CN101935272A - Rare earth type water-base gel crosslinking agent and preparation method thereof - Google Patents
Rare earth type water-base gel crosslinking agent and preparation method thereof Download PDFInfo
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- CN101935272A CN101935272A CN2010102567992A CN201010256799A CN101935272A CN 101935272 A CN101935272 A CN 101935272A CN 2010102567992 A CN2010102567992 A CN 2010102567992A CN 201010256799 A CN201010256799 A CN 201010256799A CN 101935272 A CN101935272 A CN 101935272A
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Abstract
The invention discloses a rare earth type water-base gel crosslinking agent and a preparation method thereof. The method comprises the following steps of: uniformly mixing rare earth chloride and an alkali in water to react the rare earth chloride and the alkali, adding an organic acid into the reactant after the reaction, uniformly mixing the organic acid and the reactant to react the organic acid and the reactant, and obtaining the rare earth type water-base gel crosslinking agent after the reaction. The rare earth type water-base gel crosslinking agent provided by the invention has relatively low using concentration which is 300 to 500mg/L, and has good crosslinking effect on acrylamide polymer oil displacement agents, such as partial hydrolyzed polyacrylamide, hydrophobically associating polymer, amphiphilic polymer, comb-like polymers and the like, wherein the using concentration is 500mg/L and the rare earth type water-base gel crosslinking agent can form a crosslinked structure. The soltion viscosity is increased to 824.8mPa.s from 55.6mPa.s. Thus, the rare earth type water-base gel crosslinking agent has high application value.
Description
Technical field
The present invention relates to the linking agent field, particularly a kind of rare-earth type aqueous gel linking agent and preparation method thereof.
Background technology
Crosslinked aqueous gel be by water-soluble polymers (be generally partially hydrolyzed polyacrylamide, be called for short HPAM) and linking agent form a kind of can slowly crosslinked (based on intermolecular cross-linking, intramolecular crosslinking be auxilliary), the polymer gel that viscosity is controlled.Its characteristic is not only to have certain fluidity but also have certain intensity.Be widely used in the numerous areas of oil-gas minings such as profile control, water blockoff, acidifying, pressure break in recent years, the delayed cross-linking aqueous gel oil reservoir transfer drive method of utilizing the high infiltration of this kind system shutoff water filling macropore to form especially at present receives much concern.What linking agent application at present was more is phenolic crosslinkers, organoaluminum linking agent and organic chromium linking agent.Phenolic aldehyde, organoaluminum and organic chromium class linking agent environmental pollution are serious, can not satisfy eco-friendly requirement.Present existing linking agent is difficult to overcome above problem, thereby, demand developing a kind of novel environmental close friend's linking agent urgently.
Summary of the invention
The purpose of this invention is to provide a kind of rare-earth type aqueous gel linking agent and preparation method thereof.
The method for preparing rare-earth type aqueous gel linking agent provided by the invention comprises the steps:
Mixing in water reacts with rare earth chloride and alkali, adds the organic acid mixing again after reaction finishes and reacts, and reaction finishes and obtains described rare-earth type aqueous gel linking agent.
In the aforesaid method, the effective constituent of described rare earth chloride (this effective constituent is meant the compound that contains rare earth element in the rare earth chloride) is selected from least a in group of the lanthanides rare earth chloride and the actinium series rare earth chloride, and described group of the lanthanides rare earth chloride is selected from Lanthanum trichloride (LaCl
3), Cerium II Chloride (CeCl
3), Neodymium trichloride (NdCl
3) and praseodymium chloride (PrCl
3) at least a; Described actinium series rare earth chloride is selected from least a in chlorination actinium and the Thorium tetrachloride, the mixture that the effective constituent of described rare earth chloride preferably is made up of described group of the lanthanides rare earth chloride and described actinium series rare earth chloride, the more preferably mixture of forming by Lanthanum trichloride, Cerium II Chloride, Neodymium trichloride and praseodymium chloride.This rare earth chloride can be the mixture of being made up of following compound: LaCl
3, CeCl
3, NdCl
3, PrCl
3, La
2O
3, Na
2O, CaO, MgO, BaO, SrO and Fe
2O
3LaCl in this rare earth chloride
3, CeCl
3, NdCl
3, PrCl
3, La
2O
3, Na
2O, CaO, MgO, BaO, SrO and Fe
2O
3Mass ratio be 58.4: 10.8: 4.4: 3.2: 15.6: 4.3: 2.0: 0.8: 0.2: 0.1: 0.05, this rare earth chloride can be bought from open commercial sources and obtain, as can be available from the Shenyang bag with rare earth furnace charge company limited.Described alkali is selected from least a in sodium hydroxide and the potassium hydroxide, preferred sodium hydroxide.Described rare earth chloride, described alkali and described organic acid mol ratio are 2-2.5: 6-6.5: 3-3.5, specifically can be 2: 6: 3.0,2.5: 6.5: 3.5 or 2.5: 6.5: 3.0, preferred 2-2.2: 6-6.2: 3-3.2.
In this step, described rare earth chloride and alkali mixing in water carries out in the reactions steps, and temperature is 60-70 ℃, and the reaction times is 15-20 minute.This temperature of reaction must be controlled at 60-70 ℃ (comprising 60 ℃ and 70 ℃), is lower than 60 ℃ of reactions that other type can take place, and is higher than 70 ℃, gained reaction product rare earth hydrate instability.
Described organic acid is selected from least a in oxalic acid, toluylic acid, citric acid, phenylformic acid, Whitfield's ointment and the Glacial acetic acid, preferred oxalic acid.The described organic acid mixing that adds again carries out in the reactions steps, and temperature of reaction is 60-70 ℃, and the time is 20-30 minute.
In addition, prepare gained rare-earth type aqueous gel linking agent and this rare-earth type aqueous gel linking agent according to the method described above, also belong to protection scope of the present invention preparing oil-displacing agent or transfer drive with the application in the weak gel.Wherein, this weak gel can be the weak gel of partially hydrolyzed polyacrylamide.
With reactant selective chlorination rare earth (ReCl
3), sodium hydroxide and oxalic acid be example, the chemical equation of aforesaid method, as follows:
(1)ReCl
3+3NaOH→Re(OH)
3+3NaCl
(2)2Re(OH)
3+3HOOC-COOH→Re
2(COO-OOC)
3+6H
2O
In addition, the rare-earth type aqueous gel linking agent that utilizes above-mentioned preparation method to obtain, and, also belong to protection scope of the present invention in preparation oil-displacing agent, the especially application of cross-linking type aqueous gel.
Rare-earth type aqueous gel linking agent provided by the invention belongs to organo-metallic type linking agent, and the positively charged ion in this linking agent is a rare earth class.This linking agent has following feature: (1) has lower working concentration, is 300-500mg/L; (2) propionic acid amide polymer class oil-displacing agents such as partially hydrolyzed polyacrylamide, hydrophobic associated polymer, amphiphilic polymer and comb-shaped polymer all had good crosslinked action, when working concentration is 500mg/L, can form crosslinking structure, soltion viscosity rises to 824.8mPa.s by 55.6mPa.s.The method of the above-mentioned rare-earth type aqueous gel of preparation provided by the invention linking agent, technology is easy, the productive rate height, easy handling is suitable for scale operation.This rare-earth type aqueous gel linking agent can be used as the linking agent of oil-displacing agent, has important use and is worth.
Description of drawings
Fig. 1 is the rare-earth type aqueous gel dosage of crosslinking agent and the soltion viscosity relation curve of the embodiment of the invention 1 preparation.
Fig. 2 is the HPAM ydrodynamics radius distribution figure of the embodiment of the invention 1 preparation.
Fig. 3 is the weak gel ydrodynamics radius distribution figure of the crosslinked HPAM of rare-earth type aqueous gel linking agent of the embodiment of the invention 1 preparation.
Fig. 4 is the rare-earth type aqueous gel dosage of crosslinking agent and the soltion viscosity relation curve of the embodiment of the invention 2 preparations.
Fig. 5 is the weak gel stereoscan photograph of the crosslinked HPAM of rare-earth type aqueous gel linking agent of the embodiment of the invention 3 preparations.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.Method therefor is ordinary method if no special instructions among the following embodiment.The equal mixture for forming: the LaCl of used rare earth chloride among the following embodiment by following compound
3, CeCl
3, NdCl
3, PrCl
3, La
2O
3, Na
2O, CaO, MgO, BaO, SrO and Fe
2O
3LaCl in this rare earth chloride
3, CeCl
3, NdCl
3, PrCl
3, La
2O
3, Na
2O, CaO, MgO, BaO, SrO and Fe
2O
3Mass ratio be 58.4: 10.8: 4.4: 3.2: 15.6: 4.3: 2.0: 0.8: 0.2: 0.1: 0.05, all available from Shenyang bag with rare earth furnace charge company limited.The viscosity-average molecular weight of used partially hydrolyzed polyacrylamide is 1,600 ten thousand among the following embodiment, and degree of hydrolysis is 29.8%.
Embodiment 1, preparation rare-earth type aqueous gel linking agent
Rare earth chloride 70.8g (0.2mol) and sodium hydroxide 24g (0.6mol) are dissolved in the 200mL water, be heated to 60 ℃, after under agitation condition, reacting 15min, add 37.8g (0.3mol) oxalic acid again and react 20min at 60 ℃ under agitation condition, reaction finishes and obtains rare-earth type aqueous gel linking agent provided by the invention.
Detect according to the quality percentage composition of following method the rare earth in the above-mentioned rare-earth type aqueous gel linking agent:
With the described rare-earth type aqueous gel of the accurate weighing 0.5-1g of analytical balance linking agent (claiming accurate) to 0.0002g, place the 250ml Erlenmeyer flask, add 5ml HNO
3With 20ml H
2O loads onto the air reflux condensing tube, slowly heats with little fire, keeps little boiling, after decomposed sample, be suspended in grease above the solution be transparent till.Around hot water injection's condensation tube wall and bottle stopper, take off prolong and continue heating, little boiling a moment, make transparent dispersive oil ball strata become one, stop heating, cool to room temperature adds and then adopts red test paper one fritter, with mass percentage concentration is that 28% the ammoniacal liquor test paper that neutralizes is red-purple (the pH value is 5-6) to add 10ml pH value be that 5.6 acetate-sodium acetate buffer and 3-4 drip the xylenol orange indicator, and becoming yellow to solution by red-purple with the EDTA standard solution titration of 0.04799M is terminal point.
Calculate:
Wherein, Re% is the quality percentage composition of rare earth, and V is an EDTA titration volume, and M contains rare-earth compound (LaCl in the rare earth chloride
3, CeCl
3, NdCl
3And PrCl
3) mean value of molecular weight sum, m is the quality of testing sample.
I calculates according to formula, obtains this embodiment and prepares in the gained rare-earth type aqueous gel linking agent, and the quality percentage composition (Re%) of rare earth is 30.2%.
According to following method rare-earth type aqueous gel linking agent and partially hydrolyzed polyacrylamide being mixed in a little less than the normal temperature generation crosslinking reaction gained ydrodynamics radius of gel solution measures:
Utilize the QELS annex unit of the DAWN HELEOS of U.S. Wyatt company multi-angle laser light scattering instrument to carry out the off-line sample analysis, can obtain the hydrodynamic radius of prescribed concentration polymers soln as dynamic light scattering mensuration means.By the scattering of light intensity convection cell kinetics radius Rh mapping of aggregate in the solvent, obtain the size distribution of aggregate.Wherein, the collection of light scattering data and result's calculating obtains by ASTRA 5.3.2.10 software processes.In this method, the pore size filter that the scattering of light water is MST-I-10 ultrapure water machine outfit sartorius company product is that the processing of 0.45+0.2 μ m terminal micro-strainer obtains.The testing sample water solution system of configuration aperture after filtration is that the cellulose ester filtration of material head of 0.8 μ m is (available from Millipore company, model is MA) directly to filter in the scattering of light bottle, this scattering of light bottle is clean and standby with the masking foil parcel with surface washing with the preceding acetone elutriator that all places.
By Fig. 1-Fig. 3 as can be known, the consumption of this rare-earth type aqueous gel linking agent is when 300-500mg/L, the viscosity of the weak gel solution of crosslink part hydro-polyacrylamide (viscosity is that 55.6mPa.s, ydrodynamics radius mean value are 183.5875nm) back gained is brought up to 824.8mPa.s, ydrodynamics radius mean value is brought up to 1016.2893nm, has proved that rare-earth type aqueous gel linking agent that present embodiment provides and partially hydrolyzed polyacrylamide have formed crosslinking structure after crosslinked.
By Fig. 1 and 2 as can be known, utilize the weak gel of the crosslinked HPAM of rare-earth type aqueous gel linking agent to present reticulated structure, node density is very high, also can find below big mesh, to also have the little network structure of several layers, show and the weak gelatin polymer of HPAM and this embodiment prepare gained rare-earth type aqueous gel linking agent to carry out crosslinking reaction very abundant, the complex structure that forms, the system viscosity height.
Rare earth chloride 88.5g (0.25mol) and sodium hydroxide 26g (0.65mol) are dissolved in the 200mL water, be heated to 60 ℃, after under agitation condition, reacting 15min, add 44.1g (0.35mol) oxalic acid again and react 20min at 60 ℃ under agitation condition, reaction finishes and obtains rare-earth type aqueous gel linking agent provided by the invention.
Measuring the quality percentage composition of this rare-earth type aqueous gel linking agent middle-weight rare earths according to embodiment 1 described method, is 29.8%.By among Fig. 4 as can be known, this embodiment prepares gained rare-earth type aqueous gel dosage of crosslinking agent when 300-500mg/L, the viscosity of the weak gel solution of crosslink part hydro-polyacrylamide (viscosity is that 55.6mPa.s, ydrodynamics radius mean value are 183.5875nm) back gained is brought up to 822.9mPa.s, ydrodynamics radius mean value is brought up to 1016.2893nm, has proved that rare-earth type aqueous gel linking agent that present embodiment provides and partially hydrolyzed polyacrylamide have formed crosslinking structure after crosslinked.
Embodiment 3, preparation rare-earth type aqueous gel linking agent
Rare earth chloride 70.8g (0.2mol) and sodium hydroxide 26g (0.65mol) are dissolved in the 200mL water, be heated to 70 ℃, after under agitation condition, reacting 20min, add 44.1g (0.35mol) oxalic acid again and react 30min at 70 ℃ under agitation condition, reaction finishes and obtains rare-earth type aqueous gel linking agent provided by the invention.
Measuring the quality percentage composition of this rare-earth type aqueous gel linking agent middle-weight rare earths according to embodiment 1 described method, is 28.9%.This embodiment prepares gained rare-earth type aqueous gel dosage of crosslinking agent when 300-500mg/L, and the viscosity of the weak gel solution of crosslink part hydro-polyacrylamide (viscosity is 53.2mPa.s) back gained is brought up to 817.8mPa.s.
As shown in Figure 5, utilize the weak gel of the crosslinked HPAM of rare-earth type aqueous gel linking agent to present reticulated structure, node density is very high, also can find below big mesh, to also have the little network structure of several layers, show and the weak gelatin polymer of HPAM and this embodiment prepare gained rare-earth type aqueous gel linking agent to carry out crosslinking reaction very abundant, the complex structure that forms, the system viscosity height.
Embodiment 4, preparation rare-earth type aqueous gel linking agent
Rare earth chloride 88.5g (0.25mol) and sodium hydroxide 26g (0.65mol) are dissolved in the 200mL water, be heated to 65 ℃, after under agitation condition, reacting 20min, add 37.8g (0.3mol) oxalic acid again and react 20min at 65 ℃ under agitation condition, reaction finishes and obtains rare-earth type aqueous gel linking agent provided by the invention.
Measuring the quality percentage composition of this rare-earth type aqueous gel linking agent middle-weight rare earths according to embodiment 1 described method, is 28.7%.This embodiment prepares the viscosity of gained rare-earth type aqueous gel dosage of crosslinking agent gained weak gel solution in crosslink part hydro-polyacrylamide (viscosity is 54.8mPa.s) back when 300-500mg/L and brings up to 824.6mPa.s, has proved that rare-earth type aqueous gel linking agent that present embodiment provides and partially hydrolyzed polyacrylamide have formed crosslinking structure after crosslinked.
Claims (10)
1. a method for preparing rare-earth type aqueous gel linking agent comprises the steps:
Mixing in water reacts with rare earth chloride and alkali, adds the organic acid mixing again after reaction finishes and reacts, and reaction finishes and obtains described rare-earth type aqueous gel linking agent.
2. method according to claim 1 is characterized in that: the effective constituent of described rare earth chloride is selected from least a in group of the lanthanides rare earth chloride and the actinium series rare earth chloride; Described alkali is selected from least a in sodium hydroxide and the potassium hydroxide, preferred sodium hydroxide.
3. method according to claim 2 is characterized in that: described group of the lanthanides rare earth chloride is selected from least a in Lanthanum trichloride, Cerium II Chloride, Neodymium trichloride and the praseodymium chloride; Described actinium series rare earth chloride is selected from least a in chlorination actinium and the Thorium tetrachloride, and the effective constituent of described rare earth chloride is preferably mixture of being made up of described group of the lanthanides rare earth chloride and described actinium series rare earth chloride or the mixture of being made up of Lanthanum trichloride, Cerium II Chloride, Neodymium trichloride and praseodymium chloride.
4. according to the arbitrary described method of claim 1-3, it is characterized in that: described rare earth chloride, described alkali and described organic acid mol ratio are 2-2.5: 6-6.5: 3-3.5.
5. method according to claim 4 is characterized in that: described rare earth chloride, described alkali and described organic acid mol ratio are 2-2.2: 6-6.2: 3-3.2.
6. according to the arbitrary described method of claim 1-5, it is characterized in that: described rare earth chloride and alkali mixing in water carries out in the reactions steps, and temperature is 60-70 ℃, and the time is 15-20 minute.
7. according to the arbitrary described method of claim 1-6, it is characterized in that: described organic acid is selected from least a in oxalic acid, toluylic acid, citric acid, phenylformic acid, Whitfield's ointment and the Glacial acetic acid, preferred oxalic acid.
8. according to the arbitrary described method of claim 1-7, it is characterized in that: the described organic acid mixing that adds again carries out in the reactions steps, and temperature is 60-70 ℃, and the time is 20-30 minute.
9. the rare-earth type aqueous gel linking agent for preparing of the arbitrary described method of claim 1-8.
The described rare-earth type aqueous gel of claim 9 linking agent in preparation oil-displacing agent or transfer drive with the application in the weak gel.
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Cited By (7)
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| CN102504292A (en) * | 2011-10-31 | 2012-06-20 | 扬州润达油田化学剂有限公司 | Organic cross linking system for polymer flooding and preparation method of cross linking agent |
| CN102618247A (en) * | 2012-03-08 | 2012-08-01 | 中国海洋石油总公司 | Air-foam rare earth-base gel and preparation method thereof |
| CN104072651A (en) * | 2014-07-11 | 2014-10-01 | 安徽师范大学 | Method for synthesizing polyacrylamide with high molecular weight |
| CN106047330A (en) * | 2016-06-15 | 2016-10-26 | 中国海洋石油总公司 | Secondarily crosslinked aqueous gel crosslinking agent and preparation method and application thereof |
| CN108192586A (en) * | 2018-01-12 | 2018-06-22 | 中国石油大学(华东) | A kind of betaine type amphipathic polymer supermolecule oil displacement system and its construction method |
| CN109593575A (en) * | 2018-12-21 | 2019-04-09 | 南京科技职业学院 | A kind of preparation method of cerium based nano-material |
| CN109593576A (en) * | 2018-12-21 | 2019-04-09 | 南京科技职业学院 | A kind of cerium based nano-material and its application |
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| CN102504292A (en) * | 2011-10-31 | 2012-06-20 | 扬州润达油田化学剂有限公司 | Organic cross linking system for polymer flooding and preparation method of cross linking agent |
| CN102504292B (en) * | 2011-10-31 | 2013-10-02 | 扬州润达油田化学剂有限公司 | Organic cross linking system for polymer flooding and preparation method of cross linking agent |
| CN102618247A (en) * | 2012-03-08 | 2012-08-01 | 中国海洋石油总公司 | Air-foam rare earth-base gel and preparation method thereof |
| CN104072651A (en) * | 2014-07-11 | 2014-10-01 | 安徽师范大学 | Method for synthesizing polyacrylamide with high molecular weight |
| CN104072651B (en) * | 2014-07-11 | 2016-03-30 | 安徽师范大学 | A kind of synthetic method of polyacrylamide of high molecular |
| CN106047330A (en) * | 2016-06-15 | 2016-10-26 | 中国海洋石油总公司 | Secondarily crosslinked aqueous gel crosslinking agent and preparation method and application thereof |
| CN108192586A (en) * | 2018-01-12 | 2018-06-22 | 中国石油大学(华东) | A kind of betaine type amphipathic polymer supermolecule oil displacement system and its construction method |
| CN109593575A (en) * | 2018-12-21 | 2019-04-09 | 南京科技职业学院 | A kind of preparation method of cerium based nano-material |
| CN109593576A (en) * | 2018-12-21 | 2019-04-09 | 南京科技职业学院 | A kind of cerium based nano-material and its application |
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