CN111847461A - Novel process for preparing silicon dioxide by precipitation method - Google Patents
Novel process for preparing silicon dioxide by precipitation method Download PDFInfo
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- CN111847461A CN111847461A CN202010747426.9A CN202010747426A CN111847461A CN 111847461 A CN111847461 A CN 111847461A CN 202010747426 A CN202010747426 A CN 202010747426A CN 111847461 A CN111847461 A CN 111847461A
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 58
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 238000001556 precipitation Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000047 product Substances 0.000 claims abstract description 35
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 34
- 239000007921 spray Substances 0.000 claims abstract description 33
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 28
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 28
- 239000000839 emulsion Substances 0.000 claims abstract description 23
- 239000002738 chelating agent Substances 0.000 claims abstract description 13
- 230000009920 chelation Effects 0.000 claims abstract description 11
- 230000020477 pH reduction Effects 0.000 claims description 75
- 238000003756 stirring Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 14
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000003825 pressing Methods 0.000 claims description 13
- 239000013522 chelant Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 6
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 2
- 235000013539 calcium stearate Nutrition 0.000 claims description 2
- 239000008116 calcium stearate Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims 1
- 229910021645 metal ion Inorganic materials 0.000 abstract description 14
- 238000002156 mixing Methods 0.000 abstract description 6
- 230000006872 improvement Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000015271 coagulation Effects 0.000 abstract description 2
- 238000005345 coagulation Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 11
- 229960001484 edetic acid Drugs 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 239000004576 sand Substances 0.000 description 8
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 6
- 238000000889 atomisation Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004697 chelate complex Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005008 domestic process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- -1 papermaking Substances 0.000 description 1
- 229940093429 polyethylene glycol 6000 Drugs 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
Images
Classifications
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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
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention relates to a new process for preparing silicon dioxide by a precipitation method, which reduces the coagulation effect of metal ions on generated silicon dioxide emulsion by adding a metal ion chelating agent to be chelated with a plurality of metal ions in a sodium silicate dilute solution, and simultaneously, the reduction of the metal ions brings about the improvement of the operation flexibility and the expansion of the temperature range, so that a high-quality silicon dioxide product can be obtained within the temperature variation range of +/-5 ℃; the method for mixing and reacting the chelation reaction product and the dilute sulfuric acid in a spray form is favorable for quickly dissipating the stagnation of reaction heat, the production temperature rises very slowly, workers are favorable for cooling in time, the quality of the obtained product is greatly improved, and the yield of the product is improved.
Description
Technical Field
The invention relates to the technical field of silicon dioxide preparation, in particular to a novel process for preparing silicon dioxide by a precipitation method.
Background
The silica has wide application, has important application in national life, particularly has irreplaceable effect in the fields of coating, papermaking, rubber, tires and the like, the high-quality silica is mainly applied to the fields of feed, optical glass, quartz crucibles, military copper clad plates, packaging materials and the like, and the productivity of the high-quality silica in China at present can not meet the requirements of the fields. The prior preparation method of the silicon dioxide mainly comprises a gas phase method and a precipitation method, although the gas phase method for preparing the silicon dioxide can produce high-quality products, the gas phase method for preparing the silicon dioxide is complicated in production process, high in cost and harsh in conditions, so that the gas phase method is subject to various technical requirements and cost problems, and the domestic method cannot be adopted for mass production, so that the precipitation method is mainly used for preparing the silicon dioxide in China.
The raw materials used for preparing the silicon dioxide by the precipitation method are mainly red sand or high-quality white sand, and the raw materials contain various metal ions, particularly the red sand has high impurity content and various types. The impurities exist mainly in two modes, one mode is physical existence, the other mode is chemical bond combination, wherein the physical adsorption metal impurities mainly comprise elements such as copper, lead, manganese, iron, chromium and the like, and the chemical combination impurities mainly comprise elements such as aluminum, titanium, germanium, boron, arsenic and the like. The existence of the impurities causes the defects of strict control of process parameters, small operation flexibility of workers, low yield and the like in the preparation process of the silicon dioxide by the precipitation method. Although the content of metal ions in the white sand is lower than that of red sand, the three highest-quality white sand production areas in the world are not in China, so that the transportation cost is high and the influence of international environment is great. Therefore, if the field of silicon dioxide with high added value demand is not provided, the red sand is still used in most industries.
In order to achieve the purpose of producing high-performance products from low-quality red sand, domestic enterprises mostly concentrate on the research on the modification aspect of silicon dioxide products, such as a silicon dioxide surface carbon-coated modification patent introduced in a patent CN105836749 and a silicon dioxide surface hydroxyl modification patent reported in a patent CN110746794, wherein the two improvements are both carried out on the basis of the silicon dioxide products and do not relate to the innovation and the improvement of the production process; a few scientific research units are involved in the improvement of the production mode, such as adding sodium dodecyl benzene sulfonate, polyethylene glycol 6000 and the like in the production process mentioned in the Beijing university Master graduate thesis "controllable preparation and application of nanometer white carbon black", but the method of adding the surfactant cannot fundamentally reduce the existence of metal ions, and the introduction of the surfactant is easy to cause secondary pollution in the production process.
In the preparation process of the silicon dioxide by the precipitation method, due to the existence of metal ions, the defects of massive agglomeration, difficult dispersion of silicon dioxide colloid, strict control of operation temperature in a temperature range of +/-0.5 ℃, high requirement on quality of workers, low yield and the like appear in the synthesis stage.
Disclosure of Invention
In order to solve the technical problems, one or more special chelates are added into the diluted sodium silicate solution, and then the diluted sodium silicate solution is stirred and reacted for a period of time at a certain temperature, and then the acidification reaction is carried out. And after the reaction is finished, performing filter pressing concentration, washing with water to remove salt, and finally obtaining a silicon dioxide product with low impurity content. The invention discloses a new process for precipitating silicon dioxide, which comprises the following steps,
s1, adding a sodium silicate solution and deionized water into a preparation reaction kettle, stirring to prepare a sodium silicate dilute solution with a specific concentration, adding a chelating agent into the sodium silicate dilute solution while stirring to perform a chelating reaction, wherein the addition amount of the chelating agent is 200-500 ppm of the total mass of the sodium silicate dilute solution;
s2, transferring the chelating reaction product into an acidification kettle in a spray form, adding 30-45% by mass of dilute sulfuric acid into the acidification kettle in a spray form, and carrying out an acidification reaction under a stirring condition, wherein the temperature of the acidification reaction is 70-80 ℃, the time of the acidification reaction is 1.5-3 h, and after the acidification reaction is finished, continuously adding the dilute sulfuric acid into the acidification reaction product in a spray form until the pH value of the acidification reaction product is 2.5-3.5, so as to generate an acidified silicon dioxide emulsion;
s3, keeping the acidified silicon dioxide emulsion obtained in the step S2 in the acidified kettle under the original stirring condition, and carrying out heat preservation and aging at the temperature of 70-80 ℃ for 4.5-6 h;
s4, transferring the aged emulsion obtained in the step S3 into a filter press for filter pressing after passing through a vibrating screen, and washing and filter pressing by using deionized water until a product with the conductivity of 0.6-0.8 mu S/cm is obtained;
and S5, carrying out high-speed centrifugal spray drying on the qualified product with the conductivity meeting the requirement to obtain the final silicon dioxide finished product.
Preferably, the concentration of the sodium silicate dilute solution in the step S1 is 13 wt% to 18 wt%.
Preferably, in step S1, the chelate is one or a mixture of at least two of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, phenanthroline, polyethylene glycol 200, sodium dodecyl sulfate, sodium hexametaphosphate, calcium stearate, and hexamethylphosphoramide.
Preferably, in the step S1, the chelate compound is prepared by mixing ethylene diamine tetraacetic acid 1: 1-1.5 of disodium ethylene diamine tetraacetate.
Preferably, the reaction time of the chelation reaction in step S1 is 30 to 50 min.
Preferably, the stirring speed in the acidification kettle in the step S2 is 40-50 r/min.
Preferably, the temperature of the acidification reaction in the step S2 is 72-78 ℃.
Preferably, in step S2, the mass flow ratio of the chelating reaction product to the spray of dilute sulfuric acid is 1 (1.2-1.5).
Because no report that the content of metal impurities is reduced fundamentally by adding the chelate in the production process exists at present, in order to save cost, weaken severe parameter control in the production process and improve the yield and quality of products, a special chelate is adopted to be complexed with the metal impurities in the reaction process, so that the adverse effect of the metal impurities on the quality of the products is reduced.
The invention has the beneficial effects that:
according to the invention, the chelating agent is added into the prepared sodium silicate dilute solution for reaction to reduce the content of metal ions, the chelating agent and the generated chelate are both easily soluble in water, and can be washed clean by using conventional deionized water without residue and influencing the product quality, and meanwhile, one chelating agent of ethylenediamine tetraacetic acid can react with various metal ions, so that the cost is reduced, and the pollution is reduced. For the silica colloid formed in the reaction process, the colloid coagulation phenomenon is easily influenced by positive charges, so the conventional reaction temperature control must be accurate, but the addition of the chelating agent greatly reduces the content of metal ions, the operation temperature range is greatly expanded, the operation flexibility of workers is increased, and the high-quality white carbon black product is very easy to produce. Considering that the reaction heat generated by the acid-base reaction is accumulated in the whole reaction system, the production is not easy to be accurately regulated and controlled, and the phenomenon of overhigh local temperature is easy to occur, so that unqualified products are formed, therefore, the stagnation of the reaction heat is accelerated by the chelating reaction product and the dilute sulfuric acid by a spray acidification method, and the temperature rise is very slow. The simultaneous use of the two methods reduces the strict requirement on the reaction temperature in production (plus or minus 0.5 ℃), and greatly ensures the production efficiency and the product quality.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without inventive labor.
FIG. 1 is a schematic diagram of a process for preparing silica by the novel process for preparing silica by precipitation according to the present invention.
Detailed Description
The following provides preferred embodiments of the present invention in order to facilitate the understanding of the concept of the present invention by the skilled person.
Example 1:
the process for the preparation of the silica in this example is as follows,
(1) performing chelation reaction, namely adding a sodium silicate solution and deionized water into a preparation reaction kettle for stirring to prepare a sodium silicate dilute solution with the mass fraction of 13%, adding ethylene diamine tetraacetic acid into the sodium silicate dilute solution while stirring, and stirring for carrying out chelation reaction, wherein the reaction time is 35min, and the addition amount of the ethylene diamine tetraacetic acid is 200ppm of the total mass of the sodium silicate dilute solution;
(2) carrying out acidification reaction, namely transferring a chelating reaction product into an acidification kettle in a spray form, adding 30% dilute sulfuric acid in a spray form into the acidification kettle, carrying out acidification reaction under the condition that the stirring speed is 40r/min, wherein the temperature in the acidification kettle is 72 ℃, the mass flow ratio of the chelating reaction product to the dilute sulfuric acid spray is 1:1.5, the chelating reaction product and the dilute sulfuric acid spray are both added into the acidification kettle in an atomization form, so that the mixing acidification between the chelating reaction product and the dilute sulfuric acid spray is more sufficient and the heat can be rapidly dissipated, excessive temperature rise is accumulated in the acidification process to generate a byproduct, the acidification reaction is completed after 3 hours, and then the dilute sulfuric acid is continuously added into the acidification reaction product in a spray form until the pH value of the acidification reaction product is 2.7, so as to generate acidified silica emulsion;
(3) aging, namely performing heat preservation and aging on the acidified silicon dioxide emulsion obtained in the acidification reaction in the acidification kettle under the original stirring condition, wherein the temperature is 72 ℃, and the aging treatment time is 5 hours;
(4) preparing a crude product, namely passing the aged emulsion through a vibrating screen, transferring the aged emulsion into a filter press for filter pressing, and washing and filter pressing by using deionized water until a product with the conductivity of 0.6-0.8 mu S/cm is obtained;
(5) and (4) preparing a final product, and performing high-speed centrifugal spray drying on the qualified product with the conductivity meeting the requirement to obtain the final silicon dioxide finished product.
Example 2:
the process for the preparation of the silica in this example is as follows,
(1) carrying out chelation reaction, namely adding a sodium silicate solution and deionized water into a preparation reaction kettle to stir to prepare a sodium silicate dilute solution with the mass fraction of 18%, adding a mixture of ethylene diamine tetraacetic acid and disodium ethylene diamine tetraacetic acid in a mass ratio of 1:1 into the sodium silicate dilute solution while stirring, stirring to carry out chelation reaction, wherein the reaction time is 45min, and the addition amount of the mixture of the ethylene diamine tetraacetic acid and the disodium ethylene diamine tetraacetic acid is 250ppm of the total mass of the sodium silicate dilute solution;
(2) carrying out acidification reaction, namely transferring a chelating reaction product into an acidification kettle in a spray form, adding 35% dilute sulfuric acid in a spray form into the acidification kettle, carrying out acidification reaction under the condition that the stirring speed is 45r/min, wherein the temperature in the acidification kettle is 78 ℃, the mass flow ratio of the chelating reaction product to the dilute sulfuric acid spray is 1:1.4, the chelating reaction product and the dilute sulfuric acid spray are both added into the acidification kettle in an atomization form, so that the mixing acidification between the chelating reaction product and the dilute sulfuric acid spray is more sufficient and the heat can be rapidly dissipated, the excessive temperature rise is accumulated in the acidification process to cause the generation of byproducts, the acidification reaction is completed after 2.5 hours, and then continuously adding the dilute sulfuric acid into the acidification reaction product in a spray form until the pH value of the acidification reaction product is 3.0, so as to generate acidified silica emulsion;
(3) aging, namely performing heat preservation and aging on the acidified silicon dioxide emulsion obtained in the acidification reaction in the acidification kettle under the original stirring condition, wherein the temperature is 78 ℃, and the aging treatment time is 4.5 hours;
(4) preparing a crude product, namely passing the aged emulsion through a vibrating screen, transferring the aged emulsion into a filter press for filter pressing, and washing and filter pressing by using deionized water until a product with the conductivity of 0.6-0.8 mu S/cm is obtained;
(5) and (4) preparing a final product, and performing high-speed centrifugal spray drying on the qualified product with the conductivity meeting the requirement to obtain the final silicon dioxide finished product.
Example 3:
the process for the preparation of the silica in this example is as follows,
(1) performing chelation reaction, namely adding a sodium silicate solution and deionized water into a preparation reaction kettle for stirring to prepare a sodium silicate dilute solution with the mass fraction of 16%, and adding ethylene diamine tetraacetic acid 1:1.2 parts of disodium ethylene diamine tetraacetate: sodium dodecyl sulfate 0.6: stirring a mixed chelating agent of 0.8 sodium hexametaphosphate to carry out chelation reaction, wherein the reaction time is 50min, and the addition amount of the mixed chelating agent is 300ppm of the total mass of the sodium silicate dilute solution;
(2) carrying out acidification reaction, namely transferring a chelating reaction product into an acidification kettle in a spray form, adding 50% dilute sulfuric acid into the acidification kettle in a spray form, carrying out acidification reaction under the condition that the stirring speed is 50r/min, wherein the temperature in the acidification kettle is 75 ℃, the mass flow ratio of the chelating reaction product to the dilute sulfuric acid spray is 1:1.3, the chelating reaction product and the dilute sulfuric acid spray are both added into the acidification kettle in an atomization form, so that the mixing acidification between the chelating reaction product and the dilute sulfuric acid spray is more sufficient and the heat can be rapidly dissipated, the excessive temperature rise is accumulated in the acidification process to cause the generation of byproducts, the acidification reaction is completed after 1.8h, and then continuously adding the dilute sulfuric acid into the acidification reaction product in a spray form until the pH value of the acidification reaction product is 3.0, so as to generate acidified silica emulsion;
(3) aging, namely performing heat preservation aging on the acidified silicon dioxide emulsion obtained in the acidification reaction in the acidification kettle under the original stirring condition, wherein the temperature is 75 ℃, and the aging treatment time is 5 hours;
(4) preparing a crude product, namely passing the aged emulsion through a vibrating screen, transferring the aged emulsion into a filter press for filter pressing, and washing and filter pressing by using deionized water until a product with the conductivity of 0.6-0.8 mu S/cm is obtained;
(5) and (4) preparing a final product, and performing high-speed centrifugal spray drying on the qualified product with the conductivity meeting the requirement to obtain the final silicon dioxide finished product.
Example 4:
the process for the preparation of the silica in this example is as follows,
(1) performing chelation reaction, namely adding a sodium silicate solution and deionized water into a preparation reaction kettle for stirring to prepare a sodium silicate dilute solution with the mass fraction of 16%, and adding ethylene diamine tetraacetic acid 1: stirring a chelating agent mixed with disodium ethylene diamine tetraacetate 1.2 for carrying out a chelation reaction, wherein the reaction time is 50min, and the adding amount of the mixed chelating agent is 300ppm of the total mass of the sodium silicate dilute solution;
(2) carrying out acidification reaction, namely transferring a chelating reaction product into an acidification kettle in a spray form, adding 45 mass percent of dilute sulfuric acid into the acidification kettle in a spray form, carrying out acidification reaction under the condition that the stirring speed is 50r/min, wherein the temperature in the acidification kettle is 78 ℃, the mass flow ratio of the chelating reaction product to the spray of the dilute sulfuric acid is 1:1.2, the chelating reaction product and the spray of the dilute sulfuric acid are both added into the acidification kettle in an atomization form, so that the mixing acidification between the chelating reaction product and the dilute sulfuric acid is more sufficient and the heat can be rapidly dissipated, the excessive temperature rise is accumulated in the acidification process to cause the generation of byproducts, the acidification reaction is completed after 1.5h, and then continuously adding the dilute sulfuric acid into the acidification reaction product in a spray form until the pH value of the acidification reaction product is 3.5, so as to generate acidified silica emulsion;
(3) aging, namely performing heat preservation and aging on the acidified silicon dioxide emulsion obtained in the acidification reaction in the acidification kettle under the original stirring condition, wherein the temperature is 78 ℃, and the aging treatment time is 6 hours;
(4) preparing a crude product, namely passing the aged emulsion through a vibrating screen, transferring the aged emulsion into a filter press for filter pressing, and washing and filter pressing by using deionized water until a product with the conductivity of 0.6-0.8 mu S/cm is obtained;
(5) and (4) preparing a final product, and performing high-speed centrifugal spray drying on the qualified product with the conductivity meeting the requirement to obtain the final silicon dioxide finished product.
The innovation of the invention focuses on the following aspects:
(1) the chelate complex with metal ions is cheap and easy to obtain, can react with various metal ions, is easy to dissolve in water, and can be washed away by water even if the rest of the reaction is generated.
(2) Meanwhile, the requirement of the product quality on temperature control is not strict under the action of the chelate, and the product quality is not influenced when the temperature fluctuation is within the range of +/-5 ℃ proved by experiments, the reaction temperature range is greatly expanded, the operation flexibility is wider, and the production and the preparation are easier.
(3) The atomization mode enables the heat generated by the reaction in the acidification process to be quickly dissipated, so that the heat accumulation is reduced, the reaction temperature controllability is greatly increased, and the occurrence of byproducts is reduced.
(4) After the reaction is finished, basically no condensed colloid component appears, the requirement on the rotating speed of the stirrer is low, and the service life of equipment is prolonged.
(5) The metal ion content of the whole reaction system is greatly reduced, and the product quality and the yield are greatly improved.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein. In addition, the technical solutions between the various embodiments can be combined with each other, but must be based on the realization of those skilled in the art; where combinations of features are mutually inconsistent or impractical, such combinations should not be considered as being absent and not within the scope of the claimed invention.
Claims (8)
1. A new process for preparing silicon dioxide by a precipitation method is characterized by comprising the following steps,
s1, adding a sodium silicate solution and deionized water into a preparation reaction kettle, stirring to prepare a sodium silicate dilute solution with a specific concentration, adding a chelating agent into the sodium silicate dilute solution while stirring to perform a chelating reaction, wherein the addition amount of the chelating agent is 200-500 ppm of the total mass of the sodium silicate dilute solution;
s2, transferring the chelating reaction product into an acidification kettle in a spray form, adding 30-45% by mass of dilute sulfuric acid into the acidification kettle in a spray form, and carrying out an acidification reaction under a stirring condition, wherein the temperature of the acidification reaction is 70-80 ℃, the time of the acidification reaction is 1.5-3 h, and after the acidification reaction is finished, continuously adding the dilute sulfuric acid into the acidification reaction product in a spray form until the pH value of the acidification reaction product is 2.5-3.5, so as to generate an acidified silicon dioxide emulsion;
s3, keeping the acidified silicon dioxide emulsion obtained in the step S2 in the acidified kettle under the original stirring condition, and carrying out heat preservation and aging at the temperature of 70-80 ℃ for 4.5-6 h;
s4, transferring the aged emulsion obtained in the step S3 into a filter press for filter pressing after passing through a vibrating screen, and washing and filter pressing by using deionized water until a product with the conductivity of 0.6-0.8 mu S/cm is obtained;
and S5, carrying out high-speed centrifugal spray drying on the qualified product with the conductivity meeting the requirement to obtain the final silicon dioxide finished product.
2. The novel process for preparing precipitated silica as claimed in claim 1, wherein the concentration of the diluted sodium silicate solution in step S1 is 13 wt% to 18 wt%.
3. The novel process for preparing silicon dioxide by a precipitation method according to claim 1, wherein the chelate in step S1 is one or a mixture of at least two of ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, phenanthroline, polyethylene glycol 200, sodium dodecylsulfate, sodium hexametaphosphate, calcium stearate, and hexamethylphosphoramide.
4. The novel process for preparing silicon dioxide by a precipitation method according to claim 1, wherein the chelate compound in the step S1 is an ethylenediamine tetraacetic acid 1: 1-1.5 of disodium ethylene diamine tetraacetate.
5. The novel process for preparing precipitated silica according to claim 1, wherein the reaction time of the chelation reaction in step S1 is 30-50 min.
6. The novel process for preparing precipitated silica according to claim 1, wherein the stirring speed in the acidification kettle in step S2 is 40-50 r/min.
7. The novel process for preparing precipitated silica according to claim 1, wherein the temperature of the acidification reaction in step S2 is 72-78 ℃.
8. The novel process for preparing precipitated silica according to claim 1, wherein in step S2, the mass flow ratio of the chelated reaction product to the spray of diluted sulfuric acid is 1 (1.2-1.5).
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