CN101220260A - Method of producing novel sulfonation humic acid drilling mud modifying agent - Google Patents
Method of producing novel sulfonation humic acid drilling mud modifying agent Download PDFInfo
- Publication number
- CN101220260A CN101220260A CNA2007100632995A CN200710063299A CN101220260A CN 101220260 A CN101220260 A CN 101220260A CN A2007100632995 A CNA2007100632995 A CN A2007100632995A CN 200710063299 A CN200710063299 A CN 200710063299A CN 101220260 A CN101220260 A CN 101220260A
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- Prior art keywords
- sodium
- sulfonate
- drilling mud
- acid
- humic
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention provides a new method and a new technique for preparing a novel sulphonating humid acid drilling mud regulator, and is prepared by a reaction of cheap weathered coal, lignite, and material rich in humid acid with alkylbenzene sulfonate in a method prone to be industrialized. The prepared novel mud regulator has the advantages of possessing excellent properties of high temperature resistance, depressing viscosity, salt resistance, lowering dehydration and static shearing force, etc., and properties of hydrophile and drainage, good regulating effect for properties of the mud; the method also has the advantages that equipment can not be rusted; pollution to the environment is totally avoided; the process of the reacting technique is short; the application range is wide; the decomposition after the use is easy.
Description
Technical field
The invention belongs to the modification technology of drilling mud.More particularly, relate to the method for this novel sulfonation humic acid drilling mud modifying agent of a series of preparations.
Background technology
Humic acids (Humic acid is called for short HA) is a kind of polymer substance that extracts from soil, peat and brown coal, contains the various active group, has stronger physiologically active.China's resource of humic acid reserves are big, quality better, and development and use have a high potential, and it is cheap, adjust in the agent at drilling mud to have bigger advantage.Humic-acid-type substances is different from other natural macromoleculars, does not have certain complete structure and chemical structure.Because its toxic side effect is little, the scope of application is very wide.
The sulfonation or the sulfomethylation of humic acids (HA) class material are important problems.Because the introducing of sulfonic acid group, can improve humic acid substance water-soluble, salt tolerance, resistance to hard water and with exchange capacity of metal ion etc.All need its main raw material humic acids (HA) is introduced sulfonic acid group as cement water reducing agent, drilling mud adjustment agent etc.Conventional sulfonated reagent mainly contains NaHSO
3, Na
2SO
3Chlorsulfonic acid, the vitriol oil, and mineral resources humic acids molecule is bigger, general Direct Sulfonation or sulfomethylation be difficulty, usually need after oxidative degradation, just can reach comparatively ideal effect, just compare harshness like this to temperature, and then to the requirement of plant and instrument, and the adjustment agent after the sulfonation there is not tangible viscosity reducing effect to mud, the sulfonation common method generally is a vitriol oil method, promptly goes directly and the humic acid substance reaction with the vitriol oil under comparatively high temps.Though this method can be introduced sulfonic acid group, the solvability of product reduces greatly, and also is easy to destroy biological activity that reactant itself has etc. under hot conditions.
Adjust the shortcoming and defect of agent in order to overcome above-mentioned mud.Task of the present invention is to propose a kind of viscosity reduction that has the stratigraphical drilling use of humic acids and alkylbenzene sulfonate characteristics concurrently and falls the preparation method that leak-off mud is adjusted agent.Mud of the present invention is adjusted agent and is had good high temperature resistance drilling fluid rheology, viscosity reduction, lubricant effect, filtrate-loss control, contains hydrophilic and hydrophobic two kinds of performances simultaneously, and mud is had good adjustment effect.
Major technique of the present invention is characterised in that the material that uses cheap weathered coal, brown coal or be rich in humic acids is easy to industrialized method and alkyl benzene sulphonate (ABS) reactant salt as the main raw material employing.
Mud is adjusted agent and is made indispensable important component part in the drilling technology.The adjustment agent that has high temperature resistant, anti-salt simultaneously, falls dehydration, viscosity reduction, falls multiple functions such as gel strength is more needed.
The objective of the invention is to prepare a kind of multi-functional mud and adjust agent.That this adjustment agent has is high temperature resistant, viscosity reduction, anti-salt, fall dehydration, fall the high-performance of gel strength etc., especially has to embody good multifunctionality in high specific gravity mud.Can in deep-well, hot well, ultra deep well and offshore drilling, use.
Second purpose of the present invention is that the humic-acid kind drilling mud that adopts simple prepared to go out a kind of new system is adjusted agent.
Its preparation method is at first to prepare sodium salt with ordinary method from peat, weathering matchmaker, brown coal that contain humic acids or the material that is rich in humic acids.With after alkylbenzene sulfonate mixes, can add a little additive simultaneously then, pyroreaction a few hours, the cooling after drying obtains this product.
Described ordinary method has alkali-soluble acid analysis method, electroosmose process, membrane separation process, ion exchange method, inorganic salt extraction process, hydrofluoric acid deliming method etc.
Describedly be rich in the material of humic acids and the mass ratio of alkylbenzene sulfonate is 1: 0.1～1: 10.
Described additive has NaHSO
3, Na
2SO
3, K
2S
2O
8, Sodium dodecylbenzene sulfonate, hexamethyldisiloxane, hexamethyl siloxanes, cetyl trimethylammonium bromide, class of department, 4 bromide, Tetrabutyl amonium bromide, polyacrylamide, hydrolyzed polyacrylonitrile, sulfonated-pheno-formoldehyde resin etc.
The described reaction times is 1 hour～12 hours.
Novel sulfonation humic acid drilling mud modifying agent of the present invention is through 5% bentonite base slurry of HuaBei Petroleum Administrative Bureau preparation, and the salient features that records is as follows:
R, T-room temperature; The AV-apparent viscosity; The YP-yield value; The PV-plastic viscosity; 150/16 → RT-measures the HTHP dehydration: 150 ℃, measure under the 3.45MPa at normal temperatures through 150 ℃ after aging 16 hours
The concrete mode of implementing
Embodiment 1: the weathered coal of weighing 6.0g is poured in the there-necked flask in beaker, adds 81mL concentration simultaneously and be 1.5% NaOH solution; 98 ℃ were reacted 1～1.5 hour down, the centrifugal bottom precipitation of removing, p-hydroxy benzenyl sulfonate sodium is dissolved, then under the condition of high-speed stirring, splash in the sodium humate solution 75 ℃ of following reflux 0.5～1 hour, cooling at a slow speed, being acidified to pH value with the 0.2mol/L dilute sulphuric acid is 2～3, placement is grown up, and product liquid is dried down at 70～80 ℃ after centrifugation goes out throw out, promptly gets product.
Embodiment 2: the weathered coal of weighing 6.0g is poured in the there-necked flask in beaker, adds 81mL concentration simultaneously and be 1.5% NaOH solution; 98 ℃ were reacted 1～1.5 hour down, and the centrifugal bottom precipitation of removing adds K earlier under the condition of high-speed stirring
2S
2O
81.0g, then under water-bath refrigerative situation, dissolve the p-hydroxy benzenyl sulfonate sodium of 3.0g with the deionized water of 110mL, under the condition of high-speed stirring, splash in the sodium humate solution at a slow speed, 75 ℃ of following reflux 0.5～1 hour, cooling, being acidified to pH value with the 0.2mol/L dilute sulphuric acid is 2～3, placement is grown up, product liquid is dried down at 70～80 ℃ after centrifugation goes out throw out, promptly get product.
Embodiment 3: the weathered coal of weighing 6.0g is poured in the there-necked flask in beaker, adds 81mL concentration simultaneously and be 1.5% NaOH solution; 98 ℃ were reacted 1～1.5 hour down, the centrifugal bottom precipitation of removing, under the condition of high-speed stirring, add the 3.0g p-hydroxy benzenyl sulfonate sodium gradually in wherein, 75 ℃ of following reflux 0.5～1 hour, cooling, being acidified to pH value with the 0.2mol/L dilute sulphuric acid is 2～3, placement is grown up, product liquid is dried down at 70～80 ℃ after centrifugation goes out throw out, promptly get product.
Embodiment 4: the weathered coal of weighing 6.0g is poured in the there-necked flask in beaker, adds 81mL concentration simultaneously and be 1.5% NaOH solution; 98 ℃ of following condensing refluxes 1～1.5 hour, the centrifugal bottom precipitation of removing, under the condition of high-speed stirring, add 3.0g p-hydroxy benzenyl sulfonate sodium solid gradually in wherein, airtight heating is 2～3 hours under 160 ℃, cooling, being acidified to pH value with the 0.2mol/L dilute sulphuric acid is 2～3, placement is grown up, product liquid is dried down at 70～80 ℃ after centrifugation goes out throw out, promptly get product.
Embodiment 5: the weathered coal of weighing 15.0g is poured in the there-necked flask in beaker, adds 202mL concentration simultaneously and be 1.5% NaOH solution; 98 ℃ were reacted 1～1.5 hour down; the centrifugal bottom precipitation of removing; p-hydroxy benzenyl sulfonate sodium is dissolved; then under the condition of high-speed stirring, splash in the sodium humate solution at a slow speed; 75 ℃ of following reflux 0.5～1 hour; the cooling back adds hydrolyzed polyacrylonitrile solution 150mL and 5g ammonium persulphate; under nitrogen protection, heated and stirred slowly is warming up to 65 ℃ in 1 hour to dissolving; temperature control 65-75 ℃; behind the reaction 4h, with 3g sodium bisulfite termination reaction. the question response liquid cooling is the back discharging but, and it is concentrated; drying is pulverized and is promptly made this product.
Embodiment 6: step is with embodiment 1, but reacts after the acidifying without centrifugation, continues to be condensed into moisture 60～70% mashed prod, promptly gets product.
Claims (10)
1. the invention provides a kind of preparation method of novel sulfonation humic acid drilling mud modifying agent, it is characterized in that:
With one or more of weathered coal, brown coal, the material that is rich in humic acids, humic acids, potassium humate, Sodium salts humic acids, humic acids iron, ferripotassium humic acids, sodium humate sulfomethylation, nitro-humic acid sodium is raw material and alkylbenzene sulfonate reacting by heating, pyroreaction for some time under stirring condition, cooling, be acidified to certain pH value, sedimentation, separate, be drying to obtain this adjustment agent.
2. according to the method for claim 1 defined, it is characterized in that alkylbenzene sulfonate can be a perfluoro butyl sulfosalt, p-hydroxy benzenyl sulfonate sodium, fatty acid methyl ester sulfonate, the Vasoxyl mesylate, cyclamate sodium, sodium xylene sulfonate, m-nitrobenzene sodium sulfonate, tosic acid iron, tin methane sulfonate, sodium hydroxymethane sulfonate, sodium heptanesulfonate, sodium polystyrene sulfonate, the TANSHINONES sodium sulfonate, sodium diphenylaminesulfonate, sodium paeonol sulfonate, the cornel sodium sulfonate, toluenesulfonic acid sodium salt, sodium vinyl sulfonate, sodium naphthalene sulfonate, the methylol potassium sulfonate, Sugaron, paratoluenesulfonic acid sodium salt, sodium lignosulfonate, calcium lignin sulphonate, benzene sulfonic acid sodium salt.
3. according to the method for claim 1 defined, the quality that it is characterized in that the alkylbenzene sulfonate that adds is 0.1 times～10 times of quality that are rich in humic-acid-type substances.
4. according to the method for claim 1 defined, it is characterized in that temperature of reaction is 40 ℃～160 ℃.
5. according to the method for claim 1 defined, it is characterized in that acidifying pH value is 1-7.
6. according to the method for claim 1 defined, it is characterized in that the pyroreaction time is 1～12 hour.
7. according to the method for claim 1 defined, it is levied and is that described this drilling mud is adjusted the agent drilling mud adjusts agent, with one or more composite dose carry out compositely, obtain the compound adjustment agent, join in the bentonite base slurry, can produce good drilling mud modified effect.
8. according to the method for claim 7 defined, composite dose can be Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, sodium stearate, hexamethyldisiloxane, hexamethyl siloxanes, cetyl trimethylammonium bromide, class of department, 4 bromide, Tetrabutyl amonium bromide, polyacrylamide, hydrolyzed polyacrylonitrile, sulfonated-pheno-formoldehyde resin.
9. according to the method for claim 7 defined, it is characterized in that composite dose the quality that adds is 0.01 times～100 times of this novel drilling mud quality of adjusting agent.
10. according to the method for claim 7 defined, it is characterized in that composite method has that 1. physical property is composite, is mechanically to reconcile into mixture to composite dose with this novel sulfonation humic acid drilling mud modifying agent by mass ratio.2. chemical is composite vacuum impregnation technology, microemulsion method, normal temperature synthesis method, a supercritical methanol technology.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100632995A CN101220260A (en) | 2007-01-08 | 2007-01-08 | Method of producing novel sulfonation humic acid drilling mud modifying agent |
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|---|---|---|---|
| CNA2007100632995A CN101220260A (en) | 2007-01-08 | 2007-01-08 | Method of producing novel sulfonation humic acid drilling mud modifying agent |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857798A (en) * | 2010-06-10 | 2010-10-13 | 西安石油大学 | Preparation method of aminated lignin drilling fluid treating agent |
| CN102311726A (en) * | 2011-06-08 | 2012-01-11 | 河南金马石油科技有限责任公司 | Method for preparing fluid loss agent |
| CN103342588A (en) * | 2013-07-08 | 2013-10-09 | 山东创新腐植酸科技股份有限公司 | Preparation method of high-hardness water-resistant modified potassium fulvic acid powder |
| CN103539952A (en) * | 2012-07-10 | 2014-01-29 | 厦门大学 | Novel humic acid sulfonatiion process |
| CN105858835A (en) * | 2016-04-21 | 2016-08-17 | 陈仙 | Coal slurry settling agent and coal slurry settling method |
| CN106753284A (en) * | 2017-01-05 | 2017-05-31 | 中国科学院化学研究所 | A kind of viscosity reducer for crude oil and preparation method thereof |
| CN106978152A (en) * | 2017-04-24 | 2017-07-25 | 平利县双泰重晶石粉有限责任公司 | A kind of barite thinner, its preparation method and application |
| CN109019883A (en) * | 2018-08-15 | 2018-12-18 | 鞍钢贝克吉利尼水处理有限公司 | Phosphate-free corrosion inhibition antisludging agent and preparation method thereof for Waste Water Reuse technology |
| CN109913186A (en) * | 2019-04-10 | 2019-06-21 | 陕西延长石油（集团）有限责任公司 | A kind of assistant for drilling petroleum well and preparation method thereof |
| CN111040740A (en) * | 2019-12-25 | 2020-04-21 | 濮阳中原三力实业有限公司 | Preparation method of persistent high-temperature-resistant salt-resistant filtrate reducer |
| CN111268687A (en) * | 2020-03-06 | 2020-06-12 | 浙江丰虹新材料股份有限公司 | Organic clay composition and preparation method thereof |
| CN111334278A (en) * | 2020-04-16 | 2020-06-26 | 陕西科技大学 | Sulfonated humic acid fracturing fluid and preparation method thereof |
| CN113735395A (en) * | 2021-10-19 | 2021-12-03 | 陕西科技大学 | Rhamnolipid humic acid type oil well slurry treating agent and preparation method and application thereof |
| CN114805705A (en) * | 2022-06-06 | 2022-07-29 | 河南黑色生态科技有限公司 | High-temperature-resistant filtrate loss reducer sodium humate for well drilling and preparation method thereof |
| CN115093405A (en) * | 2022-05-20 | 2022-09-23 | 河北萌帮生物科技有限公司 | High-hardness water resistant sulfonated humic acid and preparation method thereof |
| CN115364640A (en) * | 2022-08-03 | 2022-11-22 | 广西壮族自治区海洋环境监测中心站 | Modified humate and application thereof in strengthening calcium hydroxide desulfurization |
-
2007
- 2007-01-08 CN CNA2007100632995A patent/CN101220260A/en active Pending
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857798B (en) * | 2010-06-10 | 2012-12-26 | 西安石油大学 | Preparation method of aminated lignin drilling fluid treating agent |
| CN101857798A (en) * | 2010-06-10 | 2010-10-13 | 西安石油大学 | Preparation method of aminated lignin drilling fluid treating agent |
| CN102311726A (en) * | 2011-06-08 | 2012-01-11 | 河南金马石油科技有限责任公司 | Method for preparing fluid loss agent |
| CN102311726B (en) * | 2011-06-08 | 2013-08-28 | 河南金马石油科技有限责任公司 | Method for preparing fluid loss agent |
| CN103539952A (en) * | 2012-07-10 | 2014-01-29 | 厦门大学 | Novel humic acid sulfonatiion process |
| CN103342588B (en) * | 2013-07-08 | 2014-12-17 | 山东创新腐植酸科技股份有限公司 | Preparation method of high-hardness water-resistant modified potassium fulvic acid powder |
| CN103342588A (en) * | 2013-07-08 | 2013-10-09 | 山东创新腐植酸科技股份有限公司 | Preparation method of high-hardness water-resistant modified potassium fulvic acid powder |
| CN105858835A (en) * | 2016-04-21 | 2016-08-17 | 陈仙 | Coal slurry settling agent and coal slurry settling method |
| CN106753284A (en) * | 2017-01-05 | 2017-05-31 | 中国科学院化学研究所 | A kind of viscosity reducer for crude oil and preparation method thereof |
| CN106753284B (en) * | 2017-01-05 | 2019-03-19 | 中国科学院化学研究所 | A kind of viscosity reducer for crude oil and preparation method thereof |
| CN106978152A (en) * | 2017-04-24 | 2017-07-25 | 平利县双泰重晶石粉有限责任公司 | A kind of barite thinner, its preparation method and application |
| CN109019883B (en) * | 2018-08-15 | 2022-04-01 | 鞍钢栗田(鞍山)水处理有限公司 | Non-phosphorus corrosion and scale inhibitor for industrial sewage reuse technology and preparation method thereof |
| CN109019883A (en) * | 2018-08-15 | 2018-12-18 | 鞍钢贝克吉利尼水处理有限公司 | Phosphate-free corrosion inhibition antisludging agent and preparation method thereof for Waste Water Reuse technology |
| CN109913186A (en) * | 2019-04-10 | 2019-06-21 | 陕西延长石油（集团）有限责任公司 | A kind of assistant for drilling petroleum well and preparation method thereof |
| CN111040740A (en) * | 2019-12-25 | 2020-04-21 | 濮阳中原三力实业有限公司 | Preparation method of persistent high-temperature-resistant salt-resistant filtrate reducer |
| CN111268687A (en) * | 2020-03-06 | 2020-06-12 | 浙江丰虹新材料股份有限公司 | Organic clay composition and preparation method thereof |
| CN111334278A (en) * | 2020-04-16 | 2020-06-26 | 陕西科技大学 | Sulfonated humic acid fracturing fluid and preparation method thereof |
| CN113735395A (en) * | 2021-10-19 | 2021-12-03 | 陕西科技大学 | Rhamnolipid humic acid type oil well slurry treating agent and preparation method and application thereof |
| CN113735395B (en) * | 2021-10-19 | 2022-11-04 | 陕西科技大学 | Rhamnolipid humic acid type oil well slurry treating agent and preparation method and application thereof |
| CN115093405A (en) * | 2022-05-20 | 2022-09-23 | 河北萌帮生物科技有限公司 | High-hardness water resistant sulfonated humic acid and preparation method thereof |
| CN114805705A (en) * | 2022-06-06 | 2022-07-29 | 河南黑色生态科技有限公司 | High-temperature-resistant filtrate loss reducer sodium humate for well drilling and preparation method thereof |
| CN114805705B (en) * | 2022-06-06 | 2024-04-19 | 河南黑色生态科技有限公司 | High-temperature-resistant filtrate reducer sodium humate for well drilling and preparation method thereof |
| CN115364640A (en) * | 2022-08-03 | 2022-11-22 | 广西壮族自治区海洋环境监测中心站 | Modified humate and application thereof in strengthening calcium hydroxide desulfurization |
| CN115364640B (en) * | 2022-08-03 | 2023-03-17 | 广西壮族自治区海洋环境监测中心站 | Modified humate and application thereof in strengthening calcium hydroxide desulfurization |
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Open date: 20080716 |