CN101519245A - Preparation method of silicon dioxide colloid cleaning agent - Google Patents

Abstract

The invention belongs to the technical field of colloid, and in particular relates to a preparation method of silicon dioxide colloid cleaning agent. The adopted technical scheme is as follows: the preparation method of silicon dioxide colloid cleaning agent includes the preparation of silicon dioxide colloid and the modification of surface active agent on the silicon dioxide, wherein the surface active agent is silane coupling agent, the general expression is R'mSi(OR'')n, wherein R' is the hydrocarbon group with the C chain length from 1 to 20, and has a hydroxide group, a carboxyl group, a double bond, an epoxy group, an amino group, a sulfhydryl group, a carbamido group, a tetrasulfide group or halogen. The R'' is the hydrocarbon group with the C chain length from 1 to 18, n is not lower than 1 but not higher than 3, m is not lower than 1 but not higher than 3, and 2n+m is equal to 4. The modified silicon dioxide colloid prepared by the method has good dispersive stability in water, oil and the mixture of oil and water, and when being used as cleaning agent, the modified silicon dioxide colloid can induce scale-forming ions to form scale around the colloid granules, and prevent the scale from being formed in a container or on the internal wall of a pipeline to prevent the sewage from cause the phenomenon of secondary scale formation in the stratum.

Description

A kind of preparation method of silicon dioxide colloidal attractant

technical field

The invention belongs to the technical field of colloids, and in particular relates to a preparation method of a silica colloidal scale attractant.

Background technique

Under certain pressure and temperature, when solutions containing scale-forming ions meet, water-insoluble precipitates will form, crystallize and adsorb on the inner wall of containers or pipes, which brings great inconvenience to production and life. For example, calcium carbonate and magnesium carbonate scales formed in ordinary circulating water pipelines; barium sulfate and strontium sulfate scales formed in oil-water pipelines in the field of oil exploitation. Among them, the latter is the most difficult to clean and is very harmful, because: 1) Scaling may occur in gravel packing layers, downhole pumps, tubing strings, nozzles, oil storage equipment, gathering and transportation pipelines, crude oil processing equipment and water treatment systems 2) The scales of barium sulfate and strontium sulfate adhere firmly and the scale is hard, which is difficult to remove with conventional acid and alkali substances. Scaling will often cause the diameter of the transmission pipeline to shrink, the transmission volume will drop sharply, and sometimes even the gathering pipeline will be blocked, resulting in the scrapping of oil production equipment or workpieces. The problem of frequent scaling has seriously affected oilfield operations, resulting in a decline in production efficiency and a sharp rise in oil production costs.

At present, the relatively convenient and efficient antiscaling method is to add antiscaling agent to the conveying fluid. The main types of scale inhibitors are polycarboxylates, organic phosphonates, organic phosphonates, natural polymers and copolymer scale inhibitors, among which barium strontium scale inhibitors that have been commercialized include BS- 2E barium ion stabilizer, AMPS/AA binary copolymer, ZPS-01, LZG-I, disodium ethylenediaminetetraacetic acid (EDTA), etc. These antiscalants can slow down the formation of barium strontium sulfate scale to a certain extent. When the sewage is reinjected into the formation, due to the change of formation temperature, pressure and other conditions, the sewage containing a large amount of scaling ions will regenerate in the formation. Scaling phenomenon, causing oil wells to be blocked or even scrapped, and from the feedback information from industrial applications, some currently used scale inhibitors have disadvantages such as high production cost, low scale inhibition performance, poor temperature resistance and difficult biodegradation.

Colloidal particles have a large surface area and are usually charged, and are easy to adsorb scale ions, which can induce a large number of scale ions to grow with colloidal particles as crystal nuclei. They have the advantages of loose sedimentation structure and large precipitation volume, which can reduce sewage return. The secondary fouling phenomenon during injection, and the generated precipitate is suspended in the solution in flocculent form, and can be removed from the fluid by sedimentation or filtration, so as to avoid the formation of stubborn scale on the inner wall of the container or pipeline. However, in order to apply the colloid as a scale attractant in actual production, breakthroughs must be made in controlling the stability of the colloid and improving the dispersion of the colloid in the mixed phase.

Contents of the invention

The purpose of the present invention is to provide a preparation method of silica colloidal scale attractant, which has good dispersion stability in aqueous solution, oil solution and oil-water mixture, and is used to induce scaling ions to form around the colloidal particles. Scale, prevent stubborn scale from forming on the inner wall of the container or pipeline and avoid secondary scaling.

Based on the above purpose, the present invention adopts the following technical scheme: a preparation method of silica colloidal scale attractant, comprising the preparation of silica colloid and the modification of silica colloid by surfactant, the surface The active agent is a silane coupling agent, the general formula is R'mSi(OR")n, where R' is a hydrocarbon group with a C chain length of 1-20, with hydroxyl, carboxyl, double bond, epoxy, amino, mercapto , ureido, tetrathio or halogen; R" is a hydrocarbon group with a C chain length of 1 to 18; 1≤n≤3, 1≤m≤3, 2n+m=4.

The preparation steps of the colloidal silica include: (1) one or any combination of silicates of Li, B, K, Na, Zn, Al is dissolved in a mixed solvent composed of water and an organic solvent, and is prepared into A silicate solution with a concentration of 0.1-20%, the organic solvent being one or any combination of ethanol, acetone, benzene, toluene, carbon tetrachloride; (2) the silicate solution obtained in step (1) successively After being treated with cation exchange resin and anion exchange resin, the insoluble impurities are removed to obtain a colloidal silica mother liquor, and the colloidal silica is obtained after the mother liquor undergoes a granulation reaction.

The cation exchange resin is homogeneous, the pH value before use is 4.0-5.0, and the pH value of the exchange liquid after cation exchange is controlled at 1.0-6.0; the anion exchange resin is strong base type, the pH value before use is The pH value is 7.0-8.0, and the pH value of the exchange liquid after anion exchange is controlled at 2.0-6.0.

The operation method of the granulation reaction is as follows: take 1 part by weight from the mother liquor as the base liquid, and 5-20 parts by weight as the dripping liquid; use the silicate solution to adjust the pH value of the base liquid to 7.5- After 10.0°C, slowly heat to 40-120°C; add the dropping solution dropwise into the base liquid to react for 1-10 hours, and the pH value of the system during the reaction is controlled at 7.5-10.0 with the silicate solution.

When preparing colloidal silica, the granulation reaction product needs to be aged at a temperature of 40-90°C for 1-20 hours.

Concentrate the prepared colloidal silica to a solid content of 5-50%, and modify it by adding a surfactant; the modification method is: mix the surfactant and colloidal silica, react for 1-10 hours, The reaction temperature is from room temperature to 90°C. After the reaction, adjust the pH value of the system to 8.0 to 13.0 with ammonia water; the mass ratio of the surfactant to silica colloid is 1:5-200 to obtain negatively charged silica gel Body attractant.

Make the prepared silica colloid pass through the homogeneous cation exchange resin, and control the pH value of the exchange solution at 1.0-6.0; then concentrate the obtained exchange solution to silica colloid with a solid content of 5-50%, and add the surface The active agent is used to modify it; the modification method is: mix the surfactant with the concentrated silica colloid, react for 1 to 10 hours, and the reaction temperature is room temperature to 90°C. After the reaction, use hydrochloric acid to adjust the pH value of the system to Adjust to 2.0-6.0; the mass ratio of the surfactant to the silica colloid is 1:5-200 to obtain a positively charged silica colloid scale attractant.

The silicon dioxide colloidal scale attractant prepared according to the method of the present invention is actually a complex multiphase liquid dispersion system: silicon dioxide exists in colloidal form, and its particle diameter is between 2-60nm; non-polar Organic solvents and water form small droplets with larger particle sizes, that is, they exist in the form of emulsions. The finished silica colloidal scale attractant was observed for one year, and there was no precipitation, delamination or gel phenomenon. This is because the addition of the silane coupling agent promotes the stability of the entire system; at the same time, the silane coupling agent also promotes the uniform dispersion of the scale inducer into the aqueous solution, oil solution and oil-water interface liquid. The prepared modified silica colloid is used as a scale inducer, which can effectively absorb scale ions and scale, whether it is for difficult-to-treat sulfate scale (such as barium sulfate, strontium sulfate, etc.) or for easy-to-remove carbonate Salt scale (such as calcium carbonate, magnesium hydroxide, etc.) has a very good induction-anti-scaling effect. A simulated water sample is prepared, and the anti-scale rate of the scale-inducing agent of the present invention can reach 40-80% as determined by a dynamic simulation method. After the dynamic simulation experiment, use EDTA titration to measure the remaining content of scale-forming cations in the simulated water samples. By comparing the content of scale-forming cations in the water samples before and after the experiment, the precipitation of scale-forming ions can be calculated, and compared with the addition of scale-inducing agents. According to the amount of precipitation of scale-forming ions before and after, the scale-inducing agent of the present invention can induce precipitation rate of scale-forming ions up to 20-50%. The present invention can be realized by using ordinary industrial-grade raw materials, and the preparation process has strong operability and is easy to be popularized in an industrialized manner.

Detailed ways

Example 1

The preparation method of colloidal silica scale attractant comprises two steps of preparation of colloidal silica and modification of colloidal silica by surfactants:

Preparation of colloidal silica:

(1) Take 10.34g K ₂ O·4SiO ₂ , dissolve it in a mixed solvent consisting of 10g acetone, 4g ethanol, and 200g deionized water; filter and remove impurities to obtain a silicate solution.

(2) The silicate solution prepared in step (1) is subjected to ion exchange treatment through a homogeneous cation exchange resin, and the exchange liquid and deionized water washing liquid are collected and then ion exchange treatment is carried out through a strong base anion exchange resin, and the exchange solution is collected and exchanged. liquid and deionized water washing solution, centrifuged to obtain silica colloidal mother liquor. The homogeneous cation exchange resin is regenerated with acid to pH value = 4.0 before use, and the pH value of the exchange solution after cation exchange is controlled at 1.0; the strong base anion exchange resin is regenerated with alkali to pH value = 7.0 before use, The pH value of the exchange liquid after anion exchange is controlled at 2.0.

Take 1 part by weight from the above mother liquor as the base liquid, and 5 parts by weight as the dripping liquid, and carry out the granulation reaction: after adjusting the pH value of the base liquid to 9.5 with the silicate solution in step (1), slowly heat to 120°C ; The addition solution was added dropwise to the base solution to react for 1 hour, and the pH value of the system during the reaction was controlled at 9.5 with the silicate solution. After the granulation reaction, the reaction product was aged at 40° C. for 20 hours.

Modification of silica colloids with surfactants:

Concentrate the prepared colloidal silica to a solid content of 5%, and modify it by adding a surfactant H ₂ NCH ₂ ·CH ₂ NH(CH ₂ ) ₃ ·Si(OC ₂ H ₅ ) ₃ . The modification method is as follows: mix 1 part of surfactant with 5 parts of colloidal silica, react at room temperature for 10 hours, and adjust the pH value of the system to 8.0 with ammonia water after the reaction.

The modified silica colloid obtained after the reaction is negatively charged and has good dispersion stability in oil solution and oil-water interface liquid. Used as a scale inducer in oil pipelines in oil fields, it can well induce the precipitation of barium sulfate, strontium sulfate, calcium carbonate, and magnesium hydroxide, and prevent stubborn scale from forming on the inner wall of the pipeline.

Example 2

The preparation method of colloidal silica scale attractant comprises two steps of preparation of colloidal silica and modification of colloidal silica by surfactants:

Preparation of colloidal silica:

(1) Take 36.12g Li ₂ O·SiO ₂ , dissolve it in a mixed solvent consisting of 5g toluene, 5g ethanol and 200g deionized water; filter to remove impurities to obtain a silicate solution.

(2) The silicate solution prepared in step (1) is subjected to ion exchange treatment through a homogeneous cation exchange resin, and the exchange liquid and deionized water washing liquid are collected and then ion exchange treatment is carried out through a strong base anion exchange resin, and the exchange solution is collected and exchanged. liquid and deionized water washing solution, centrifuged to obtain silica colloidal mother liquor. The homogeneous cation exchange resin is regenerated with an acid to a pH value of 4.1 before use, and the pH value of the exchange solution after the cation exchange is controlled at 1.4; the strong base anion exchange resin is regenerated with an alkali to a pH value of 7.2 before use. The pH value of the exchange liquid after anion exchange is controlled at 2.7.

Take 1 part by weight from the above mother liquor as the base liquid, and 8 parts by weight as the dripping liquid, and carry out the granulation reaction: after adjusting the pH value of the base liquid to 10.0 with the silicate solution in step (1), slowly heat to 45°C ; The addition solution was added dropwise to the base solution to react for 8 hours, and the pH value of the system during the reaction was controlled at 10.0 with the silicate solution. After the granulation reaction, the reaction product was aged at 45° C. for 12 hours.

Modification of silica colloids with surfactants:

Concentrate the prepared colloidal silica to a solid content of 30%, add a surfactant (H ₅ C ₂ O) ₃ Si(CH ₂ ) ₃ ·S ₄ ·(CH ₂ ) ₃ ·Si(OC ₂ H ₅ ) ₃ to modify it. The modification method is: mix 1 part of surfactant with 20 parts of colloidal silica, react at 90°C for 1 hour, and adjust the pH value of the system to 10.0 with ammonia water after the reaction.

The modified silica colloid obtained after the reaction is negatively charged and has good dispersion stability in aqueous solution and oil aqueous solution. Used as a scale inducer in oil pipelines in oil fields, it can well induce the precipitation of barium sulfate, strontium sulfate, calcium carbonate, and magnesium hydroxide, and prevent stubborn scale from forming on the inner wall of the pipeline.

Example 3

The preparation method of colloidal silica scale attractant comprises two steps of preparation of colloidal silica and modification of colloidal silica by surfactants:

Preparation of colloidal silica:

(1) Take 43.60g K ₂ O·2.4SiO ₂ , dissolve it in a mixed solvent consisting of 5g toluene, 5g ethanol, 8g acetone, and 200g deionized water; filter to remove impurities to obtain a silicate solution.

(2) The silicate solution prepared in step (1) is subjected to ion exchange treatment through a homogeneous cation exchange resin, and the exchange liquid and deionized water washing liquid are collected and then ion exchange treatment is carried out through a strong base anion exchange resin, and the exchange solution is collected and exchanged. liquid and deionized water washing solution, centrifuged to obtain silica colloidal mother liquor. The homogeneous cation exchange resin is regenerated with acid to pH=4.3 before use, and the pH value of the exchange solution after cation exchange is controlled at 2.5; the strong base anion exchange resin is regenerated with alkali to pH=7.5 before use, The pH value of the exchange liquid after anion exchange is controlled at 3.2.

Take 1 part by weight from the above mother liquor as the base liquid, and 10 parts by weight as the dripping liquid, and carry out the granulation reaction: after adjusting the pH value of the base liquid to 7.5 with the silicate solution in step (1), slowly heat to 100°C ; The addition solution was added dropwise to the base solution to react for 3 hours, and the pH value of the system during the reaction was controlled at 7.5 with the silicate solution. After the granulation reaction, the reaction product was aged at 80° C. for 9 hours.

Modification of silica colloids with surfactants:

Concentrate the prepared silica colloid to a solid content of 50%, and modify it by adding a surfactant H ₂ NCH ₂ ·CH ₂ NH(CH ₂ ) ₃ ·Si(OCH ₃ ) ₃ . The modification method is: mix 1 part of surfactant with 200 parts of colloidal silica, react at 45°C for 5 hours, and adjust the pH value of the system to 13.0 with ammonia water after the reaction.

The modified silica colloid obtained after the reaction is negatively charged and has good dispersion stability in oil solution and oil-water interface liquid. Used as a scale inducer in oil pipelines in oil fields, it can well induce the precipitation of barium sulfate, strontium sulfate, calcium carbonate, and magnesium hydroxide, and prevent stubborn scale from forming on the inner wall of the pipeline.

Example 4

The preparation method of colloidal silica scale attractant comprises two steps of preparation of colloidal silica and modification of colloidal silica by surfactants:

Preparation of colloidal silica:

(1) Take 0.223g ZnO·SiO ₂ , dissolve it in a mixed solvent consisting of 4g toluene, 5g ethanol, 6g carbon tetrachloride, 8g acetone, and 200g deionized water; filter to remove impurities to obtain a silicate solution.

(2) The silicate solution prepared in step (1) is subjected to ion exchange treatment through a homogeneous cation exchange resin, and the exchange liquid and deionized water washing liquid are collected and then ion exchange treatment is carried out through a strong base anion exchange resin, and the exchange solution is collected and exchanged. liquid and deionized water washing solution, centrifuged to obtain silica colloidal mother liquor. The homogeneous cation exchange resin is regenerated with acid to pH=4.5 before use, and the pH value of the exchange solution after cation exchange is controlled at 3.0; the strong base anion exchange resin is regenerated with alkali to pH=7.7 before use, The pH value of the exchange liquid after anion exchange was controlled at 4.9.

Take 1 part by weight from the above mother liquor as the base liquid, and 15 parts by weight as the dripping liquid, and carry out the granulation reaction: after adjusting the pH value of the base liquid to 9.0 with the silicate solution in step (1), slowly heat to 80°C ; The addition solution was added dropwise to the base solution to react for 5 hours, and the pH value of the system during the reaction was controlled at 9.0 with the silicate solution. After the granulation reaction was completed, the reaction product was aged at 60° C. for 17 hours.

Modification of silica colloids with surfactants:

Make the prepared colloidal silica pass through the homoporous cation exchange resin, and the pH value of the exchange solution is controlled at 4.5; then the exchange solution obtained is concentrated to a colloidal silica with a solid content of 5%, and surfactant Cl. It is modified by CH ₂ ·CH ₂ ·CH ₂ ·Si(OC ₂ H ₅ ) ₃ .

The modification method is: mix 1 part of surfactant with 5 parts of concentrated colloidal silica, react at 90° C. for 1 hour, and adjust the pH value of the system to 4.5 with hydrochloric acid after the reaction.

The prepared silica colloid has a positive charge and has good dispersibility in oil solution and oil-water interface liquid. It is used as a scale inducer in oilfield water treatment, and has a certain effect on inducing precipitation of barium sulfate and strontium sulfate scale and preventing pipeline scaling.

Example 5

The preparation method of colloidal silica scale attractant comprises two steps of preparation of colloidal silica and modification of colloidal silica by surfactants:

Preparation of colloidal silica:

(1) Take 21.38g Na ₂ O·SiO ₂ ·9H ₂ O and dissolve it in a mixed solvent consisting of 5g toluene, 5g benzene, 6g carbon tetrachloride, 8g acetone, and 200g ionized water; filter and remove impurities to obtain silicon Salt solution.

(2) The silicate solution prepared in step (1) is subjected to ion exchange treatment through a homogeneous cation exchange resin, and the exchange liquid and deionized water washing liquid are collected and then ion exchange treatment is carried out through a strong base anion exchange resin, and the exchange solution is collected and exchanged. liquid and deionized water washing solution, centrifuged to obtain silica colloidal mother liquor. The homogeneous cation exchange resin is regenerated with an acid to a pH value of 4.9 before use, and the pH value of the exchange solution after the cation exchange is controlled at 4.2; the strong base anion exchange resin is regenerated with an alkali to a pH value of 7.9 before use. The pH value of the exchange liquid after anion exchange is controlled at 5.6.

Take 1 part by weight from the above mother liquor as the base liquid, and 18 parts by weight as the dripping liquid, and carry out the particle increase reaction: after adjusting the pH value of the base liquid to 8.0 with the silicate solution in step (1), slowly heat to 60°C ; The addition solution was added dropwise to the base solution to react for 6 hours, and the pH value of the system during the reaction was controlled at 8.0 with the silicate solution. After the granulation reaction, the reaction product was aged at 70° C. for 5 hours.

Modification of silica colloids with surfactants:

The prepared colloidal silica is passed through the homoporous cation exchange resin, and the pH value of the exchange solution is controlled at 1.0; then the exchange solution obtained is concentrated to a colloidal silica with a solid content of 35%, and a surfactant (H ₅ C ₂ O) ₃ Si(CH ₂ ) ₃ ·S ₄ ·(CH ₂ ) ₃ ·Si(OC ₂ H ₅ ) ₃ to modify it.

The modification method is: mix 1 part of surfactant with 21 parts of concentrated colloidal silica, react at room temperature for 10 hours, and adjust the pH value of the system to 2.0 with hydrochloric acid after the reaction.

The prepared silica colloid has a positive charge and has good dispersibility in aqueous solution and oil-water interface liquid. It is used as a scale inducer in oilfield water treatment, and has a certain effect on inducing precipitation of barium sulfate and strontium sulfate scale and preventing pipeline scaling.

Example 6

The preparation method of colloidal silica scale attractant comprises two steps of preparation of colloidal silica and modification of colloidal silica by surfactants:

Preparation of colloidal silica:

(1) Get 34.16g Al ₂ O ₃ ·SiO ₂ , dissolve it in a mixed solvent consisting of 5g toluene, 5g ethanol, 6g benzene, 8g acetone, 10g carbon tetrachloride, and 200g deionized water; silicate solution.

(2) The silicate solution prepared in step (1) is subjected to ion exchange treatment through a homogeneous cation exchange resin, and the exchange liquid and deionized water washing liquid are collected and then ion exchange treatment is carried out through a strong base anion exchange resin, and the exchange solution is collected and exchanged. liquid and deionized water washing solution, centrifuged to obtain silica colloidal mother liquor. The homogeneous cation exchange resin is regenerated with acid to pH value=5.0 before use, and the pH value of the exchange liquid after cation exchange is controlled at 6.0; the strong base anion exchange resin is regenerated with alkali to pH value=8.0 before use, The pH value of the exchange liquid after anion exchange is controlled at 6.0.

Take 1 part by weight from the above mother liquor as the base liquid, and 20 parts by weight as the dripping liquid, and carry out the granulation reaction: after adjusting the pH value of the base liquid to 8.5 with the silicate solution in step (1), slowly heat to 40°C ; The addition solution was added dropwise to the base solution to react for 10 hours, and the pH value of the system during the reaction was controlled at 8.5 with the silicate solution. After the granulation reaction, the reaction product was aged at 90° C. for 1 hour.

Modification of silica colloids with surfactants:

Make the prepared colloidal silica pass through a homoporous cation exchange resin, and control the pH value of the exchange solution at 6.0; then concentrate the obtained exchange solution to silica colloid with a solid content of 50%, and add surfactant _H2 It is modified by NCH ₂ ·CH ₂ NH(CH ₂ ) ₃ ·Si(OCH ₃ ) ₃ .

The modification method is: mix 1 part of surfactant with 200 parts of concentrated colloidal silica, react at 50°C for 4 hours, and adjust the pH value of the system to 6.0 with hydrochloric acid after the reaction.

The prepared silica colloid has a positive charge and has good dispersibility in oil solution and oil-water interface liquid. It is used as a scale inducer in oilfield water treatment, and has a certain effect on inducing precipitation of barium sulfate and strontium sulfate scale and preventing pipeline scaling.

Claims (7)

1, a kind of preparation method of silicon dioxide colloid cleaning agent, it is characterized in that, comprise the modification of the preparation of silicon dioxide colloid and tensio-active agent to silicon dioxide colloid, described tensio-active agent is a silane coupling agent, general formula is R ' mSi (OR ＂) n, wherein R ' is the alkyl of C chain length 1～20, on have hydroxyl, carboxyl, two key, epoxy group(ing), amino, sulfydryl, urea groups, four sulfenyls or halogen; R ＂ is the alkyl of C chain length 1～18; 1≤n≤3,1≤m≤3,2n+m=4.

2, the preparation method of silicon dioxide colloid cleaning agent as claimed in claim 1, it is characterized in that, the preparation process of described silicon dioxide colloid comprises: a kind of or arbitrary combination in the silicate of (1) Li, B, K, Na, Zn, Al is dissolved in the mixed solvent of water and organic solvent composition, be mixed with the silicate solutions that concentration is 0.1-20%, described organic solvent is a kind of or arbitrary combination in ethanol, acetone, benzene, toluene, the tetracol phenixin; (2) step (1) gained silicate solutions is earlier after Zeo-karb, anion exchange process, obtains the silicon dioxide colloid mother liquor after removing insoluble impurities again, and described mother liquor promptly gets silicon dioxide colloid after increasing the grain reaction.

3, the preparation method of silicon dioxide colloid cleaning agent as claimed in claim 2 is characterized in that, described Zeo-karb is equal pass, and the pH value before using is 4.0～5.0, and the pH value of exchange liquid is controlled at 1.0～6.0 after cationic exchange; Described anionite-exchange resin is strong base, and the pH value before using is 7.0～8.0, and the pH value of exchange liquid is controlled at 2.0～6.0 after the anionresin.

4, the preparation method of silicon dioxide colloid cleaning agent as claimed in claim 2 is characterized in that, the described working method that increases the grain reaction is: get 1 weight part as base fluid from described mother liquor, 5～20 weight parts are as dropping liquid; After with described silicate solutions base fluid pH value being adjusted to 7.5～10.0, slowly be heated to 40～120 ℃; Dropping liquid dropwise joined react 1～10 hour in the base fluid, the pH value of system is controlled at 7.5～10.0 with described silicate solutions in the reaction.

5, the preparation method of silicon dioxide colloid cleaning agent as claimed in claim 2 is characterized in that, preparation is during silicon dioxide colloid, and increasing a reaction product also need be under 40-90 ℃ temperature condition ageing 1-20 hour.

As the preparation method of the arbitrary described silicon dioxide colloid cleaning agent of claim 1-5, it is characterized in that 6, it is 5～50% that the silicon dioxide colloid for preparing is concentrated into solid content, add tensio-active agent it is carried out modification; Method of modifying is: tensio-active agent is mixed with silicon dioxide colloid, reacted 1～10 hour, temperature of reaction is room temperature～90 ℃, and the reaction back transfers to 8.0～13.0 with ammoniacal liquor with the pH value of system; The mass ratio of described tensio-active agent and silicon dioxide colloid is 1:5-200.

As the preparation method of the arbitrary described silicon dioxide colloid cleaning agent of claim 1-5, it is characterized in that 7, make the silicon dioxide colloid for preparing through equal pass Zeo-karb, the pH value of exchange liquid is controlled at 1.0～6.0; Then the exchange liquid of gained is concentrated into solid content and is 5～50% silicon dioxide colloid, add tensio-active agent it is carried out modification; Method of modifying is: with tensio-active agent with concentrate after silicon dioxide colloid mixes, react 1～10 hour, temperature of reaction is room temperature～90 ℃, reacts afterwards with hydrochloric acid the pH value of system is adjusted to 2.0～6.0; The mass ratio of described tensio-active agent and silicon dioxide colloid is 1:5-200.