CN106542534A - A kind of method of impurity natrium in de-sodium agent removing afwillite - Google Patents
A kind of method of impurity natrium in de-sodium agent removing afwillite Download PDFInfo
- Publication number
- CN106542534A CN106542534A CN201510598695.2A CN201510598695A CN106542534A CN 106542534 A CN106542534 A CN 106542534A CN 201510598695 A CN201510598695 A CN 201510598695A CN 106542534 A CN106542534 A CN 106542534A
- Authority
- CN
- China
- Prior art keywords
- sodium
- calcium silicate
- water
- product
- mass
- 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.)
- Pending
Links
- 239000011734 sodium Substances 0.000 title claims abstract description 50
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 15
- 239000012535 impurity Substances 0.000 title claims abstract description 15
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 title 1
- 239000000047 product Substances 0.000 claims abstract description 105
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims abstract description 69
- 239000000378 calcium silicate Substances 0.000 claims abstract description 68
- 229910052918 calcium silicate Inorganic materials 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 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 claims abstract description 46
- 239000012065 filter cake Substances 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 20
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 19
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 18
- 239000002585 base Substances 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 20
- 238000009993 causticizing Methods 0.000 claims description 18
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 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
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 150000002681 magnesium compounds Chemical class 0.000 claims description 3
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000008237 rinsing water Substances 0.000 claims 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 claims 1
- -1 compounds Compounds Chemical class 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 18
- 229910001948 sodium oxide Inorganic materials 0.000 abstract description 18
- 239000010881 fly ash Substances 0.000 abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- DEPUMLCRMAUJIS-UHFFFAOYSA-N dicalcium;disodium;dioxido(oxo)silane Chemical compound [Na+].[Na+].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O DEPUMLCRMAUJIS-UHFFFAOYSA-N 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 description 1
- OSMSIOKMMFKNIL-UHFFFAOYSA-N calcium;silicon Chemical compound [Ca]=[Si] OSMSIOKMMFKNIL-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
本发明提供了一种利用粉煤灰脱硅液制备水合硅酸钙过程中，通过脱钠剂有效脱除产品中杂质钠的方法，包括以下步骤：将主要成分为硅酸钠和氢氧化钠混合溶液的脱硅液苛化，得到水合硅酸钙浆液固液分离后淋洗得滤饼，即水合硅酸钙；将所得水合硅酸钙与水混合形成悬浊液后加入脱钠剂，充分搅拌后过滤，水淋洗得滤饼；滤饼干燥后即得低含钠量水合硅酸钙产品(氧化钠小于1％)。该方法具有成本低廉，工艺简单，条件温和，易于工业化生产等优点，能够实现在较低洗水量条件下显著降低水合硅酸钙产品中的钠含量，避免钠在生产过程中的流失，同时可以得到低钠水合硅酸钙产品，为其下游高附加值利用提供了基础。
The invention provides a method for effectively removing impurity sodium in the product through a sodium removing agent in the process of preparing hydrated calcium silicate by utilizing fly ash desiliconization liquid, comprising the following steps: the main components are sodium silicate and sodium hydroxide The desiliconization solution of the mixed solution is causticized to obtain the calcium silicate hydrate slurry, which is separated from the solid and liquid, and then rinsed to obtain a filter cake, that is, the calcium silicate hydrate; the obtained calcium silicate hydrate is mixed with water to form a suspension, and then the sodium removal agent is added. After fully stirring, filter and rinse with water to obtain a filter cake; after the filter cake is dried, a hydrated calcium silicate product with low sodium content (sodium oxide is less than 1%) can be obtained. The method has the advantages of low cost, simple process, mild conditions, and easy industrial production, etc., and can significantly reduce the sodium content in calcium silicate hydrate products under the condition of relatively low washing water volume, avoiding the loss of sodium in the production process, and at the same time can The low-sodium hydrated calcium silicate product is obtained, which provides a basis for its downstream high value-added utilization.
Description
技术领域 technical field
本发明涉及固体废弃物资源化利用技术领域，尤其涉及一种水合硅酸钙产品脱除杂质钠的方法。 The invention relates to the technical field of resource utilization of solid waste, in particular to a method for removing impurity sodium from a hydrated calcium silicate product.
背景技术 Background technique
粉煤灰主要产生于燃煤电厂，排放量巨大，其大量堆存导致了大气、水体和土壤的严重污染。近年来，国内外普遍开展了粉煤灰高值化利用研究，形成了高铝粉煤灰提取氧化铝、制备莫来石耐火材料、石油压裂支撑剂等多条技术路线。这些工艺中均涉及到粉煤灰预脱硅过程，不可避免的产生了大量高碱性脱硅液，主要成分为硅酸钠和氢氧化钠，其高效利用集中在以脱硅液和氧化钙为原料，合成水合硅酸钙系列产品，其在涂料、油墨、日化、建材、装饰材料、蓄电池制造等各个行业均有广泛应用，具体的合成方法已在“一种利用高铝粉煤灰生产莫来石和硅酸钙的方法(CN201210005531.0)”，“一种利用粉煤灰脱硅母液生产硅酸钙的方法(CN201210005534.4)”两项发明专利中有详细记述。 Fly ash is mainly produced in coal-fired power plants, with huge emissions, and its large-scale stockpiling has led to serious pollution of the atmosphere, water and soil. In recent years, research on the high-value utilization of fly ash has been widely carried out at home and abroad, and many technical routes have been formed, such as extracting alumina from high-alumina fly ash, preparing mullite refractory materials, and oil fracturing proppants. These processes all involve the pre-desilication process of fly ash, which inevitably produces a large amount of highly alkaline desiliconization liquid, the main components of which are sodium silicate and sodium hydroxide. As a raw material, synthesize hydrated calcium silicate series products, which are widely used in various industries such as coatings, inks, daily chemicals, building materials, decorative materials, and battery manufacturing. The method for producing mullite and calcium silicate (CN201210005531.0)” and “A method for producing calcium silicate using fly ash desilication mother liquor (CN201210005534.4)” are described in detail in two invention patents.
在脱硅液苛化过程中，水合硅酸钙的形成会夹杂大量的钠，这些钠难以通过普通洗涤的方法去除，而钠含量的高低直接决定水合硅酸钙及后续制品的产品质量；同时，这些产品中杂质钠的去除还会提高钠的回收率，降低了碱耗及生产成本。普通洗涤方法得到的氧化钠含量为3-8％，洗水用量为干基产品质量的3-5倍，大量低浓度洗液无法利用。CN 103204530 A及CN 102992368 A中，使用盐酸，硫酸等去除氧化铝和氢氧化铝产品中除钠，但使用酸会对产品造成太大的影响，且由于产品性质的差别，不适用于水合硅酸钙除钠；CN 102432035 A则公布了一种通过球磨后水热处理硅酸钠钙的方法，该法通过水热分解硅酸 钠钙得到低碱含量水合硅酸钙产品，但水热处理过程温度较高(160-240℃)，能耗较大成本较高。 During the causticizing process of the desiliconization solution, the formation of calcium silicate hydrate will contain a large amount of sodium, which is difficult to remove by ordinary washing methods, and the level of sodium content directly determines the product quality of calcium silicate hydrate and subsequent products; at the same time , The removal of impurity sodium in these products will also increase the recovery rate of sodium, reducing alkali consumption and production costs. The content of sodium oxide obtained by ordinary washing methods is 3-8%, and the amount of washing water is 3-5 times of the dry product quality, and a large amount of low-concentration washing liquid cannot be used. In CN 103204530 A and CN 102992368 A, hydrochloric acid, sulfuric acid, etc. are used to remove sodium from aluminum oxide and aluminum hydroxide products, but the use of acid will cause too much impact on the product, and due to the difference in product properties, it is not suitable for hydrated silicon Calcium acid removes sodium; CN 102432035 A discloses a method for hydrothermally treating sodium calcium silicate after ball milling, which obtains low alkali content hydrated calcium silicate products by hydrothermally decomposing sodium calcium silicate, but the hydrothermal treatment process temperature Higher (160-240°C), higher energy consumption and higher cost.
发明内容 Contents of the invention
本发明的目的在于针对水合硅酸钙产品中钠含量高，难以脱除的问题，提供一种通过脱钠剂有效脱除水合硅酸钙中杂质钠的方法，该方法能够实现在较低洗水量条件下显著降低水合硅酸钙产品中的钠含量，避免钠在生产过程中的流失，同时可以得到低钠的高质量水合硅酸钙产品，为其下游高附加值利用提供了基础。该方法具有成本低廉，工艺简单，条件温和，易于工业化生产等优点。 The purpose of the present invention is to provide a method for effectively removing impurity sodium in calcium silicate hydrate by using a sodium removing agent for the high sodium content in hydrated calcium silicate products, which is difficult to remove. Under water conditions, the sodium content in hydrated calcium silicate products is significantly reduced to avoid the loss of sodium in the production process, and at the same time, low-sodium, high-quality hydrated calcium silicate products can be obtained, which provides a basis for its downstream high value-added utilization. The method has the advantages of low cost, simple process, mild conditions, easy industrial production and the like.
为达此目的，本发明采用以下技术方案： For reaching this purpose, the present invention adopts following technical scheme:
一种脱钠剂脱除水合硅酸钙中杂质钠的方法，包括以下步骤： A method for removing impurity sodium in calcium silicate hydrate by a sodium removing agent, comprising the following steps:
(1)将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，固体即高钠含量水合硅酸钙； (1) The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from solid to liquid, and the solid is high sodium content hydrated calcium silicate;
(2)将所得水化硅酸钙用10-100℃，干基产品质量0.1-10倍的水淋洗得滤饼后，与10-200℃，干基产品质量0.1-10倍的水混合形成悬浊液后加入干基产品质量0.001-2倍的脱钠剂剂，充分搅拌0.5-24h后过滤，用10-100℃，干基产品质量0.1-10倍的水淋洗得滤饼。所述脱钠剂为铝系化合物、钙系化合物、镁系化合物的一种或多种的混合物，或主体成分(质量分数大于50％)为上述物质的其它种类的混合物。所述的铝系化合物包括但不限于氧化铝，草酸铝，氢氧化铝，氯化铝，硝酸铝中的一种或多种的混合物，所述的钙系化合物包括但不限于氧化钙，草酸钙，氢氧化钙，氯化钙，硝酸钙中的一种或多种的混合物，所述的镁系化合物包括但不限于氧化镁，草酸镁，氢氧化镁，氯化镁，硝酸镁中的一种或多种的混合物。 (2) Rinse the obtained calcium silicate hydrate with water at 10-100°C and 0.1-10 times the mass of the dry product to obtain a filter cake, and then mix it with water at 10-200°C and 0.1-10 times the mass of the dry product After the suspension is formed, add a sodium-removing agent that is 0.001-2 times the mass of the product on a dry basis, stir well for 0.5-24 hours, filter, and rinse with water at 10-100°C that is 0.1-10 times the mass of the product on a dry basis to obtain a filter cake. The sodium-removing agent is a mixture of one or more of aluminum-based compounds, calcium-based compounds, and magnesium-based compounds, or other types of mixtures in which the main component (mass fraction is greater than 50%) is the above-mentioned substances. The aluminum-based compounds include but are not limited to aluminum oxide, aluminum oxalate, aluminum hydroxide, aluminum chloride, aluminum nitrate, and the calcium-based compounds include but are not limited to calcium oxide, oxalic acid A mixture of one or more of calcium, calcium hydroxide, calcium chloride, and calcium nitrate, the magnesium compound includes but not limited to one of magnesium oxide, magnesium oxalate, magnesium hydroxide, magnesium chloride, and magnesium nitrate or a mixture of several.
(3)上述洗涤过程均可以采用逆流洗涤方式，从而大大减少总洗涤水量。 (3) The above-mentioned washing process can all adopt the countercurrent washing method, thereby greatly reducing the total washing water volume.
本发明针对钠的存在特点，采用脱钠剂与逆流洗涤结合的方式去除水合硅酸钙中杂质钠；相对于普通洗涤方式，本方法更能够有效去除水合硅酸钙中的钠，且方法简单，减少了用水量，提高了钠去除效果。实践证明，采用本发明方法制备的水合硅酸钙，其氧化钠含量小于1％，洗涤水用量仅为干基产品质量0.1-10倍。 Aiming at the characteristics of sodium, the present invention adopts the combination of sodium removing agent and countercurrent washing to remove impurity sodium in calcium silicate hydrate; compared with ordinary washing methods, this method can more effectively remove sodium in calcium silicate hydrate, and the method is simple , reduces water consumption and improves sodium removal. Practice has proved that the hydrated calcium silicate prepared by the method of the present invention has a sodium oxide content of less than 1%, and the amount of washing water is only 0.1-10 times the mass of the product on a dry basis.
附图说明 Description of drawings
图1是粉煤灰脱硅液制备水合硅酸钙过程使用脱钠剂脱除杂质钠的流程图。 Fig. 1 is a flow chart of using a sodium removing agent to remove impurity sodium in the process of preparing hydrated calcium silicate from fly ash desiliconization solution.
具体实施方式 detailed description
下面结合具体实施方式来进一步说明本发明的技术方案，但本发明的保护范围应包括权利要求的全部内容，不仅仅限于以下实施例。 The technical solutions of the present invention will be further described below in conjunction with specific embodiments, but the scope of protection of the present invention should include the entire content of the claims, not only limited to the following examples.
实施例1 Example 1
将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，用70℃，干基产品质量3倍的水淋洗得滤饼；然后将所得水合硅酸钙滤饼与70℃，干基产品质量3倍的水混合形成悬浊液后加入0.05干基产品质量0.05倍的草酸钙，充分搅拌24h后过滤，用70℃，干基产品质量3倍的水淋洗得滤饼，干燥后测得水合硅酸钙产品中氧化钠含量0.79％。 The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from the solid and liquid, and washed with water at 70°C, which is three times the mass of the product on a dry basis, to obtain a filter cake; Mix water with 3 times the mass of the base product to form a suspension, add 0.05 calcium oxalate with a mass of 0.05 times the mass of the dry base product, stir thoroughly for 24 hours, filter, rinse with water at 70 ° C, 3 times the mass of the dry base product to obtain a filter cake, and dry After measuring the sodium oxide content in the hydrated calcium silicate product was 0.79%.
实施例2 Example 2
将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，用90℃，干基产品质量1倍的水淋洗得滤饼；然后将所得水合硅酸钙滤饼与90℃，干基产品质量1倍的水混合形成悬浊液后加入干基产品质量0.001倍的氯化钙，充分搅拌0.5h后过滤，用90℃，干基产品质量1倍的水淋洗得滤饼，干燥后测得水合硅酸钙产品中氧化钠含量0.67％。 The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from the solid and liquid, and washed with water at 90°C, which is 1 times the mass of the product on a dry basis, to obtain a filter cake; Water with 1 times the mass of the base product was mixed to form a suspension, and then calcium chloride with 0.001 times the mass of the dry product was added, stirred thoroughly for 0.5 h, filtered, and washed with water at 90°C, which was 1 times the mass of the dry product, to obtain a filter cake. After drying, the sodium oxide content in the hydrated calcium silicate product was measured to be 0.67%.
实施例3 Example 3
将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，用10℃，干基产品质 量1倍的水淋洗得滤饼；然后将所得水合硅酸钙滤饼与10℃，干基产品质量1倍的水混合形成悬浊液后加入干基产品质量0.5倍的氢氧化钙，充分搅拌12h后过滤，用10℃，干基产品质量1倍的水淋洗得滤饼，干燥后测得水合硅酸钙产品中氧化钠含量0.54％。 The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from the solid and liquid, and washed with water at 10°C, which is 1 times the mass of the product on a dry basis, to obtain a filter cake; Mix water with 1 times the mass of the base product to form a suspension, then add calcium hydroxide with 0.5 times the mass of the dry base product, stir thoroughly for 12 hours, filter, rinse with water at 10°C, 1 times the mass of the dry base product to obtain a filter cake, and dry After measuring the sodium oxide content in the hydrated calcium silicate product was 0.54%.
实施例4 Example 4
将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，用80℃，干基产品质量5倍的水淋洗得滤饼；然后将所得水合硅酸钙滤饼与80℃，干基产品质量5倍的水混合形成悬浊液后加入干基产品质量1倍的氧化钙，充分搅拌6h后过滤，用70℃，5干基产品质量5倍的水淋洗得滤饼，干燥后测得水合硅酸钙产品中氧化钠含量0.50％。 The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from the solid and liquid, and washed with water at 80°C, which is 5 times the mass of the product on a dry basis, to obtain a filter cake; Mix water with 5 times the weight of the base product to form a suspension, add calcium oxide with 1 times the weight of the dry base product, stir thoroughly for 6 hours, then filter, rinse with water at 70 °C, 5 times the weight of the dry base product to obtain a filter cake, and dry Measure 0.50% sodium oxide content in the hydrated calcium silicate product afterward.
实施例5 Example 5
将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，用70℃，干基产品质量2倍的水淋洗得滤饼；然后将所得水合硅酸钙滤饼与70℃，干基产品质量2倍的水混合形成悬浊液后加入干基产品质量0.3倍的硝酸钙和干基产品质量0.2倍的氯化钙，充分搅拌15h后过滤，用70℃，干基产品质量2倍的水淋洗得滤饼，干燥后测得水合硅酸钙产品中氧化钠含量0.46％。 The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from the solid and liquid, and washed with water twice the mass of the dry product at 70°C to obtain a filter cake; After mixing water with 2 times the mass of the base product to form a suspension, add calcium nitrate with a mass of 0.3 times the mass of the dry base product and calcium chloride with a mass of 0.2 times the mass of the dry base product, stir thoroughly for 15 hours and then filter. times of water to obtain a filter cake, and after drying, the sodium oxide content in the hydrated calcium silicate product was measured to be 0.46%.
实施例6 Example 6
将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，用60℃，干基产品质量4倍的水淋洗得滤饼；然后将所得水合硅酸钙滤饼与60℃，干基产品质量4倍的水混合形成悬浊液后加入干基产品质量0.2倍的氧化镁，干基产品质量0.1倍的氢氧化镁和干基产品质量0.1倍的草酸镁，充分搅拌2h后过滤，用60℃，干基产品质量4倍的水淋洗得滤饼，干燥后测得水合硅酸钙产品中氧化钠含量0.61％。 The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from solid and liquid, and washed with water at 60°C, which is 4 times the quality of the dry product, to obtain a filter cake; After mixing water with 4 times the mass of the base product to form a suspension, add magnesium oxide with a mass of 0.2 times the mass of the dry base product, magnesium hydroxide with a mass of 0.1 times the mass of the dry base product, and magnesium oxalate with a mass of 0.1 times the mass of the dry base product, stir thoroughly for 2 hours and then filter , with 60 DEG C, rinsing with water 4 times the weight of the product on a dry basis to obtain a filter cake, and after drying, the content of sodium oxide in the hydrated calcium silicate product was measured to be 0.61%.
实施例7 Example 7
将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，用50℃，干基产品质量3倍的水淋洗得滤饼；然后将所得水合硅酸钙滤饼与50℃，干基产品质量3倍的水混合形成悬浊液后加入干基产品质量0.3倍的硝酸镁，充分搅拌20h后过滤，用50℃，干基产品质量3倍的水淋洗得滤饼，干燥后测得水合硅酸钙产品中氧化钠含量0.91％。 The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from the solid and liquid, and washed with water at 50°C, which is three times the mass of the product on a dry basis, to obtain a filter cake; Mix water with 3 times the mass of the base product to form a suspension, add magnesium nitrate with 0.3 times the mass of the dry base product, stir thoroughly for 20 hours, filter, rinse with water at 50 °C, 3 times the mass of the dry base product to obtain a filter cake, and dry The sodium oxide content in the hydrated calcium silicate product was measured to be 0.91%.
实施例8 Example 8
将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，用10℃，干基产品质量5倍的水淋洗得滤饼；然后将所得水合硅酸钙滤饼与120℃，干基产品质量3倍的水混合形成悬浊液后加入干基产品质量0.3倍的硝酸镁，充分搅拌14h后过滤，用10℃，干基产品质量5倍的水淋洗得滤饼，干燥后测得水合硅酸钙产品中氧化钠含量0.98％。 The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from the solid and liquid, and washed with water at 10°C, which is 5 times the mass of the product on a dry basis, to obtain a filter cake; Mix water with 3 times the mass of the base product to form a suspension, then add magnesium nitrate with 0.3 times the mass of the dry base product, stir thoroughly for 14 hours, filter, rinse with water at 10°C, 5 times the mass of the dry base product to obtain a filter cake, and dry The sodium oxide content in the hydrated calcium silicate product was measured to be 0.98%.
实施例9 Example 9
将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，用20℃，干基产品质量3倍的水淋洗得滤饼；然后将所得水合硅酸钙滤饼与20℃，干基产品质量3倍的水混合形成悬浊液后加入干基产品质量0.5倍的氧化镁和干基产品质量0.3倍的氯化镁，充分搅拌0.5h后过滤，用20℃，干基产品质量3倍的水淋洗得滤饼，干燥后测得水合硅酸钙产品中氧化钠含量0.77％。 The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from the solid and liquid, and washed with water at 20°C, which is 3 times the mass of the product on a dry basis, to obtain a filter cake; After mixing water with 3 times the mass of the base product to form a suspension, add magnesium oxide with a mass of 0.5 times the mass of the product on a dry basis and magnesium chloride with a mass of 0.3 times the mass on a dry basis, stir thoroughly for 0.5 hours and then filter. The filter cake was obtained by rinsing with water, and the sodium oxide content in the hydrated calcium silicate product was measured to be 0.77% after drying.
实施例10 Example 10
将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，用50℃，干基产品质量3倍的水淋洗得滤饼；然后将所得水合硅酸钙滤饼与50℃，干基产品质量3倍的水混合形成悬浊液后加入干基产品质量2倍的氢氧化镁，充分搅拌3h后过滤，用50℃，干基产品质量3倍的水淋洗得滤饼，干燥后测得水合硅酸钙产品 中氧化钠含量0.25％。 The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from the solid and liquid, and washed with water at 50°C, which is three times the mass of the product on a dry basis, to obtain a filter cake; Mix water with 3 times the mass of the base product to form a suspension, then add magnesium hydroxide with 2 times the mass of the dry base product, stir thoroughly for 3 hours, then filter, rinse with water at 50 ° C, 3 times the mass of the dry base product to obtain a filter cake, and dry Measure 0.25% of sodium oxide content in the hydrated calcium silicate product afterward.
实施例11 Example 11
将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，用100℃，干基产品质量5倍的水淋洗得滤饼；然后将所得水合硅酸钙滤饼与160℃，干基产品质量5倍的水混合形成悬浊液后加入干基产品质量0.9倍的氯化铝，充分搅拌5h后过滤，用100℃，干基产品质量5倍的水淋洗得滤饼，干燥后测得水合硅酸钙产品中氧化钠含量0.39％。 The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from solid and liquid, and washed with water at 100°C, which is 5 times the quality of the dry product, to obtain a filter cake; then the obtained hydrated calcium silicate filter cake is mixed with 160°C, Mix water with 5 times the mass of the base product to form a suspension, add aluminum chloride with 0.9 times the mass of the dry base product, stir thoroughly for 5 hours, filter, rinse with water at 100 ° C, 5 times the mass of the dry base product to obtain a filter cake, and dry After measuring the sodium oxide content in the hydrated calcium silicate product was 0.39%.
实施例12 Example 12
将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，用10℃，干基产品质量7倍的水淋洗得滤饼；然后将所得水合硅酸钙滤饼与10℃，干基产品质量7倍的水混合形成悬浊液后加入干基产品质量0.5倍的氧化铝和干基产品质量0.1倍的氯化镁，充分搅拌8h后过滤，用10℃，干基产品质量7倍的水淋洗得滤饼，干燥后测得水合硅酸钙产品中氧化钠含量0.85％。 The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from the solid and liquid, and washed with water 7 times the mass of the product on a dry basis at 10°C to obtain a filter cake; After mixing water with 7 times the mass of the base product to form a suspension, add alumina with a mass of 0.5 times the mass of the dry base product and magnesium chloride with a mass of 0.1 times the mass of the dry base product, stir thoroughly for 8 hours and then filter. The filter cake was washed with water, and after drying, the sodium oxide content in the hydrated calcium silicate product was measured to be 0.85%.
实施例13 Example 13
将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，用70℃，干基产品质量0.1倍的水淋洗得滤饼；然后将所得水合硅酸钙滤饼与70℃，干基产品质量0.1倍的水混合形成悬浊液后加入干基产品质量0.3倍的硝酸铝，充分搅拌8h后过滤，用70℃，干基产品质量0.1倍的水淋洗得滤饼，干燥后测得水合硅酸钙产品中氧化钠含量0.93％。 The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from solid and liquid, and rinsed with water at 70°C, which is 0.1 times the product quality on a dry basis, to obtain a filter cake; then the obtained hydrated calcium silicate filter cake is mixed with 70°C, Mix water with 0.1 times the mass of the base product to form a suspension, add aluminum nitrate with a mass of 0.3 times the mass of the dry base product, stir thoroughly for 8 hours, filter, rinse with water at 70°C, and 0.1 times the mass of the dry base product to obtain a filter cake, and after drying The sodium oxide content in the hydrated calcium silicate product was measured to be 0.93%.
实施例14 Example 14
将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，用90℃，干基产品质量1倍的水淋洗得滤饼；然后将所得水合硅酸钙滤饼与100℃，干基产品质量1倍的水混合形成悬浊液后加入干基产品质量0.1倍的草酸铝，充分搅拌2h后过 滤，用90℃，干基产品质量1倍的水淋洗得滤饼，干燥后测得水合硅酸钙产品中氧化钠含量0.44％。 The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from the solid and liquid, and washed with water at 90°C, which is 1 times the mass of the product on a dry basis, to obtain a filter cake; Mix water with 1 times the mass of the base product to form a suspension, add aluminum oxalate with 0.1 times the mass of the dry base product, stir thoroughly for 2 hours, filter, rinse with water at 90 °C, 1 times the mass of the dry base product to obtain a filter cake, and dry The sodium oxide content in the hydrated calcium silicate product was measured to be 0.44%.
实施例15 Example 15
将硅酸钠溶液苛化得到的水合硅酸钙浆液固液分离，用90℃，干基产品质量10倍的水淋洗得滤饼；然后将所得水合硅酸钙滤饼与200℃，干基产品质量10倍的水混合形成悬浊液后加入干基产品质量0.1倍的氧化铝和干基产品质量0.2倍的氧化钙，充分搅拌6h后过滤，用90℃，干基产品质量10倍的水淋洗得滤饼，干燥后测得水合硅酸钙产品中氧化钠含量0.35％。 The hydrated calcium silicate slurry obtained by causticizing the sodium silicate solution is separated from the solid and liquid, and washed with water 10 times the mass of the product on a dry basis at 90°C to obtain a filter cake; Mix water with 10 times the mass of the base product to form a suspension, then add alumina with a mass of 0.1 times the mass of the dry base product and calcium oxide with a mass of 0.2 times the mass of the dry base product, stir thoroughly for 6 hours, then filter, and use 90 ° C to 10 times the mass of the dry base product The filter cake was obtained by leaching with water, and after drying, the sodium oxide content in the hydrated calcium silicate product was measured to be 0.35%.
本发明未详细阐述部分属于本领域技术人员的公知技术。 Parts not described in detail in the present invention belong to the known techniques of those skilled in the art.
申请人声明，本发明通过上述实施例来说明本发明的详细方法，但本发明并不局限于上述详细方法，即不意味着本发明必须依赖上述详细方法才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。 The applicant declares that the present invention illustrates the detailed methods of the present invention through the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed methods, that is, it does not mean that the present invention must rely on the above-mentioned detailed methods to be implemented. Those skilled in the art should understand that any improvement of the present invention, the equivalent replacement of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the scope of protection and disclosure of the present invention.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510598695.2A CN106542534A (en) | 2015-09-18 | 2015-09-18 | A kind of method of impurity natrium in de-sodium agent removing afwillite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510598695.2A CN106542534A (en) | 2015-09-18 | 2015-09-18 | A kind of method of impurity natrium in de-sodium agent removing afwillite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106542534A true CN106542534A (en) | 2017-03-29 |
Family
ID=58362421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510598695.2A Pending CN106542534A (en) | 2015-09-18 | 2015-09-18 | A kind of method of impurity natrium in de-sodium agent removing afwillite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106542534A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107697923A (en) * | 2017-09-29 | 2018-02-16 | 临沂三禾生物质科技有限公司 | A kind of synthesis high activity, the production method of Lower alrali content calcium silicates |
| CN108178547A (en) * | 2017-12-29 | 2018-06-19 | 上海建工集团股份有限公司 | A kind of CSH gel-types early strength agent and its purification redisperse preparation method |
| CN109777960A (en) * | 2019-02-25 | 2019-05-21 | 河北工程大学 | A method for separating and recovering lithium and aluminum from fly ash |
| RU2700607C1 (en) * | 2018-10-09 | 2019-09-18 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method of producing pigment for thermally stabilizing coatings |
| CN110586312A (en) * | 2019-08-26 | 2019-12-20 | 昆明理工大学 | Method for recovering vanadium and chromium iron from vanadium-chromium tailings |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734673A (en) * | 2008-11-20 | 2010-06-16 | 贵阳宝源阳光硅业有限公司 | Calcium silicate and preparation method thereof |
| CN102190309A (en) * | 2011-01-06 | 2011-09-21 | 内蒙古大唐国际再生资源开发有限公司 | Method for lowering pH value of active calcium silicate |
| CN103145136A (en) * | 2013-01-08 | 2013-06-12 | 东北大学 | Production method of active calcium silicate |
-
2015
- 2015-09-18 CN CN201510598695.2A patent/CN106542534A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734673A (en) * | 2008-11-20 | 2010-06-16 | 贵阳宝源阳光硅业有限公司 | Calcium silicate and preparation method thereof |
| CN102190309A (en) * | 2011-01-06 | 2011-09-21 | 内蒙古大唐国际再生资源开发有限公司 | Method for lowering pH value of active calcium silicate |
| CN103145136A (en) * | 2013-01-08 | 2013-06-12 | 东北大学 | Production method of active calcium silicate |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107697923A (en) * | 2017-09-29 | 2018-02-16 | 临沂三禾生物质科技有限公司 | A kind of synthesis high activity, the production method of Lower alrali content calcium silicates |
| CN108178547A (en) * | 2017-12-29 | 2018-06-19 | 上海建工集团股份有限公司 | A kind of CSH gel-types early strength agent and its purification redisperse preparation method |
| RU2700607C1 (en) * | 2018-10-09 | 2019-09-18 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Method of producing pigment for thermally stabilizing coatings |
| CN109777960A (en) * | 2019-02-25 | 2019-05-21 | 河北工程大学 | A method for separating and recovering lithium and aluminum from fly ash |
| CN109777960B (en) * | 2019-02-25 | 2020-12-01 | 河北工程大学 | A method for separating and recovering lithium and aluminum from fly ash |
| CN110586312A (en) * | 2019-08-26 | 2019-12-20 | 昆明理工大学 | Method for recovering vanadium and chromium iron from vanadium-chromium tailings |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106542534A (en) | A kind of method of impurity natrium in de-sodium agent removing afwillite | |
| CN102320615B (en) | A kind of take SILICA FUME as the method that precipitated silica is prepared in raw material carbonization | |
| CN103214013B (en) | A kind of preparation method of high purity alumina powder | |
| CN104562180A (en) | Method for preparing calcium sulfate whisker from phosphogypsum | |
| CN104920449A (en) | Nano-zinc oxide composite triazophos pesticide and preparation method therefor | |
| CN106865586B (en) | A kind of method for preparing alumina type aeroge | |
| CN103288091A (en) | Method for preparing white carbon black by utilizing water glass with low modulus through carbonizing method of precipitation | |
| CN108238832A (en) | A kind of method that alkali activation potassium feldspar prepares soluble potassium and calcium silicates soil conditioner | |
| CN102976353A (en) | Method for preparing 4A molecular sieve from bauxite tailings | |
| CN105800643A (en) | Method for preparing 13X molecular sieve by cooperation of coal gangue and coal ash desilication liquid | |
| CN105255458B (en) | A kind of preparation method of high-efficient drilling fluid heat and salinity tolerance fluid loss additive | |
| CN107758715A (en) | A kind of method for preparing high-crystallinity high-purity boehmite | |
| CN104556073A (en) | Process for purifying inorganic nonmetallic minerals | |
| CN104386725A (en) | Method for preparing high-whiteness ultrafine aluminum hydroxide from aluminum hydroxide prepared by Bayer process | |
| CN101475328A (en) | Gypsum rotating crystal excitant and use for producing construction gypsum from marine gypsum | |
| CN107022681A (en) | A kind of comprehensive recovering process of aluminium scrap silicon middle rare earth, aluminium and silicon | |
| CN103332711B (en) | Deep desilicication method of high-alumina fly ash | |
| CN106629743B (en) | A method of ceramic glaze quartz sand is produced using quartz tail sand | |
| JP6080980B2 (en) | Preparation of silica-alumina composition | |
| CN107324352A (en) | A kind of method that blast furnace slag prepares ordered mesoporous silica dioxide | |
| CN105271332B (en) | A kind of method preparing sial composite oxides for raw material with discarded Si-Al molecular sieve | |
| CN105254273B (en) | The desulfurization dephosphorization method of chemical coating of welding electrode clay | |
| CN107311192A (en) | The method that the hot method processing Bayer process red mud of the step alkali of andradite one produces 4A zeolites | |
| CN107792870B (en) | Comprehensive utilization method of bauxite | |
| CN110482887A (en) | A kind of technique using chemical gypsum production α high strength gypsum powder |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170329 |
|
| RJ01 | Rejection of invention patent application after publication |