CN1124757A - Process for preparing quick-dissolving multi-hydroxy positively charged solid sol mixed with metallic salt - Google Patents
Process for preparing quick-dissolving multi-hydroxy positively charged solid sol mixed with metallic salt Download PDFInfo
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- CN1124757A CN1124757A CN 94120136 CN94120136A CN1124757A CN 1124757 A CN1124757 A CN 1124757A CN 94120136 CN94120136 CN 94120136 CN 94120136 A CN94120136 A CN 94120136A CN 1124757 A CN1124757 A CN 1124757A
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Abstract
The positive solid sols used as fluid regulator, shale inhibitor and well wall stabilizer for well drilling is prepared through such steps as washing mixed metal salt suspension, treating with ion exchange resin, then addition of low-molecular cationic disperser, peptizing at 30-100 deg.C for 30 min, dewatering with organic solvent, addition of solid colloid protector, kneading and air drying to obtain granular product, and features high electric potential greater than 50 mv, high sol-forming speed less than 15 seconds, 100% stability of sol-forming rate, and low cost.
Description
The present invention relates to a kind of preparation method who is used as the instant ultracrystallite multi-hydroxy positively charged solid sol mixed with metallic salt of water-base drilling fluid, well finishing liquid, well cementation liquid, workover fluid and of the fracturing fluid flow pattern regulator, shale control agent and borehole wall stabilizer, belong to field of fine chemical.
For improving the rheological of water-base drilling fluid, shale inhibition and borehole wall stability, people begin to use in a large number positive colloid, be MMLHC (mixed metal layer hydroxide compound) (MMH), or title poly-hydroxy hybrid metal salt sol (MSF), or claim active mixed metal oxide (AMMO), require this positive colloid in water, can be dispersed into stable sols rapidly, and has a greater activity, be higher positive Zeta potential EP207810A2, CN86104606A has disclosed a kind of preparation method who is used as single dispersing and mixing metal hydroxides of water fluid or drilling fluid thickening material, it is to be " instantaneous " co-precipitation under 15-80 ℃ the quasi steady-state condition in temperature by stoichiometry with mixed salt solution and bases precipitant solution, after filtration with distilled water or deionized water wash, made the water-sol in loose naturally then about 7 days again.The method of the dry this water-sol is the hydrophilic organic thing that adds a large amount of glycerine or polyoxyethylene glycol and so in the water-sol, drying is 16 hours in baking oven, or with spray-dryer or cabinet drier drying, pulverize, the solid sols dry powder that makes can disperse within 5 minutes automatically.Domestic employing co-precipitation suspended substance with deionized water wash after directly under comparatively high temps peptization prepare the water-sol, yet add the colloid protecting resistance of Zulkovsky starch or dextrin or treated starch and so on, the spray-dried dry glue powder that makes.But the main drawback of the above-mentioned preparation water-sol and solid sols method is that washing time is long, impurity is difficult for eliminating, the loose naturally one-tenth glue cycle of filter cake is long, yield poorly product poor activity, water-sol zeta-potential≤40mV, though it is domestic with peptisation replacement nature method of relaxation, but still have peptization temperature height, and the deficiency of time length, drying time is long during the preparation solid sols, big with the spray dryer apparatus investment, the energy consumption height, the product cost height, of poor quality, it is slow to revert to glue speed, become glue rate and stability low, active low, general zeta-potential≤35mV.
The present invention is intended to overcome the deficiency of above-mentioned prior art, provides a kind of prescription and facility investment of solid sols of excellent property few, and technology is simple, and raw material is extensively honest and clean, and energy consumption is little, the preparation method that cost is low.
The present invention is by fundamental research, invention adds micro-small molecules cation dispersing agent in the mixed metal hydroxides gel of purifying, the quick dispersion peptization that helps the purifying gel, and improve the activity of the water-sol greatly, thereby the shale that improves positive colloid suppresses ability, and this is the prerequisite that the present invention prepares the high-performance solid sols.With water-sol hydrophilic organic solvent room temperature dehydration concentrating and separating, and directly add a large amount of solid colloid protecting resistances, the evaporation of water-absorbing-retaining and rapid and natural is carried out simultaneously, need not heat drying and pulverize just to make instant granular positive electricity solid sols, avoided positive colloid crystallite that heat drying causes because of losing the coalescent drawback that is difficult for redispersion of crystal water and water of hydration, the colloidal property of positive electricity solid sols is greatly improved, shale inhibition further strengthens, and this is the key that the present invention prepares the high-performance solid sols.
Purpose of the present invention can reach by the following technical programs: the mixed metal hydroxides suspended substance of reaction is used with tap water washing back mixed the anion-cation exchange resin purifying, add micro-small molecules cation dispersing agent again, in temperature is under the 30-100 ℃ of condition peptization 10-90 minute, preferably 50-80 ℃ peptization 30-50 minute, treat that temperature reduces to the 1-5 times of organic solvent that adds sol volume after the room temperature, preferably 1.5～3.0 times, contrary molten extraction concentrating and separating, the 5-25 solid colloid protecting resistance doubly that adds colloidal sol butt weight again, preferably 7-10 doubly mediates evenly air-dry fast.Promptly get instant positive electricity solid sols.
The preparation flow of the instant positive electricity solid sols of the present invention is as follows:
Washing-purifying-peptization-concentrate-mediate-air-dry
It is soluble small molecular quaternary ammonium salt compound or oligopolymer that the present invention disperses to add the small molecules cation dispersing agent in the peptization step, and its dosage is the 0.02-0.4% of purifying gel butt weight, preferably 0.05-0.1%.
One of the present invention dewaters, and used organic solvent is water-soluble alcohol compounds or pure ether compound in the enrichment step, or ketone compounds, or the mixture of two or three classes.Alcohol compound is methyl alcohol, ethanol (alcohol), Virahol, isopropylcarbinol at least, the trimethyl carbinol, ethylene glycol, propylene glycol, glycerine or two or a plurality of their one of mixture, the mixture of preferably ethanol, or ethylene glycol or ethanol and glycerine; The alcohol ether compound is measured ethylene glycol monomethyl ether at least, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycol ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triglycol, Macrogol 200-400, molecular weight polypropylene glycol, perhaps two or a plurality of their one of mixture, preferably diethylene glycol monobutyl ether, or triglycol; Ketone compounds is acetone at least, butanone, methylene acetone, diacetone alcohol, 5-hydroxyl-2 pentanone, perhaps two or a plurality of their one of mixture, preferably acetone or butanone, the volume ratio of components of mixed solvent is an alcohol: alcohol ether: ketone=1.5-4: 0.5～1.5: 0.5-2 is best than being 2: 1: 1.5.
The solid colloid protecting resistance that adds in the kneading step of the present invention is the water-soluble carbohydrate or derivatives thereof, it comprises monosaccharide component, the oligose component, two or a plurality of mixture of monosaccharides, two or a plurality of oligosaccharide mixture, or the mixture of one or more oligose and one or more monose, or Xylitol or sorbyl alcohol, or positively charged ion or nonionic modified starch.Water-soluble carbon hydrate additive is that natural materials comprises the syrup extract of starch, sugarcane, beet and Fructus Hordei Germinatus grain or their mixture.
Compared with prior art, unusual effect of the present invention and advantage are:
1. after adopting the tap water pre-wash, straight by with mixing the anion-cation exchange resin purifying, the soluble impurity content in the mixture gel is significantly reduced, average anionic residue surplus≤200ppm, shorten the purifying time, improve work efficiency and quality product, provide guarantee for the water-sol obtains high reactivity.
2. in the purifying gel, add micro-soluble small molecular cation dispersing agent and carry out peptization, reduce the peptization temperature, shorten peptization time, significantly improve the activity of the water-sol, make zeta-potential 〉=+50mV.
3. adopt the organic solvent room temperature dehydration to concentrate, avoided concentrating the coalescent possibility of water-sol crystallite that causes because of heating.Contain trace solvent in the solid sols simultaneously, help quick dispersion.
4. mediate air-dry in concentrating and separating colloidal sol, directly adding a large amount of solid colloid protecting resistances under the room temperature, the evaporation of water-absorbing-retaining and rapid and natural is carried out simultaneously, avoided in any type of heat drying process water-sol crystallite because of losing crystal water and water of hydration is coalescent, make the zeta-potential of solid sols unaffected, gelation time significantly shortens＜and 15 seconds, become glue rate and stability to significantly improve, reach 100%.
5. the freeze proof inhibition of instant positive electricity solid sols of the present invention's preparation obviously improves, and can directly use also to be dispersed into water-sol use, and the drilling fluid that is particularly suited for loose and broken formation and water-sensitive strata is made shale control agent, wellbore stability well and flow pattern regulator.
6. adopt preparation method of the present invention, raw material is extensively honest and clean, and technology is simple, reduces facility investment, cuts down the consumption of energy and cost.
Further specify with embodiment below, but do not limit the present invention:
Embodiment 1
Produce reaction mixture suspension 400g by the EP207810 method, filter and with tap water drip washing three times, filter cake adds 0.01gNW-1 (a kind of small molecules quaternary amine) and places the three-necked bottle stirring to be warming up to 75 ℃, constant temperature peptization 30 minutes with after mixing the zwitterion plastic resin treatment, be cooled to wet back, chamber and add 350ml 95% alcohol, stir, filter or centrifugation, add 140g fructose again, it is air-dry fast to stir, and promptly getting granular positive electricity solid sols is sample 1.
Embodiment 2-4
Adopt the preparation technology similar to embodiment 1, different is to use triglycol, acetone and mixed solvent substituted alcohol respectively.The volume ratio of components of mixed solvent is an ethanol: diethylene glycol monobutyl ether: acetone=2: 1: 1.5.Make the positive electricity solid sols and be respectively sample 2-4.
Embodiment 5-7
Adopt the preparation technology similar with embodiment 1, different is is 1: 4 the mixture and the concentrated extract replacement fructose of sugarcane syrup with sucrose, fructose/sucrose weight ratio respectively, makes positive electricity solid sols sample 5-7.
Embodiment 8
Prepare solid sols sample 8 in contrast by method described in the CN86104606A.
Embodiment 9
Measure the zeta-potential of invention sample and control sample respectively, become glue speed, become glue rate and stability, the results are shown in Table 1
Table 1
* Shandong University's technology North China Oilfield drilling well two company auxiliary reagent factories produce
Example 10
Measure respectively invention sample and control sample shale inhibition, the results are shown in Table 2, test conditions is:
The preparation of artificial " shale ": the sodium of 75% (wt) is removed soil+25% (wt) kaolin clay mixture under 154MPa, add and be pressed into hard " artificial shale " sheet.
The preparation of testing liquid: 350ml deionized water+1.5% solid sols sample.
Measuring condition: will measure turgidity and penetration degree (g/mm) after 10 hours in 60 ℃ of immersions in the shale sheet immersion solution.
Table 2
Claims (16)
1. preparation method that in water, can be dispersed into the instant ultracrystallite multi-hydroxy positively charged solid sol mixed with metallic salt of stable colloid fast, it is characterized in that suspended substance that mixed metal salt and precipitation agent react is through washing, ion-exchange resin purification under stable state, add micro-cation dispersing agent, control optimal temperature peptization, again under room temperature through the dehydration of organic solvent concentrating and separating, add the solid colloid protecting resistance, mediate air-dryly, the instant positive electricity solid sols of gained is as water-base drilling fluid flow pattern regulator, shale control agent and borehole wall stabilizer.
2. method according to claim 1 is characterized in that directly using tap water washing reaction suspended substance, then with mixing the anion-cation exchange resin purifying, makes that soluble impurity content significantly reduces in the filtrate, average anionic residue surplus≤200ppm.
3. method according to claim 1, it is characterized in that in the gel of purifying adding micro-cation dispersing agent, is under the 30-100 ℃ of condition peptization 10-90 minute in temperature then, preferably 50-80 ℃ peptization 30-50 minute, the gained water-sol is active obviously to be improved, zeta-potential 〉=+50mV.
4. method according to claim 1 is characterized in that the cation dispersing agent that adds is small molecules quaternary ammonium salt compound or oligopolymer, and its dosage is the 0.02-0.4% of colloidal sol butt weight, preferably 0.05-0.1%.
5. method according to claim 1, it is characterized in that positive electrosol under room temperature with organic solvent counter-current extraction dehydration concentrating and separating.
6. method according to claim 1, it is characterized in that used organic solvent is the water-soluble alcohol compounds, at least be methyl alcohol, ethanol (alcohol), Virahol, isopropylcarbinol, the trimethyl carbinol, ethylene glycol, propylene glycol and glycerine, or two or a plurality of their one of mixture, the preferably mixture of ethanol or ethylene glycol or ethanol and glycerine.
7. method according to claim 1, it is characterized in that used organic solvent is the water-soluble alcohol ether compound, is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether at least, glycol ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triglycol, Macrogol 200-400, molecular weight polypropylene glycol, perhaps two or a plurality of their one of mixture, preferably diethylene glycol monobutyl ether or triglycol.
8. method according to claim 1 is characterized in that used organic solvent is the water-soluble ketone compounds, is acetone at least, butanone, methylene acetone, diacetone alcohol, 5-hydroxyl-2 pentanone, person person two or a plurality of their one of mixture, preferably acetone or butanone.
9. method according to claim 1, it is characterized in that used organic solvent is the mixture of alcohols, pure ethers and ketone compounds two or three classes, its volume ratio of components is alcohol: alcohol ether: ketone=1.5～4: 0.5～1.5: 0.5～2, best than being 2: 1: 1.5.
10. method according to claim 1, the dosage that it is characterized in that organic solvent be the positive electricity sol volume 1-5 doubly, preferably 1.5～3.0 times.
11. method is characterized in that the solid colloid protecting resistance that adds is the water-soluble carbohydrate or derivatives thereof according to claim 1.
12. as method as described in claim 1 or 11, it is characterized in that the water-soluble carbohydrate or derivatives thereof that adds comprises the monose component, the oligose component, two or a plurality of mixture of monosaccharides, two or a plurality of oligosaccharide mixture, or the mixture of one or more oligose and a plurality of monose, or Xylitol or sorbyl alcohol, or positively charged ion or nonionic modified starch.
13., it is characterized in that water-soluble carbohydrate is that natural materials comprises the syrup extract of starch, sugarcane, beet and Fructus Hordei Germinatus grain or their mixture as method as described in claim 1 or 11.
14. method according to claim 1, the dosage that it is characterized in that the solid colloid protecting resistance should make the water-sol can be air-dry fast, be at least colloidal sol butt weight 5-25 doubly, preferably 7-10 is doubly.
15 methods according to claim 1 is characterized in that directly adding the solid colloid protecting resistance in concentrating colloidal sol, mediate air-dryly fast under room temperature, make the granular positive electricity solid sols of gained revert to glue speed＜15 second, become glue rate and stability 100%.
16. method according to claim 1, it is characterized in that the instant positive electricity solid sols for preparing has improved inhibition, the frost resistance of the positive electricity water-sol, the drilling fluid that is particularly suitable for loose and broken formation and water-sensitive strata is made shale control agent, borehole wall stabilizer and flow pattern regulator.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94120136 CN1124757A (en) | 1994-12-31 | 1994-12-31 | Process for preparing quick-dissolving multi-hydroxy positively charged solid sol mixed with metallic salt |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 94120136 CN1124757A (en) | 1994-12-31 | 1994-12-31 | Process for preparing quick-dissolving multi-hydroxy positively charged solid sol mixed with metallic salt |
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| CN1124757A true CN1124757A (en) | 1996-06-19 |
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| CN 94120136 Pending CN1124757A (en) | 1994-12-31 | 1994-12-31 | Process for preparing quick-dissolving multi-hydroxy positively charged solid sol mixed with metallic salt |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108430964A (en) * | 2015-10-09 | 2018-08-21 | 医学研究理事会 | For generating method and compositions related and purposes through the ligand modified ferric hydroxide colloid of carboxylate radical |
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1994
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108430964A (en) * | 2015-10-09 | 2018-08-21 | 医学研究理事会 | For generating method and compositions related and purposes through the ligand modified ferric hydroxide colloid of carboxylate radical |
| CN108430964B (en) * | 2015-10-09 | 2021-05-11 | 英国研究与创新署 | Methods for producing carboxylate ligand-modified ferric hydroxide colloids, and related compositions and uses |
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