CN112250074B - Preparation method and application of silicon dioxide with high oil absorption and high specific surface area - Google Patents
Preparation method and application of silicon dioxide with high oil absorption and high specific surface area Download PDFInfo
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- CN112250074B CN112250074B CN202011158397.9A CN202011158397A CN112250074B CN 112250074 B CN112250074 B CN 112250074B CN 202011158397 A CN202011158397 A CN 202011158397A CN 112250074 B CN112250074 B CN 112250074B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 208
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 104
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 63
- 239000003921 oil Substances 0.000 title claims abstract description 62
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 47
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 47
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 47
- 238000005406 washing Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 23
- 230000032683 aging Effects 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 19
- 239000008236 heating water Substances 0.000 claims description 7
- 230000020477 pH reduction Effects 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 6
- 230000000694 effects Effects 0.000 abstract description 10
- 238000005202 decontamination Methods 0.000 abstract description 6
- 230000003588 decontaminative effect Effects 0.000 abstract description 6
- 235000020610 powder formula Nutrition 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 239000012752 auxiliary agent Substances 0.000 description 5
- 235000013350 formula milk Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000002431 foraging effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/126—Preparation of silica of undetermined type
- C01B33/128—Preparation of silica of undetermined type by acidic treatment of aqueous silicate solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/19—Oil-absorption capacity, e.g. DBP values
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The invention belongs to the technical field of silicon dioxide preparation, and particularly relates to a preparation method and application of silicon dioxide with high oil absorption and high specific surface area. In the preparation process, a two-stage product aging method is creatively adopted, sodium silicate with the modulus of 2-4 and sulfuric acid are used as reaction raw materials, and the sodium silicate and the sulfuric acid are prepared through acid-base simultaneous drip theory. According to the preparation method of the silicon dioxide with high oil absorption and high specific surface area, provided by the invention, the prepared silicon dioxide is uniform in particle size, has higher oil absorption value and specific surface area, has the pH value of 5.0-7.0, can effectively improve the stability of a washing powder formula, can be used as a washing assistant to be added into washing powder, obviously improves the decontamination capability and anti-caking and flow aiding effects of the washing powder, meets the living demands of people, and has good market prospect.
Description
Technical Field
The invention belongs to the technical field of silicon dioxide preparation, and particularly relates to a preparation method of silicon dioxide with high oil absorption and high specific surface area.
Background
With the national attention on the environmental protection problem, the washing powder taking sodium tripolyphosphate as an auxiliary agent gradually exits the market due to the fact that water eutrophication is easily caused and the environment is polluted in the morning, and the 4A zeolite is used as a flow-aiding and anti-caking auxiliary agent in the washing powder and is gradually widely used in common washing powder. However, in the formula of the concentrated washing powder with high efficiency, energy conservation, concentration and environmental protection, the 4A zeolite has weak dispersing ability, poor water solubility and poor effect of being used as an auxiliary agent. Therefore, the development of a better formula of the auxiliary agent matched with the concentrated washing powder is urgently needed.
The precipitated silica is used as an amorphous porous substance, has a high oil absorption value and a large specific surface area, and is a good adsorbent. The silicon dioxide used as the synergistic auxiliary agent has strong decontamination capability and can also be used for synergistic action with other surfactants, and the washing effect is ideal, but the silicon dioxide used for the existing precipitation method washing powder has the following problems:
(1) the preparation process is complex and the cost is high;
(2) silica having good adsorbability is poor in flowability.
In the prior art, a gel precipitation method is mostly adopted to prepare silicon dioxide with a high oil absorption value, but the silicon dioxide prepared by the method has a low specific surface area when the oil absorption value is high, and has a low oil absorption value when the specific surface area is high, so that products with high oil absorption values and high specific surface areas cannot be prepared. For example, Chinese patent CN110395740B discloses a silica for high-fluidity high-oil-absorption-value washing powder and a preparation method thereof, which comprises the following steps: s1, adding water into the reaction kettle, adding a sulfuric acid solution while stirring, heating, dropwise adding a sodium silicate solution until the pH value is 3.5-4.5, then dropwise adding the sodium silicate solution and the sulfuric acid solution simultaneously for a parallel-flow neutralization reaction, controlling the pH value to be 3.0-5.0, stopping adding the sulfuric acid solution when the dropwise adding of the sodium silicate solution is finished, and stirring again; s2, continuously adding the sodium silicate solution, stopping adding the sodium silicate solution when the pH value is 7.0-8.0, and curing; and S3, performing filter pressing and washing on the formed silicon dioxide, and performing spray drying treatment to obtain the silicon dioxide. The invention adopts a gel method to prepare the silicon dioxide for the washing powder by the precipitation method, the oil absorption value of the prepared silicon dioxide is less than 300mL/100g, and the specific surface area is less than 400m2The problems of low specific surface area, low oil absorption value and the like still exist, and the pH value of the product is high, so that the stability of the washing powder formula is greatly influenced. In addition, the pH value of the finished product after washing and drying is too high due to the pH value of 7.0-8.0 at the end point of the product preparation, which can affect the stability of the washing powder formula.
Therefore, it is necessary to provide silica with high specific surface area and high oil absorption value and a preparation method thereof so as to meet the requirement of good application in washing powder.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a preparation method of silica with high oil absorption and high specific surface area. According to the preparation method of the silicon dioxide with high oil absorption and high specific surface area, provided by the invention, the prepared silicon dioxide is uniform in particle size, has higher oil absorption value and specific surface area, has the pH value of 5.0-7.0, can effectively improve the stability of a washing powder formula, can be used as a washing assistant to be added into washing powder, obviously improves the decontamination capability and anti-caking and flow aiding effects of the washing powder, meets the living demands of people, and has good market prospect.
The silica with the specific surface area and the high oil absorption value is prepared by taking sodium silicate with the modulus of 2-4 and sulfuric acid as reaction raw materials and performing acid-base co-drip reaction. The specific process flow is as follows:
a preparation method of silica with high oil absorption and high specific surface area comprises the following steps:
s1, adding water to dilute, dissolve and age sodium silicate with the modulus of 2-4 for 5-8 h, and then adding water to dilute to prepare a sodium silicate solution with the concentration of 0.3-0.8 mol/L;
s2, adding 8m into the reaction tank3Heating water to 80-90 ℃, keeping the temperature of the whole reaction process at 80-90 ℃, then dropwise adding a sulfuric acid solution while stirring until the pH value is 3.0-4.5, and dropwise adding the sodium silicate solution and the sulfuric acid solution obtained in the step S1 at the same time, wherein the pH value in the reaction process is controlled to be 3.0-4.5;
s3, continuously dripping triethanolamine for alkalization, and controlling the dripping speed of the triethanolamine to be 5-10 m3Stopping dripping when the reaction pH value reaches 5.0-6.0, stirring and aging for 40 min;
s4, continuously dripping sulfuric acid solution for acidification, wherein the dripping speed of the sulfuric acid solution is 1.0-3.0 m3Stopping dripping when the reaction pH value reaches 3.0-3.5, stirring and aging for 5 min;
s5, performing filter pressing and washing treatment on the formed silicon dioxide, wherein the conductivity of washing water is less than or equal to 5000 mu S/cm, and performing spray drying treatment on the silicon dioxide slurry to obtain the silicon dioxide.
Further, the modulus of the sodium silicate in the step S1 is 3.3.
Further, the concentration of the sodium silicate solution in the step S1 is 0.6 mol/L.
Further, the dropping speed of the sodium silicate solution in the step S2 is 10-15 m3The total amount of the sodium silicate solution is 4.0-7.0 m3。
Further, the dropping speed of the sodium silicate solution in the step S2 is 12m3H, total amount of sodium silicate solution is 5.5m3。
Further, the concentration of the sulfuric acid solution in the step S2 and the step S4 is 4.0 mol/L.
Further, the dropping speed of the triethanolamine in the step S3 is 7m3/h。
Further, the dropping speed of the sulfuric acid solution in the step S4 is 1.8m3/h。
Further, the particle size of the silica obtained in the step S5 is 40-50 μm.
The invention also provides application of the silica with high oil absorption and high specific surface area in preparation of washing powder.
The invention provides a preparation method of silica with high oil absorption and high specific surface area, which creatively adopts a two-stage aging method in the preparation steps, triethanolamine is used for adjusting the pH value of the reaction end point to be 5.0-6.0 for aging for 40min, then sulfuric acid is used for adjusting the pH value of the reaction end point to be 3.0-3.5 for aging for 5min, the prepared silica has uniform particle size which is distributed in 40-50 mu m, the oil absorption value is more than or equal to 280ml/100g, and the specific surface area is 550-600 m2The angle of repose is less than or equal to 30 degrees, and the reaction principle is as follows:
precipitated hydrated silicas resemble amorphous spherical particles of carbon black, with the individual particles in surface contact to form branched linkages. It is known from the prior art that the specific surface area of silica depends on the particle size and the way of packing. In the preparation process of the invention, 8m of the catalyst is firstly added into a reaction tank3Heating water to 80-90 ℃, dropwise adding a sulfuric acid solution while stirring until the pH value is 3.0-4.5, and neutralizing the acid at a pH value of 3.0-4.5And (2) a large number of particles with small particle size can be rapidly generated, then the sodium silicate solution and the sulfuric acid solution obtained in the step S1 are simultaneously dripped, the pH value in the reaction process is controlled to be 3.0-4.5, and under the condition of pH value of 3.0-4.5, hydrogen ions with high concentration effectively inhibit hydrogen bond formation among silicon dioxide molecules, reduce hydrogen bond force among silicon dioxide molecules, reduce chain branch structures, increase specific surface area, but also reduce oil absorption value. However, in the growth stage of the particles, the high temperature can make the activity of the large clusters large, the movement is violent, and the oil absorption value can be increased.
In order to further effectively improve the oil absorption value and the specific surface area, the inventor of the application finds that in the aging stage after the reaction is finished, triethanolamine is used for improving the pH value of the reaction, the reaction is aged for 40min, sulfuric acid is used for neutralizing redundant triethanolamine after the aging is finished, the pH value is adjusted to be 3.0-3.5, and the pH value of a finished product is reduced. The step can effectively promote the increase of the chain-branch structure among the silicon dioxide molecules, so that the oil absorption value and the specific surface area of the prepared silicon dioxide are improved, and the final pH value of the prepared silicon dioxide is between 5.0 and 7.0, which is beneficial to the stability of the formula of the washing powder.
Compared with the prior art, the preparation method of the silicon dioxide with high oil absorption and high specific surface area provided by the invention has the following advantages:
(1) the preparation method of the silicon dioxide with high oil absorption and high specific surface area provided by the invention creatively adopts a two-stage aging method, and simultaneously controls the temperature, pH value, time, substance concentration and the like in the reaction process, so that the specific surface area and the oil absorption value of the silicon dioxide are obviously improved.
(2) The preparation method of the silicon dioxide with high oil absorption and high specific surface area provided by the invention has the advantages that the prepared silicon dioxide has uniform particle size which is distributed in the range of 40-50 mu m, the oil absorption value is more than or equal to 280ml/100g,the specific surface area is 550-600 m2The angle of repose is less than or equal to 30 degrees, can be used as a washing assistant to be added into washing powder, remarkably improves the decontamination capability and the anti-caking and flow-assisting effects of the washing powder, meets the living demands of people, and has good market prospect.
Detailed Description
The present invention is further illustrated by the following description of specific embodiments, which are not intended to limit the invention, and various modifications and improvements can be made by those skilled in the art based on the basic idea of the invention, but the invention is within the protection scope of the invention.
Wherein, the reagents used in the invention are all common reagents and can be purchased from common reagent production and sale companies.
Example 1 preparation of silica having high oil absorption and high specific surface area
The preparation method of the silica with high oil absorption and high specific surface area comprises the following steps:
s1, adding water into sodium silicate with the modulus of 2 to dilute, dissolve and age for 5 hours, and then adding water to dilute to prepare a sodium silicate solution with the concentration of 0.3 mol/L;
s2, adding 8m into the reaction tank3Heating water to 80 ℃, keeping the temperature of the whole reaction process at 80 ℃, then dropwise adding a sulfuric acid solution under stirring until the pH value is 3.0, and dropwise adding the sodium silicate solution and the sulfuric acid solution obtained in the step S1 at the same time, wherein the pH value in the reaction process is controlled to be 3.0; the dropping speed of the sodium silicate solution is 10m3H, total amount of sodium silicate solution is 4.0m3；
S3, continuously dripping triethanolamine for alkalization, and controlling the dripping speed of the triethanolamine to be 5m3Stopping dripping when the pH value of the reaction reaches 5.0, stirring and then aging for 40 min;
s4, continuously dripping sulfuric acid solution for acidification, wherein the dripping speed of the sulfuric acid solution is 1.0m3Stopping dripping when the pH value of the reaction reaches 3.0, stirring and then aging for 5 min;
s5, performing filter pressing and washing treatment on the formed silicon dioxide, wherein the electric conductivity of the washing water is 600 mu S/cm, and performing spray drying treatment on the silicon dioxide slurry to obtain the silicon dioxide.
The concentration of the sulfuric acid solution in the step S2 and the step S4 is 4.0 mol/L.
The particle size of the silica obtained in the step S5 is 40 μm.
Example 2 method for preparing silica having high oil absorption and high specific surface area
The preparation method of the silica with high oil absorption and high specific surface area comprises the following steps:
s1, adding water into sodium silicate with the modulus of 3.3 to dilute, dissolve and age for 6.5h, and then adding water to dilute to prepare a sodium silicate solution with the concentration of 0.6 mol/L;
s2, adding 8m into the reaction tank3Heating water to 85 ℃, keeping the temperature of the whole reaction process at 80 ℃, then dropwise adding a sulfuric acid solution under stirring until the pH value is 4.0, and dropwise adding the sodium silicate solution and the sulfuric acid solution obtained in the step S1 at the same time, wherein the pH value in the reaction process is controlled to be 4.0; the dropping speed of the sodium silicate solution is 12m3H, total amount of sodium silicate solution is 5.5m3；
S3, continuously dripping triethanolamine for alkalization, and controlling the dripping speed of the triethanolamine to be 7m3Stopping dripping when the pH value of the reaction reaches 5.5, stirring and then aging for 40 min;
s4, continuously dripping sulfuric acid solution for acidification, wherein the dripping speed of the sulfuric acid solution is 1.8m3Stopping dripping when the pH value of the reaction reaches 3.3, stirring and then aging for 5 min;
s5, performing filter pressing and washing treatment on the formed silicon dioxide, wherein the electric conductivity of washing water is 1000 mu S/cm, and performing spray drying treatment on the silicon dioxide slurry to obtain the silicon dioxide.
The concentration of the sulfuric acid solution in the step S2 and the step S4 is 4.0 mol/L.
The particle size of the silica obtained in the step S5 was 45 μm.
Example 3 preparation of silica having high oil absorption and high specific surface area
The preparation method of the silica with high oil absorption and high specific surface area comprises the following steps:
s1, adding water to dilute, dissolve and age the sodium silicate with the modulus of 4 for 8 hours, and then adding water to dilute to prepare a sodium silicate solution with the concentration of 0.8 mol/L;
s2, adding 8m into the reaction tank3Heating water to 90 ℃, keeping the temperature of the whole reaction process at 80 ℃, then dropwise adding a sulfuric acid solution under stirring until the pH value is 4.5, and dropwise adding the sodium silicate solution and the sulfuric acid solution obtained in the step S1 at the same time, wherein the pH value in the reaction process is controlled to be 4.5;
s3, continuously dripping triethanolamine for alkalization, and controlling the dripping speed of the triethanolamine to be 10m3Stopping dripping when the pH value of the reaction reaches 6.0, stirring and then aging for 40 min;
s4, continuously dripping sulfuric acid solution for acidification, wherein the dripping speed of the sulfuric acid solution is 3.0m3Stopping dripping when the pH value of the reaction reaches 3.5, stirring and then aging for 5 min;
s5, performing filter pressing and washing treatment on the formed silicon dioxide, wherein the electric conductivity of the washing water is 2000 mu S/cm, and performing spray drying treatment on the silicon dioxide slurry to obtain the silicon dioxide.
The concentration of the sulfuric acid solution in the step S2 and the step S4 is 4.0 mol/L.
The particle size of the silica obtained in the step S5 is 50 μm.
Comparative example 1 preparation method of silica having high oil absorption and high specific surface area
In comparison with example 2, comparative example 1 is different in that the reaction temperature in step S2 and the temperature in the entire reaction are 75 ℃, and other parameters and operations are the same as those of example 2.
Comparative example 2 a method for preparing silica
Comparative example 2 is different from example 2 in that the reaction temperature in step S2 and the temperature in the entire reaction are 95 deg.c, and other parameters and operations are the same as example 2.
Comparative example 3 a method for preparing silica
In comparison with example 2, comparative example 3 is different in that the reaction process pH is controlled to 2.5 in step S2, and other parameters and operations are the same as example 2.
Comparative example 4a method for preparing silica
In comparison with example 2, comparative example 4 is different in that the reaction process pH is controlled to 5.5 in step S2, and other parameters and operations are the same as example 2.
Comparative example 5 a method for preparing silica
Comparative example 5 is different from example 2 in that the triethanolamine solution added during the alkalization in step S3 is replaced with a sodium silicate solution, and other parameters and operations are the same as in example 2.
Comparative example 6 a method for preparing silica
The preparation method of the silica with high oil absorption and high specific surface area comprises the following steps:
s1, adding water into sodium silicate with the modulus of 3.3 to dilute, dissolve and age for 6.5h, and then adding water to dilute to prepare a sodium silicate solution with the concentration of 0.6 mol/L;
s2, adding 8m into the reaction tank3Heating water to 85 ℃, keeping the temperature of the whole reaction process at 80 ℃, then dropwise adding a sulfuric acid solution under stirring until the pH value is 4.0, and dropwise adding the sodium silicate solution and the sulfuric acid solution obtained in the step S1 at the same time, wherein the pH value in the reaction process is controlled to be 4.0; the dropping speed of the sodium silicate solution is 12m3H, total amount of sodium silicate solution is 5.5m3；
S3, continuously dripping triethanolamine for alkalization, and controlling the dripping speed of the triethanolamine to be 7m3Stopping dripping when the pH value of the reaction reaches 5.5, stirring and then aging for 40 min;
s4, performing filter pressing and washing treatment on the formed silicon dioxide, wherein the electric conductivity of washing water is 1000 mu S/cm, and performing spray drying treatment on the silicon dioxide slurry to obtain the silicon dioxide.
The concentration of the sulfuric acid solution in the step S2 is 4.0 mol/L.
The particle size of the silica obtained in the step S4 was 45 μm.
Comparative example 6 is different from example 2 in that the preparation step is not carried out with acidification treatment, and other parameters and operations are the same as example 2.
Test example I, Performance test of silica having high oil absorption and high specific surface area according to the present invention
1. Test materials: the silica with high oil absorption and high specific surface area prepared in the examples 1 to 3 and the comparative examples 1 to 6.
2. The test method comprises the following steps:
(1) specific surface area: determination of the specific surface area (m) of the solid Material by the gas adsorption BET method (GB/T19587-2004)2/g)；
(2) Oil absorption value: the oil absorption value (mL/100g) of the silica was determined according to the method in GB/T3780.2-2007 (determination of oil absorption value in second part);
(3) pH value: the pH of the silica was determined according to the method in HG/T3067-2008 (P41).
3. Test results
The test results are shown in table 1.
TABLE 1 measurement of silica Properties
| Group of | Specific surface area (m)2/g) | Oil absorption number (mL/100g) | pH |
| Example 1 | 555 | 280 | 6.3 |
| Example 2 | 600 | 286 | 6.4 |
| Example 3 | 580 | 282 | 6.5 |
| Comparative example 1 | 634 | 200 | 6.2 |
| Comparative example 2 | 307 | 285 | 6.3 |
| Comparative example 3 | 650 | 180 | 6.7 |
| Comparative example 4 | 350 | 290 | 6.6 |
| Comparative example 5 | 530 | 235 | 6.4 |
| Comparative example 6 | 420 | 280 | 8.2 |
As can be seen from Table 1: the specific surface area of the silicon dioxide prepared by the method of the embodiment 1-3 is 550-600 m2The oil absorption value is more than or equal to 280mL/100g, wherein the group of the example 2 has the best effect, and the specific surface area is 600m2The oil absorption value is 286mL/100g, the pH value is 6.4, and the method is the best embodiment of the invention.
In comparative example 1 (the reaction temperature in the step S2 is reduced to 75 ℃) and comparative example 3 (the pH in the reaction process is controlled to be reduced to 2.5 in the step S2), the specific surface area of the prepared silicon dioxide is increased, but the oil absorption value is greatly reduced compared with that of example 2, the overall effect is poorer than that of example 2, and the product stability is reduced and the decontamination capability is influenced when the silicon dioxide is applied to washing powder;
in comparative example 2 (the reaction temperature in the step S2 is increased to 95 ℃) and comparative example 4 (the pH in the reaction process is controlled to be 5.5 in the step S2), although the oil absorption value of the prepared silicon dioxide can reach a higher level, the specific surface area of the prepared silicon dioxide is greatly reduced compared with that of example 2, the total effect is poorer than that of example 2, and the adsorption capacity of the prepared silicon dioxide is reduced when the prepared silicon dioxide is applied to washing powder;
comparative example 5 after the triethanolamine solution added during the alkalization in step S3 was replaced with the sodium silicate solution, the specific surface area and oil absorption of the produced silica were both reduced as compared with example 2;
the preparation process of comparative example 6 does not carry out acidification treatment, the specific surface area and the oil absorption value of the prepared silica are reduced compared with those of example 2, and the pH value is 8.2, which is not beneficial to the stability of the washing powder formula.
In conclusion, the silicon dioxide prepared by the method has high specific surface area and high oil absorption value, the pH is 5.0-7.0, the stability of the formula of the washing powder can be effectively improved, the silicon dioxide can be used as a washing assistant to be added into the washing powder, the decontamination capability and the anti-caking and flow-assisting effects of the washing powder are obviously improved, the living requirements of people are met, and the silicon dioxide has good market prospect.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. A preparation method of silica with high oil absorption and high specific surface area is characterized by comprising the following steps:
s1, adding water to dilute, dissolve and age sodium silicate with the modulus of 2-4 for 5-8 h, and then adding water to dilute to prepare a sodium silicate solution with the concentration of 0.3-0.8 mol/L;
s2, adding 8m into the reaction tank3Heating water to 80-90 ℃, keeping the temperature of the whole reaction process at 80-90 ℃, then dropwise adding a sulfuric acid solution while stirring until the pH value is 3.0-4.5, and dropwise adding the sodium silicate solution and the sulfuric acid solution obtained in the step S1 at the same time, wherein the pH value in the reaction process is controlled to be 3.0-4.5;
s3, continuously dripping triethanolamine for alkalization, and controlling the dripping speed of the triethanolamine to be 5-10 m3Stopping dripping when the reaction pH value reaches 5.0-6.0, stirring and aging for 40 min;
s4, continuously dripping sulfuric acid solution for acidification, wherein the dripping speed of the sulfuric acid solution is 1.0-3.0 m3Stopping dripping when the reaction pH value reaches 3.0-3.5, stirring and aging for 5 min;
s5, performing filter pressing and washing treatment on the formed silicon dioxide, wherein the conductivity of washing water is less than or equal to 5000 mu S/cm, and performing spray drying treatment on the silicon dioxide slurry to obtain the silicon dioxide.
2. The method for preparing silica having high oil absorption and high specific surface area according to claim 1, wherein the modulus of sodium silicate in the step S1 is 3.3.
3. The method for preparing silica having high oil absorption and high specific surface area according to claim 1, wherein the concentration of the sodium silicate solution in the step S1 is 0.6 mol/L.
4. The method for preparing silica with high oil absorption and high specific surface area according to claim 1, wherein the dropping speed of the sodium silicate solution in the step S2 is 10-15 m3The total amount of the sodium silicate solution is 4.0-7.0 m3。
5. The method for preparing silica having high oil absorption and high specific surface area according to claim 4, wherein the dropping speed of the sodium silicate solution in the step S2 is 12m3H, total amount of sodium silicate solution is 5.5m3。
6. The method for preparing silica having high oil absorption and high specific surface area according to claim 1, wherein the concentration of the sulfuric acid solution in the step S2 and the step S4 is 4.0 mol/L.
7. The method for preparing silica having high oil absorption and high specific surface area according to claim 1, wherein the dropping speed of triethanolamine in step S3 is 7m3/h。
8. The method for preparing silica having high oil absorption and high specific surface area according to claim 1, wherein the sulfuric acid solution is added at a dropping speed of 1.8m in the step S43/h。
9. The method for preparing silica with high oil absorption and high specific surface area according to claim 1, wherein the silica obtained in step S5 has a particle size of 40 to 50 μm.
10. Use of the silica prepared by the method for preparing the silica with high oil absorption and high specific surface area according to any one of claims 1 to 9 in the preparation of washing powder.
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