carbon black. However, silicon and other elements in the alkaline mud are often in a symbiotic state, selective separation is difficult to realize, the effective treatment amount of the alkaline mud is not high, the obtained product amount is low, and the actual treatment cost is too high due to the complex treatment process and raw material input.
The invention will be further illustrated by the following examples
Example 1
The technical scheme of the invention is adopted to successfully prepare the 4A molecular sieve product by taking alkali mud of certain sodium silicate production enterprises in Shandong province as a raw material. The preparation method of the product comprises the following steps:
(1) The wet alkali mud is taken and placed in an environment of 110 ℃ to be fully dried for 6 hours, and the final water content is 6.1 percent;
(2) Crushing the agglomerates adhered together in the drying process to recover the powder with the original granularity;
(3) 30 parts of alkali mud, 30 parts of aluminum hydroxide and 64 parts of sodium hydroxide are placed in a sealed mixing device and stirred and mixed for 40min, so that the mixed materials are uniform in composition.
(4) The materials which are mixed are conveyed into a roasting furnace, roasted for 3 hours at the temperature of 685 ℃, and then cooled to 60 ℃.
(5) And (3) putting the roasting product into a crystallization kettle containing 550 parts of softened water, controlling the temperature in the kettle at 50 ℃, stirring for 2 hours at a low speed, standing and aging for 2 hours to obtain gel.
(6) The temperature of the crystallization kettle is increased to 98 ℃ and the reaction is carried out for 5.5h.
(7) Immediately filtering the product after the crystallization reaction is finished, and removing filtrate;
(8) After the filtration was completed, the solid product was continuously washed with demineralized water to a pH of 10.5, and the filtrate was observed to be colorless. And drying the washed product to obtain a white powder product.
As shown in figure 2, the 4A molecular sieve product with a relatively regular appearance is obtained by the scheme, and the grain diameter of the crystal is about 2 um.
Example 2
The technical scheme of the invention is adopted to successfully prepare the 4A molecular sieve product by taking alkali mud of a certain metasilicate production enterprise in Shandong as a raw material. The preparation method of the product comprises the following steps:
(1) The wet alkali mud is taken and placed in an environment of 118 ℃ to be fully dried for 4 hours, and the final water content is 6%;
(2) Crushing the agglomerates adhered together in the drying process to recover the powder with the original granularity;
(3) 30 parts of alkali mud, 34 parts of aluminum hydroxide and 58 parts of sodium hydroxide are placed in a sealed mixing device and stirred and mixed for 30 minutes, so that the mixed materials are uniform in composition.
(4) The mixed materials are conveyed into a roasting furnace, roasted for 3.5 hours at 635 ℃, and then cooled to 60 ℃.
(5) And (3) putting the roasting product into a crystallization kettle containing 485 parts of softened water, controlling the temperature in the kettle at 40 ℃, stirring for 2 hours at a low speed, standing and aging for 1 hour to obtain gel.
(6) The temperature of the crystallization kettle is increased to 96 ℃ and the reaction is carried out for 6 hours.
(7) Immediately filtering the product after the crystallization reaction is finished, and removing filtrate;
(8) After the filtration was completed, the solid product was continuously washed with demineralized water to a pH of 10.5, and the filtrate was observed to be colorless. And drying the washed product to obtain a white powder product.
As shown in figure 3, the 4A molecular sieve product with a relatively regular appearance is obtained by the scheme, and the grain diameter of the crystal 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 alkali mud of a silicate production enterprise in Shandong as a raw material. The preparation method of the product comprises the following steps:
(1) The wet alkali mud is taken and placed in an environment of 95 ℃ to be fully dried for 10 hours, and the final water content is 7.2%;
(2) Crushing the agglomerates adhered together in the drying process to recover the powder with the original granularity;
(3) 30 parts of alkali mud, 26 parts of aluminum hydroxide and 47 parts of sodium hydroxide are placed in a sealed mixing device and stirred and mixed for 40min, so that the mixed materials are uniform in composition.
(4) And (3) conveying the materials which are mixed into a roasting furnace, roasting for 5 hours at 600 ℃, and then cooling to 60 ℃.
(5) And (3) putting the roasting product into a crystallization kettle containing 400 parts of softened water, controlling the temperature in the kettle to be 55 ℃, stirring for 3 hours at a low speed, standing and aging for 2 hours, and thus obtaining gel.
(6) The temperature of the crystallization kettle is increased to 102.5 ℃ and the reaction is carried out for 6 hours.
(7) Immediately filtering the product after the crystallization reaction is finished, and removing filtrate;
(8) After the filtration was completed, the solid product was continuously washed with demineralized water to a pH of 10.5, and the filtrate was observed to be colorless. And drying the washed product to obtain a white powder product.
As shown in figure 4, the 4A molecular sieve product with a relatively regular appearance is obtained by the scheme, and the grain diameter of the crystal is about 1.2 um.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
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 from a precipitation or press filtration process of liquid sodium silicate after 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) Carrying out crystallization reaction on the gel product to obtain a crystallization product after the crystallization reaction, wherein the solid crystallization product obtained after the crystallization product is filtered contains a 4A molecular sieve;
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;
preparing a 4A molecular sieve by using a one-pot method, namely roasting and preprocessing a silicon source, an aluminum source and caustic soda together, wherein the gelling process and the crystallization process are completed in the same reactor;
the alkali mud mainly contains silicon, other impurity elements can be removed in an insoluble impurity form in the treatment after calcination, and the alkali mud is removed through hot filtration after the synthesis reaction, so that the silicon is retained to the greatest extent, and the other impurity elements are removed.
2. The method for preparing the 4A molecular sieve by recycling the alkali mud according to claim 1, which is characterized by comprising the following steps: 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 according to claim 2, which is characterized by comprising the following steps: the drying temperature is 80-130 ℃.
4. The method for preparing the 4A molecular sieve by recycling the alkali mud according to claim 1, which is characterized by comprising the following steps: the mass ratio of the alkali mud to the aluminum hydroxide to the sodium hydroxide is 1.0:1.05-1.77:1.83-2.58.
5. The method for preparing the 4A molecular sieve by recycling the alkali mud according to claim 1, which is characterized by comprising the following steps: the roasting temperature is 500-750 ℃.
6. The method for preparing the 4A molecular sieve by recycling the alkali mud according to claim 5, which is characterized in that: the roasting temperature is 550-735 ℃.
7. The method for preparing the 4A molecular sieve by recycling the alkali mud according to claim 1, which is characterized by comprising the following steps: the roasted product is added into water according to the mass ratio of alkali mud to water of 1:12-25.
8. The method for preparing the 4A molecular sieve by recycling the alkali mud according to claim 7, which is characterized in that: the mass ratio of the alkali mud to the water is 1:13.4-22.7.
9. The method for preparing the 4A molecular sieve by recycling the alkali mud according to claim 7, which is characterized in that: the temperature of the water is 30-65 ℃.
10. The method for preparing the 4A molecular sieve by recycling the alkali mud according to claim 1, which is characterized by comprising the following steps: standing and ageing for 1-3h.
11. The method for preparing the 4A molecular sieve by recycling the alkali mud according to claim 1, which is characterized by comprising the following steps: the temperature of the crystallization reaction is 90-110 ℃, and the reaction time is 2-12h.
12. The method for preparing the 4A molecular sieve by recycling the alkali mud according to claim 11, which is characterized in that: the crystallization reaction temperature is 93.8-105.6 ℃, and the reaction time is 2.5-10.5h.
13. The method for preparing the 4A molecular sieve by recycling the alkali mud according to claim 1, which is characterized by comprising the following steps: after the crystallization reaction, the crystallized product is directly filtered to remove the filtrate.
14. The method for preparing the 4A molecular sieve by recycling the alkali mud according to claim 1, which is characterized by comprising the following steps: the filtered solid product was washed with water and then dried.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210288709.0A CN114538464B (en) | 2022-03-23 | 2022-03-23 | Method for preparing 4A molecular sieve by alkali mud recycling |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210288709.0A CN114538464B (en) | 2022-03-23 | 2022-03-23 | Method for preparing 4A molecular sieve by alkali mud recycling |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114538464A CN114538464A (en) | 2022-05-27 |
| CN114538464B true CN114538464B (en) | 2024-03-26 |
Family
ID=81665619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210288709.0A Active CN114538464B (en) | 2022-03-23 | 2022-03-23 | Method for preparing 4A molecular sieve by alkali mud recycling |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114538464B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274760A (en) * | 2008-05-18 | 2008-10-01 | 沙利 | Production method for silicon sludge recycle |
| 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 |
| CN104340989A (en) * | 2013-07-24 | 2015-02-11 | 中国科学院过程工程研究所 | Hydrothermal synthesis method of 4A molecular sieve |
| KR101533093B1 (en) * | 2015-04-10 | 2015-07-02 | 주식회사 이레하이테크이앤씨 | High-Early Strength cement concrete composition and concrete pavement repair it using the same method using silicon sludge |
| WO2018177294A1 (en) * | 2017-03-27 | 2018-10-04 | 储晞 | Method, apparatus, and system for producing silicon-containing product by utilizing silicon mud byproduct of cutting silicon material with diamond wire |
| 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 |
-
2022
- 2022-03-23 CN CN202210288709.0A patent/CN114538464B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101274760A (en) * | 2008-05-18 | 2008-10-01 | 沙利 | Production method for silicon sludge recycle |
| 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 |
| CN104340989A (en) * | 2013-07-24 | 2015-02-11 | 中国科学院过程工程研究所 | Hydrothermal synthesis method of 4A molecular sieve |
| KR101533093B1 (en) * | 2015-04-10 | 2015-07-02 | 주식회사 이레하이테크이앤씨 | High-Early Strength cement concrete composition and concrete pavement repair it using the same method using silicon sludge |
| WO2018177294A1 (en) * | 2017-03-27 | 2018-10-04 | 储晞 | Method, apparatus, and system for producing silicon-containing product by utilizing silicon mud byproduct of cutting silicon material with diamond wire |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114538464A (en) | 2022-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102249253B (en) | Method for producing aluminum oxide and co-producing active calcium silicate through high-alumina fly ash | |
| RU2644169C1 (en) | Method of recovery of alkali and aluminum during processing of the red mud obtained in the bayer process using liming and carbonization technology | |
| CN1903725A (en) | Comprehensive utilization treatment tachnology of aluminium waste slag, waste ash | |
| CN112570419B (en) | Aluminum ash recycling method, harmless aluminum ash and application of harmless aluminum ash | |
| CN101811711A (en) | Method for extracting aluminum oxide from fly ash | |
| CN113716583A (en) | Method for preparing 4A zeolite by using MSWI fly ash and red mud hydrothermal method | |
| WO2017101746A1 (en) | Bauxite desiliconization method | |
| CN109336147B (en) | Method for producing alumina by using industrial solid waste rich in alumina | |
| CN111348669A (en) | Preparation method of sodium hexafluoroaluminate | |
| CN112551658A (en) | High-alumina fly ash defluorination flocculant and preparation method and application thereof | |
| CN110482564B (en) | Method for synthesizing zeolite molecular sieve by treating illite through microwave heating solid-phase acid steam conversion method | |
| CN1062252C (en) | Potash fertilizer producing method by using potassium-rock | |
| CN106517277A (en) | Method for producing aluminum oxide co-production silicon fertilizer from bauxite | |
| CN114538464B (en) | Method for preparing 4A molecular sieve by alkali mud recycling | |
| CN113371749A (en) | Method for treating calcium-containing sludge in semiconductor industry | |
| CN101139099B (en) | Technique for producing 4A zeolite by using sodium white slime | |
| CN102643710A (en) | Silicon wafer-cutting waste slurry recovery method | |
| CN114804673A (en) | Comprehensive utilization method of red mud | |
| CN112047422B (en) | Production process of composite phosphorus removal agent for sewage treatment | |
| CN105668597A (en) | Method of acid-alkali combined extraction of aluminum-based products and silicon-based products from fly ash | |
| CN114890443A (en) | System and process method for high-value utilization of lithium-containing waste | |
| CN105753025A (en) | Method utilizing high-alumina fly ash to produce aluminum oxide | |
| CN102701228A (en) | Recycling method of caustic alkaline liquid for treatment of high-silicon aluminum ore material | |
| CN100402430C (en) | Method and technology of producing precipitated barium sulphate using white carbon black waste liquor | |
| CN110078463B (en) | CO solidification by steel slag2Production process for manufacturing building blocks |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |