CN102146140B - Method for preparing temperature-resistance modified water soluble cellulose ether - Google Patents
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- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/08—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with hydroxylated hydrocarbon radicals; Esters, ethers, or acetals thereof
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- C08B11/00—Preparation of cellulose ethers
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- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
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- C08B11/193—Mixed ethers, i.e. ethers with two or more different etherifying groups
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- C08B11/20—Post-etherification treatments of chemical or physical type, e.g. mixed etherification in two steps, including purification
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Abstract
The invention discloses a method for preparing temperature-resistance modified water soluble cellulose ether, which is characterized in that 20 parts of water soluble cellulose ether, 10 to 900 parts of solvent, 0.01 to 10 parts of catalyst are added into a three-opening reaction flask with a reflux condenser in part by weight; stirring and swelling the mixture for 24 hours at room temperature, heating to the temperature of 40 to 85 DEG C, slowly adding 0.1-15 parts of hydrochloric ether or hydrobromic ether modifier with the benzene rings, performing the reaction for 6 to 72 hours, removing the unreacted modifier and catalyst by precipitating and washing a reaction product by acetone, normal propyl alcohol or isopropanol, and filtering and drying for 4 to 8 hours in a vacuum oven at a temperature of 30 to 70 DEG C to obtain the temperature-resistance modified water soluble cellulose ether. Compared with the unmodified water soluble cellulose ether, the temperature-resistance modified water soluble cellulose ether has better temperature resistance, salt resistance and ageing resistance and smaller using amount. The temperature-resistance modified water soluble cellulose ether can be used as an oil displacement agent for tertiary oil recovery of intermediate and low permeability reservoirs, can also be used as a thickener and a polymer surfactant in drilling fluid or fracturing fluid and can also be subjected to crosslinking with an inorganic or organic agent to obtain weak gel used as the oil displacement agent, an oil displacement profile control agent, a profile control agent or a water shutoff agent.
Description
One, technical field
The present invention relates to a kind of preparation method of heatproof modified soluble ether of cellulose; This polymkeric substance can be used as the thickening material in oil-displacing agent, polymeric surface active agent, drilling fluid or the fracturing liquid in the TOR, belongs to organic chemistry, macromolecular material and raising oil recovery field.
Two, technical background
Mierocrystalline cellulose is the abundantest, reproducible in the world natural polymer; Because its aggregated structure characteristics and intermolecular and intramolecularly exist a lot of hydrogen bonds and higher percent crystallinity; Therefore; Can not be dissolved in water and the general organic and inorganic solvent, its intensity is also poor, causes its application to receive many restrictions.But with the Mierocrystalline cellulose is basic raw material, obtains soda cellulose through the alkalization swelling treatment, and carrying out ether of cellulose that etherification reaction obtains with etherifying agent halogenated alkane, halogenated carboxylic acid, halogenosulfonic acid or epoxy alkane then can be water-soluble.Ether of cellulose has widely in engineerings such as the probing of oil, Sweet natural gas, exploitation to be used; But common ether of cellulose can not be adapted to the exploitation requirement of high-temperature stratum and complex geological condition, and its use temperature is no more than 70 ℃, therefore; Be badly in need of improving its heatproof, tackify and ageing resistance; And generally compare at partially hydrolyzed polyacrylamide more than 10,000,000 and polyacrylamide derivative thereof with molecular weight, the molecular weight of ether of cellulose is lower, and its molecular weight is in 2.0 * 104～100 * 104 scopes; Compare with the synthetic polymer of polyacrylamide, its thickening property is relatively poor.But its molecular chain size can satisfy water survey rate of permeation be 50～500 (10-3 μ m) in, the requirement of low-permeability oil deposit; And also do not have at present reported in literature can be applicable in, the industrial polymer of development of low-permeability oil reservoir; China still adopts water injection technology to this type reservoir development; But because the nonuniformity of this type oil reservoir is serious; The water flooding recovery weak effect is trapped in the reservoir a large amount of irreducible oils, and secular water filling is washed away the pore texture that also makes oil reservoir, porosity, rate of permeation, rock surface wettability etc. significant change is taken place.Continuous expansion along with its Application Areas; Every profession and trade improves constantly what its use properties required; Though both at home and abroad the investigator has carried out a lot of modifications to water-soluble cellulose ether, mainly is in the molecular chain of water-soluble cellulose ether, to introduce chain alkyl, or with vinylformic acid, acrylic ester compound, acrylic amide and derivatives graft copolymerization thereof; But these modified soluble ether of cellulose at high temperature still are prone to oxidative degradation, and its maximum operation (service) temperature still is no more than 70 ℃.Li Qin; Hydrophobic association Natvosol and supramolecular aggregation structural research (Master's thesis thereof; Sichuan University); 2004,52-61 uses 1-bromododecane (BD), epoxy ten alkane (EP10), epoxy n-Hexadecane (EP16) and epoxy octadecane (EP18) that Natvosol (HEC) is carried out modification respectively; Obtained hydrophobic association Natvosol BD-HAHEC, EP10-HAHEC, EP16-HAHEC, EP18-HAHEC, found that 0.3g/dL BD-HAHEC and the viscosity of 0.25g/dL EP16-HAHEC in the 1.5%NaCl aqueous solution all raise with temperature and obviously decline; When temperature when 25 ℃ are increased to 50 ℃, the viscosity of BD-HAHEC solution is reduced to 20mPa.s from 165mPa.s, the viscosity conservation rate is 12%; Place the 0.3g/dL BD-HAHEC salt brine solution (not deoxygenation) that contains 1.5%NaCl 70 ℃ thermostat container after aging 20 days; The viscosity conservation rate reduces to 33%, the also further raising of this explanation modified soluble ether of cellulose solution thermostability at high temperature from 100%.Wei Yuping, the synthetic and performance characterization (Ph D dissertation, University Of Tianjin) of cellulose base polymeric surface active agent, 2005; 60-67 is a raw material with the Mierocrystalline cellulose, and capryl(yl)chloride is an acylating reagent; Prepared the Mierocrystalline cellulose decoyl ester of DS=0.43, and then be raw material, with HCIS0 with this modified-cellulose
3/ DMF is a sulfur acidizing reagent, has prepared polymeric surface active agent Mierocrystalline cellulose decoyl ester sodium sulfate.The ester group that this polymeric surface active agent contains makes polymkeric substance lose octyl group, thereby makes polymkeric substance lose surfactivity being higher than facile hydrolysis under 65 ℃ the temperature.
Three, summary of the invention
The objective of the invention is the present Research that remains further raising according at present heatproof, the ageing resistance high temperature (being higher than 70 ℃) under and the thickening property in pure water and salt solution of ether of cellulose; A kind of preparation method of heatproof modified soluble ether of cellulose is provided; And this modified cellulose ethers has the molecular association ability; Because of molecular weight low energy is used for, low-permeability oil deposit, be characterized in the water-soluble cellulose ether being raw material, with 4-C
1-18Alkyl benzyl bromine (C
mH
2m+1-C
6H
4-CH
2Br, m=1～18) and 4-C
1-18Alkyl benzyl chlorine (C
mH
2m+1-C
6H
4-CH
2Cl, m=1～18) at least a in is properties-correcting agent, with sodium hydroxide (NaOH), Pottasium Hydroxide (KOH), salt of wormwood (K
2CO
3), yellow soda ash (Na
2CO
3), saleratus (KHCO
3) and sodium hydrogencarbonate (NaHCO
3) at least a be catalyzer, with THF (THF), N, dinethylformamide (DMF), methyl alcohol, ethanol, 1, at least a in 4-dioxane, DMSO 99.8MIN. and the pyridine is solvent, reaction has obtained heatproof modified soluble ether of cellulose.
The mass ratio of various reaction conditionss such as water-soluble cellulose ether total concn, properties-correcting agent/water-soluble cellulose ether, temperature of reaction, catalyst levels, the solution behavior of reaction times to the modified soluble ether of cellulose had very big influence during the present inventor found to react.
The object of the invention is realized that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
1. the recipe ingredient of heatproof modified soluble ether of cellulose is:
20 parts of water-soluble cellulose ethers
0.1～15 part of properties-correcting agent
0.01～10 part of catalyzer
10～900 parts of solvents
Wherein water-soluble cellulose ether is CMC 99.5, sulfonic acid TKK 021, Tylose CH 50, hydroxyethylmethyl-cellulose, Vltra tears, hydroxy butyl methyl cellulose, Natvosol or hydroxypropylcellulose; Properties-correcting agent is 4-C
1-18Alkyl benzyl bromine (C
mH
2m+1-C
6H
4-CH
2Br, m=1～18) and 4-C
1-18Alkyl benzyl chlorine (C
mH
2m+1-C
6H
4-CH
2Cl, m=1～18) at least a in; Catalyzer is sodium hydroxide (NaOH), Pottasium Hydroxide (KOH), salt of wormwood (K
2CO
3), yellow soda ash (Na
2CO
3), saleratus (KHCO
3) and sodium hydrogencarbonate (NaHCO
3) at least a; Solvent is THF (THF), N, dinethylformamide (DMF), methyl alcohol, ethanol, 1, at least a in 4-dioxane, DMSO 99.8MIN. and the pyridine.
2. the preparation of heatproof modified soluble ether of cellulose
With 20 parts of water-soluble cellulose ethers, 10～900 parts of solvents, 0.01～10 part of adding of catalyzer is equipped with in three mouthfuls of reaction flasks of reflux condensate device; At room temperature stirred swelling 24 hours; Be warming up to 40～85 ℃ then, slowly add 0.1～15 part of properties-correcting agent, reacted 6～72 hours; Reaction product with acetone, n-propyl alcohol or isopropanol precipitating, washing, is removed unreacted properties-correcting agent and catalyzer, filter; Under 30～70 ℃ of temperature in vacuum drying oven dry 4-8 hour, obtain heatproof modified soluble ether of cellulose.
Wherein water-soluble cellulose ether is CMC 99.5, sulfonic acid TKK 021, Tylose CH 50, hydroxyethylmethyl-cellulose, Vltra tears, hydroxy butyl methyl cellulose, Natvosol or hydroxypropylcellulose; Properties-correcting agent is 4-C
1-18Alkyl benzyl bromine (C
mH
2m+1-C
6H
4-CH
2Br, m=1～18) and 4-C
1-18Alkyl benzyl chlorine (C
mH
2m+1-C
6H
4-CH
2Cl, m=1～18) at least a in; Catalyzer is sodium hydroxide (NaOH), Pottasium Hydroxide (KOH), salt of wormwood (K
2CO
3), yellow soda ash (Na
2CO
3), saleratus (KHCO
3) and sodium hydrogencarbonate (NaHCO
3) at least a; Solvent is THF (THF), N, dinethylformamide (DMF), methyl alcohol, ethanol, 1, at least a in 4-dioxane, DMSO 99.8MIN. and the pyridine.
3. the performance of heatproof modified soluble ether of cellulose
Following water-soluble cellulose ether is a Natvosol.
(1) relation of the solution AV of heatproof modified soluble ether of cellulose and concentration is as shown in table 1.The result shows, compares with unmodified water-soluble cellulose ether, and the modified soluble ether of cellulose has better tackifying ability, and the aqueous solution of its lower concentration also has higher AV.
(2) sodium chloride concentration is as shown in table 2 to the influence of heatproof modified soluble ether of cellulose solution AV.The result shows, compares with unmodified water-soluble cellulose ether, and modified soluble ether of cellulose solution shows as tangible salt thickening behavior, has better anti-salt property, and the polymers soln of high salt concentration (60g/LNaCl) has the highest viscosity number.
(3) relation of the temperature of heatproof modified soluble ether of cellulose and soltion viscosity is as shown in table 3, and in certain temperature range, polymers soln shows as tangible hot thickening behavior, explains that polymkeric substance has good heat resistance.
(4) aging resistance of heatproof modified soluble ether of cellulose is as shown in table 4.The result shows, compares with unmodified water-soluble cellulose ether, and the modified soluble ether of cellulose has better ageing resistance, and solution wears out and still has higher viscosity after three months.
4. the purposes of heatproof modified soluble ether of cellulose
During heatproof modified soluble ether of cellulose can be used as, the oil-displacing agent of low-permeability oil deposit TOR, also can be used as the thickening material in drilling fluid or the fracturing liquid, polymeric surface active agent; Also can obtain weak gel, as oil-displacing agent, adjusting driving agnet, amendment or plugging agent with inorganic or organic agent is crosslinked.
(1) heatproof modified soluble ether of cellulose being made into volume mass concentration is 0.3～3g/L; The molarity of tensio-active agent is the aqueous solution of 0.01～4mmol/L; Add and have in the mixing tank of whipping appts; At room temperature stir, i.e. acquisition is used for, the polymer oil-displacing agent of low-permeability oil deposit.
Wherein tensio-active agent is AS C
8-16Sodium alkyl benzene sulfonate or C
8-16Sodium alkyl sulfate; Cats product C
8-16Alkyl trimethyl bromine or ammonium chloride; Nonionogenic tenside C
8-16Alkyl dimethyl ammonium oxide or C
8-16At least a in the TX10.
(2) heatproof modified soluble ether of cellulose is made into the aqueous solution that volume mass concentration is 0.3～8g/L, adding has in the mixing tank of whipping appts, at room temperature stirs, and promptly obtains the thickening material in drilling fluid additive or the fracturing liquid.
(3) heatproof modified soluble ether of cellulose molecular weight is low, that modifier content is high is made into the aqueous solution that volume mass concentration is 0.3～4g/L, adds to have in the mixing tank of whipping appts, at room temperature stirs, and promptly obtains polymeric surface active agent solution.
(4) heatproof modified soluble ether of cellulose being made into volume mass concentration is 0.1～4g/L; The volume mass concentration of linking agent is 0.01～2.0g/L; The volume mass concentration of thermo-stabilizer S-WAT is the aqueous solution of 0.005～1.0g/L; Adding has in the mixing tank of whipping appts, at room temperature stirs regulator solution pH=4～11; Obtain the polymer solution system as the efficient gel of the displacement of reservoir oil, transfer drive, profile control or water blockoff, little gel that is cross-linked to form takes place in this polymer solution system in the flow process in oil reservoir.
Wherein linking agent be aluminum chloride, chromium chloride, SRM 935a/S-WAT, chromic formate, Chromic lactate, chromium acetate, chromium propionate, chromium butyrate, chromium+oxalic acid, propanedioic acid chromium, Tiorco 677, oligomeric resol, formaldehyde, oxalic dialdehyde, at least a in LUTARALDEHYDE, terpolycyantoamino-formaldehyde resin, phenol, pyrocatechol, Resorcinol, Resorcinol and the vulkacit H.
Heatproof modified soluble ether of cellulose of the present invention has following advantage:
The present invention is (4-C through the hydroxy functional group on the water-soluble cellulose ether molecular chain
1-18Alkyl) benzyl is incorporated into and prepares heatproof modified soluble ether of cellulose in its molecular chain; This modified cellulose ethers can as in, the displacement of reservoir oil polymkeric substance of low-permeability oil deposit; Compare with unmodified water-soluble cellulose ether; The heatproof and the ageing resistance of its solution obviously improve, and have the molecular association ability, and its consumption is lower.Though the molecular weight of the heatproof modified soluble ether of cellulose that the present invention obtains is not high; But the supramolecular structure that forms through intermolecular association makes it have the tackifying ability stronger than unmodified water-soluble cellulose ether, in having solved, low permeability pay requirement molecular weight is low and can anti-salt, the contradiction of heatproof, high tackify.Because properties-correcting agent 4-C
1-18Alkyl benzyl bromine (C
mH
2m+1-C
6H
4-CH
2Br, m=1～18) and 4-C
1-18Alkyl benzyl chlorine (C
mH
2m+1-C
6H
4-CH
2Cl; M=1～18) contain rigid heat resistant group phenyl ring in; Therefore, the introducing of properties-correcting agent not only makes water-soluble cellulose ether produce intermolecular association, has strengthened the tackifying ability of polymkeric substance; And increased whole molecule chain rigidity, thereby the heatproof of polymkeric substance, anti-salt and ageing resistance have been improved.In, in the low permeability pay; In having, the molecular dimension of low-molecular-weight modified soluble ether of cellulose determined this analog copolymer that the shearing as ultra-high molecular weight HPAM and high molecular weight acrylamide modified copolymer, the degraded or stop up of stretching can not take place, during its solution property also can meet fully, low-permeability oil deposit is to the requirement of displacement of reservoir oil polymkeric substance.In addition, molecular weight is lower than 30,000, and the heatproof modified soluble ether of cellulose that modifier content is high has good table/interfacial activity, can be used as polymeric surface active agent, can also be compound with other tensio-active agent.
Four, embodiment
Through embodiment the present invention is carried out concrete description below; Be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the researchist in this field can make some nonessential improvement and adjustment to the present invention according to the content of the invention described above.
Embodiment 1
With 20 parts of sulfonic acid TKK 021s, 30 parts of THFs, 0.8 part of adding of catalyzer is equipped with in three mouthfuls of reaction flasks of reflux condensate device, at room temperature stirs swelling 24 hours, is warming up to 55 ℃ then, slowly adds 1.5 parts of 4-tertiary butyl benzyl bromines, reacts 8 hours; Reaction product with acetone precipitation, washing, is filtered; Under 50 ℃ of temperature in vacuum drying oven dry 6 hours, obtain heatproof modification sulfonic acid TKK 021.
Embodiment 2
With 20 parts of CMC 99.5s, 105 parts of methyl alcohol, 3 parts of addings of catalyzer are equipped with in three mouthfuls of reaction flasks of reflux condensate device, at room temperature stir swelling 24 hours, are warming up to 65 ℃ then, slowly add 8 parts of 4-n-octyl benzyl bromines, react 16 hours; Reaction product with n-propyl alcohol deposition, washing, is filtered; Under 60 ℃ of temperature in vacuum drying oven dry 6 hours, obtain the heatproof modified carboxy methyl cellulose.
Embodiment 3
With 20 parts of Tylose CH 50s, N, 280 parts of dinethylformamides; 5 parts of addings of catalyzer are equipped with in three mouthfuls of reaction flasks of reflux condensate device, at room temperature stir swelling 24 hours, are warming up to 70 ℃ then; Slowly add 6 parts of 4-tertiary butyl benzyl chlorine, reacted 24 hours; Reaction product with isopropanol precipitating, washing, is filtered; Under 65 ℃ of temperature in vacuum drying oven dry 8 hours, obtain heatproof modified carboxy methyl Natvosol.
Embodiment 4
With 20 parts of Vltra tearss, 450 parts of ethanol, 7 parts of addings of catalyzer are equipped with in three mouthfuls of reaction flasks of reflux condensate device, at room temperature stir swelling 24 hours, are warming up to 80 ℃ then, slowly add 11 parts of 4-hexadecyl benzyl bromines, react 48 hours; Reaction product with acetone precipitation, washing, is filtered; Under 70 ℃ of temperature in vacuum drying oven dry 8 hours, obtain heatproof modification Vltra tears.
Embodiment 5
With 20 parts of hydroxypropylcelluloses, 1,700 parts of 4-dioxane, 9 parts of addings of catalyzer are equipped with in three mouthfuls of reaction flasks of reflux condensate device, at room temperature stir swelling 24 hours, are warming up to 85 ℃ then, slowly add 15 parts of 4-dodecyl benzyl chlorine, react 72 hours; Reaction product with isopropanol precipitating, washing, is filtered; Under 70 ℃ of temperature in vacuum drying oven dry 6 hours, obtain heatproof modification hydroxypropylcellulose.
Five, subordinate list explanation
The relation of table 1 polymer concentration and pure water solution AV
Table 2NaCl concentration is to the influence of salt brine solution AV
Annotate: polymer solution concentration: 3.0g/L
Table 3 temperature is to the influence of solution AV
Annotate: polymer solution concentration: 3.0g/L, NaCl concentration: 1.5g/dL
Table 4 copolymer solution viscosity is with the variation of digestion time
Annotate: polymer solution concentration: 3.0g/L, NaCl concentration: 1.5g/dL, aging temperature: 75 ℃
More than the AV in the table is except that specifying, test condition is 30 ℃, 7.34s
-1
Claims (1)
1. the preparation method of heatproof modified soluble ether of cellulose is characterized in that:
Each component by weight; With 20 parts of water-soluble cellulose ethers, 10～900 parts of solvents, 0.01～10 part of adding of catalyzer is equipped with in three mouthfuls of reaction flasks of reflux condensate device; At room temperature stirred swelling 24 hours; Be warming up to 40～85 ℃ then, slowly add 0.1～15 part of properties-correcting agent, reacted 6～72 hours; Reaction product with acetone, n-propyl alcohol or isopropanol precipitating, washing, is removed unreacted properties-correcting agent and catalyzer, filter; Under 30～70 ℃ of temperature in vacuum drying oven dry 4-8 hour, obtain heatproof modified soluble ether of cellulose;
Wherein water-soluble cellulose ether is CMC 99.5, sulfonic acid TKK 021, Tylose CH 50, hydroxyethylmethyl-cellulose, Vltra tears, hydroxy butyl methyl cellulose, Natvosol or hydroxypropylcellulose; Properties-correcting agent is 4-C
4-18Alkyl benzyl bromine C
mH
2m+1-C
6H
4-CH
2Br, m=4～18 and 4-C
4-18Alkyl benzyl chlorine C
mH
2m+1-C
6H
4-CH
2Cl, at least a in m=4～18; Catalyzer is at least a in sodium hydroxide, Pottasium Hydroxide, salt of wormwood, yellow soda ash, saleratus and the sodium hydrogencarbonate; Solvent is THF, N, dinethylformamide, methyl alcohol, ethanol, 1, at least a in 4-dioxane, DMSO 99.8MIN. and the pyridine.
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| CN102633887B (en) * | 2012-04-27 | 2014-03-26 | 泸州北方化学工业有限公司 | Modifying method of low viscosity cellulose ether |
| CN104449616A (en) * | 2014-11-24 | 2015-03-25 | 天津大港油田滨港集团博弘石油化工有限公司 | Compound cellulose indepth water shutoff modifying and flooding agent for oil production and preparation method thereof |
| CN104600318B (en) * | 2015-02-05 | 2017-05-10 | 天津市捷威动力工业有限公司 | Modified CMC and gel battery thereof |
| CN104804715B (en) * | 2015-03-18 | 2017-11-24 | 西南石油大学 | A kind of drilling well modified hydroxyethylcellulosadsorbing tackifier and preparation method thereof |
| CN106995685B (en) * | 2017-05-05 | 2019-11-15 | 东营黄蓝知识产权运营管理有限公司 | A method of preparing treating agent of drilling mud |
| CN108164607A (en) * | 2018-01-10 | 2018-06-15 | 成都理工大学 | A kind of preparation method of the water-soluble cellulose ether of organic branched modification |
| CN108906333A (en) * | 2018-07-05 | 2018-11-30 | 江西理工大学 | A kind of mineral floating separation inhibitor and preparation method thereof |
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| Shanshan Dai，et al."A Study on the Solution Behavior of IPBC-Hydrophobically-Modified Hydroxyethyl Cellulose".《Journal of Applied Polymer Science》.2006,第100卷(第4期),2824-2831. |
| Shanshan Dai,et al."A Study on the Solution Behavior of IPBC-Hydrophobically-Modified Hydroxyethyl Cellulose".《Journal of Applied Polymer Science》.2006,第100卷(第4期),2824-2831. * |
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