WO2009127104A1 - Procédé de production de zéolite 4a utilisé dans du détergent - Google Patents

Procédé de production de zéolite 4a utilisé dans du détergent Download PDF

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Publication number
WO2009127104A1
WO2009127104A1 PCT/CN2008/072109 CN2008072109W WO2009127104A1 WO 2009127104 A1 WO2009127104 A1 WO 2009127104A1 CN 2008072109 W CN2008072109 W CN 2008072109W WO 2009127104 A1 WO2009127104 A1 WO 2009127104A1
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WIPO (PCT)
Prior art keywords
zeolite
added
sodium aluminate
aluminate solution
solution
Prior art date
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Ceased
Application number
PCT/CN2008/072109
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English (en)
Chinese (zh)
Inventor
杜善国
赵善雷
张华�
成宝武
蔡转红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aluminum Corp of China Ltd
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Aluminum Corp of China Ltd
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Publication date
Application filed by Aluminum Corp of China Ltd filed Critical Aluminum Corp of China Ltd
Publication of WO2009127104A1 publication Critical patent/WO2009127104A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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

Definitions

  • the present invention relates to a method for synthesizing 4A zeolite, and more particularly to a method for synthesizing 4A zeolite for detergent. Background technique
  • 4A zeolite is widely used in non-phosphorus detergents because of its high ion exchange capacity, comprehensive cleaning performance, safety and economy, and various other excellent properties. It mainly uses the refined sodium aluminate solution in the alumina production process to synthesize 4A zeolite hydrothermally with industrial water glass. The high cost of the sodium aluminate solution after desiliconization filtration reduces the profitability of 4A zeolite, which is difficult to meet. Further production requirements for 4A zeolite.
  • the sodium aluminate solution without desiliconization contains a high content of organic complex iron. Due to the strong adsorption of 4A zeolite, the organic complex iron is tightly adsorbed during the crystallization of 4A zeolite. On its surface, it is difficult to remove. This directly leads to an increase in the b value of the zeolite product, which seriously affects the color of the 4A zeolite product, which affects the downstream users' use of the 4A zeolite product.
  • the amorphous guiding agent is generally added at one time before the crystallization of the gel. Due to the peculiar properties of the gel, the addition mode makes it difficult for the amorphous guiding agent to be uniformly dispersed in the coagulation. In the rubber, the consistency of the crystallization process of the 4A zeolite has a great influence, which causes fluctuations in the calcium exchange capacity index of the product. Moreover, due to the inconsistency in the crystallization process, the 4A zeolite product has defects such as uneven particle size distribution and easy sedimentation of the powder. Summary of the invention
  • An object of the present invention is to provide a method for synthesizing 4A zeolite for detergent which is simple, simple, low in cost and good in product quality.
  • the method for synthesizing 4A zeolite for detergent according to the present invention uses a source of aluminum and a source of silicon to react into a gel, and after crystallization, a 4A zeolite product is obtained, and the technical point is to adopt an alumina production process.
  • industrial raw water glass is used as the main silicon source for synthesizing 4A zeolite, and SiO 2 contained in the sodium aluminate solution not removed from silicon is used as a supplementary silicon source for synthesizing 4A zeolite, thereby effectively reducing the amount of industrial raw water glass and making synthetic raw materials. It is fully utilized, simplifies the process and greatly reduces production costs.
  • the undissolved sodium aluminate solution can be prepared by using the mother liquor produced in the production of zeolite, and the A1 2 0 3 content of the solution after formulation is 30-120 g /L, more preferably 50_80 g / L, 65_70 g / L the best.
  • the addition of an amorphous directing agent by continuous addition before gel crystallization can improve the consistency of the crystallization process of 4A zeolite, and reduce the agglomeration of 4A zeolite powder, which can make the crystal of 4A zeolite more perfect and can further Improve the microscopic quality of 4A zeolite products, significantly improve the particle size distribution of 4A zeolite, and improve the quality of finished products.
  • the company's amorphous director is added in an amount of 2-3% by weight of the theoretical dry zeolite. .
  • the singularity is 0. 10-2.
  • OOmVh more preferably 0. 40-0. 80m 3 /h, preferably 0. 50-0. 60m
  • the lime milk, the solid content is 200g / L, the decolorization of the sodium aluminate solution after the preparation, so that the b value of the solution is reduced from about 00 to less than 0.60, which solves the organic problem in the sodium aluminate solution which is not desiliconized.
  • the total amount of lime milk added was determined based on the solution b value.
  • the amount of lime milk added is too small to ensure the decolorization effect of the sodium aluminate solution without desiliconization.
  • the amount of lime milk added is too large, and the AL 2 0 3 content in the sodium aluminate solution after the blending is lost, resulting in waste of raw materials.
  • the amount of lime milk added is 1-10% of the volume of the sodium aluminate solution. , better for 1-5%. 00 ⁇ The best 1-2 liters of lime milk is added in two portions, the first time is to use the zeolite mother liquor to adjust the complex solution after adding 50% of the total volume of the milk, the filtered b value of the solution from 2. 00 The left and right are reduced to around 1.00. The remaining 50% lime milk was then added to the filtrate and filtered.
  • the filtrate b value is reduced to about 0.40. This can make full use of the adsorption and complexing ability of lime milk to iron, better utilize the lime milk to remove iron, further ensure the color of 4A zeolite product, and minimize the amount of lime milk to achieve the purpose of optimizing product indicators. .
  • the method for synthesizing the zeolite for detergent of the present invention is simple and convenient, has low cost, and has good quality of the obtained product, and can satisfy the operation of large-scale continuous production. It can be realized in the current 4A zeolite production line without adding any equipment.
  • the invention utilizes the crystallization mother liquid to reconfigure the water glass and the compounding liquid, thereby minimizing the waste liquid discharge, and the obtained product can meet the requirements of the detergent user. It can also meet the needs of high-grade molecular sieve users.
  • the product cost can be reduced by about 200 yuan/ton, and the economic and social benefits are significant, which is of great significance.
  • FIG. 1 is a block diagram of the process flow of the present invention.
  • Figure 2 is a SME picture of a 4A zeolite product. detailed description
  • the undesiliconized sodium aluminate solution in the alumina production process was prepared and formulated into a A1 2 0 3 content of 65 g/L using a 4A zeolite mother liquor. 0% ⁇ The total amount of 1. 0%. , 3. 0
  • %o the volume percentage of sodium aluminate solution which is not desiliconized after compounding, the same as below
  • the amount of lime milk added is 50% of the total volume, that is, after the sodium aluminate solution is qualified after the preparation 50% lime milk was added, filtered, and the remaining 50% lime milk was added to the filtrate and filtered.
  • the filtrate temperature was controlled at 65 ° C and was used.
  • the above two solutions were simultaneously fed into the synthesis reactor by means of two metering pumps, and 2% by weight of the dry-base zeolite was added at once after the synthesis.
  • the amorphous guiding agent is heated to 75 ⁇ 5 ° C after stirring for 15 minutes, and is discharged after two hours of crystallization. After conventional separation, washing and drying, the product is obtained.
  • the experimental results are listed in the table below.
  • Example 1 The remaining steps and experimental conditions were the same as in Example 1 except that the amorphous directing agent was added in a different manner from that in Example 1.
  • the amorphous director was added in an amount of 3% by weight based on the dry zeolite. And simultaneously with the synthetic gel at a flow rate of 0.56 m7h, it is driven into the crystallization reactor, and then subjected to temperature crystallization.
  • Example 3 The method for synthesizing 4A zeolite for detergent according to the present invention uses a sodium aluminate solution which is not desiliconized in the alumina production process and a 4A zeolite for industrial water glass synthetic detergent, wherein:
  • the sodium aluminate solution not desiliconized is prepared by using the mother liquor produced in the production of zeolite, and the content of A1 2 0 3 is 80 g /L after the preparation, and the volume of the sodium aluminate solution is added to the sodium aluminate solution after the preparation. 4%.
  • the lime milk has a solid content of 200g/L, and the lime milk is added twice. The first time is added in the solution after adjusting the lattice with the mother liquor of the zeolite, which is 50% of the total volume of the lime milk, and the second time is filtering. It was then added to the filtrate and filtered.
  • the amorphous director was added by continuous addition in an amount of 2.5% by weight based on the weight of the dry zeolite. After the gel is crystallized, the product is obtained by conventional separation, washing and drying.
  • the method for synthesizing 4A zeolite for detergent according to the present invention comprises a sodium aluminate solution which is not desiliconized in the alumina production process and a 4A zeolite for industrial water glass synthetic detergent, wherein:
  • the sodium aluminate solution not desiliconized is prepared by using the mother liquor produced in the zeolite production, and the A1 2 0 3 content is 100 g /L after the preparation, and the volume of the sodium aluminate solution is added to the sodium aluminate solution after the preparation. 2. 5%.
  • the lime milk has a solid content of 200g/L, and the lime milk is added twice. The first time is added in the solution after adjusting the lattice with the mother liquor of the zeolite, which is 50% of the total volume of the lime milk, and the second time is filtering. It was then added to the filtrate and filtered.
  • the amorphous director was added by continuous addition in an amount of 2.7% by weight of the dry zeolite. After the gel is crystallized, the product is obtained by conventional separation, washing and drying.
  • the method for synthesizing 4A zeolite for detergent according to the present invention comprises a sodium aluminate solution which is not desiliconized in the alumina production process and a 4A zeolite for industrial water glass synthetic detergent, wherein:
  • the sodium aluminate solution which was not desiliconized was formulated with the mother liquor produced in the zeolite production, and the A1A content after the preparation was 68 g / L, and 6% of the volume of the sodium aluminate solution was added to the sodium aluminate solution after the preparation.
  • the lime milk has a solid content of 200g/L, and the lime milk is added twice. The first time is added in the solution after adjusting the lattice with the mother liquor of the zeolite, which is 50% of the total volume of the lime milk, and the second time is filtering. It is then added to the filtrate and filtered.
  • the amorphous director was added by continuous addition in an amount of 3% by weight based on the dry zeolite. After the gel is crystallized, the product is obtained by conventional separation, washing, and drying.

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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)

Abstract

La présente invention concerne un procédé de production de zéolithe 4A utilisé dans du détergent, comprenant la réaction d’une source d’aluminium et d’une source de silicium pour obtenir un gel, suivie de la cristallisation du gel pour obtenir une zéolithe 4A, selon lequel une solution d’aluminate de sodium produite lors du procédé de production d’alumine non siliciée, et une solution de métasilicate de sodium sont utilisées pour produire de la zéolithe 4A dans du détergent. Le procédé est simple, économique, et la qualité du produit est élevée, et le procédé peut être utilisé pour une production en continu à grande échelle. Le procédé peut être effectué sur la ligne de production de zéolithe 4A de l’art antérieur, sans équipements additionnels. La liqueur mère après cristallisation est utilisée pour ajuster les concentrations de la solution de métasilicate de sodium et la solution d’ajustement, la quantité de liquide de décharge est réduite autant que possible, et le produit peut satisfaire à la fois la demande du consommateur de détergent et la demande du consommateur de tamis moléculaire de première qualité. Le coût de production est inférieur par environ 200¥/t que celui du procédé de l’art antérieur. Par conséquent, les avantages économique et social du procédé sont importants.
PCT/CN2008/072109 2008-04-18 2008-08-22 Procédé de production de zéolite 4a utilisé dans du détergent Ceased WO2009127104A1 (fr)

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CN200810015565.1 2008-04-18
CN2008100155651A CN101264899B (zh) 2008-04-18 2008-04-18 利用经济性铝源合成洗涤剂用4a沸石工艺

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111170331A (zh) * 2020-02-27 2020-05-19 中国日用化学研究院有限公司 一种连续化制备超细4a沸石的工艺及装置
CN117263202A (zh) * 2023-10-07 2023-12-22 中铝山东新材料有限公司 一种沸石分子筛的制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103787362B (zh) * 2014-01-20 2016-10-12 石家庄健达高科化工有限公司 一种利用进口三水型铝土矿制备4a分子筛的工艺

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86106033A (zh) * 1986-09-11 1988-03-23 山东铝厂 用工业铝酸钠溶液生产洗涤剂用分子筛—4a沸石的方法
US5474753A (en) * 1990-11-09 1995-12-12 Laviosa Rhone-Poulenc Preparation of crystalline 4A zeolites
CN1613766A (zh) * 2004-11-12 2005-05-11 山东铝业股份有限公司 生产洗涤用4a沸石的方法
CN1623899A (zh) * 2004-11-12 2005-06-08 山东铝业股份有限公司 制备4a沸石用导向剂
CN1632095A (zh) * 2004-11-24 2005-06-29 山东铝业股份有限公司 洗涤助剂用改性4a沸石的生产方法
CN101125661A (zh) * 2007-08-03 2008-02-20 中国铝业股份有限公司 一种生产4a沸石的方法
CN101139098A (zh) * 2007-08-10 2008-03-12 林成基 4a沸石的生产工艺

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN86106033A (zh) * 1986-09-11 1988-03-23 山东铝厂 用工业铝酸钠溶液生产洗涤剂用分子筛—4a沸石的方法
US5474753A (en) * 1990-11-09 1995-12-12 Laviosa Rhone-Poulenc Preparation of crystalline 4A zeolites
CN1613766A (zh) * 2004-11-12 2005-05-11 山东铝业股份有限公司 生产洗涤用4a沸石的方法
CN1623899A (zh) * 2004-11-12 2005-06-08 山东铝业股份有限公司 制备4a沸石用导向剂
CN1632095A (zh) * 2004-11-24 2005-06-29 山东铝业股份有限公司 洗涤助剂用改性4a沸石的生产方法
CN101125661A (zh) * 2007-08-03 2008-02-20 中国铝业股份有限公司 一种生产4a沸石的方法
CN101139098A (zh) * 2007-08-10 2008-03-12 林成基 4a沸石的生产工艺

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111170331A (zh) * 2020-02-27 2020-05-19 中国日用化学研究院有限公司 一种连续化制备超细4a沸石的工艺及装置
CN117263202A (zh) * 2023-10-07 2023-12-22 中铝山东新材料有限公司 一种沸石分子筛的制备方法

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CN101264899A (zh) 2008-09-17

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