CN103087202A - Preparation method of polyanionic cellulose with ultrahigh viscosity for water-based drilling fluid - Google Patents

Preparation method of polyanionic cellulose with ultrahigh viscosity for water-based drilling fluid Download PDF

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CN103087202A
CN103087202A CN2012105552663A CN201210555266A CN103087202A CN 103087202 A CN103087202 A CN 103087202A CN 2012105552663 A CN2012105552663 A CN 2012105552663A CN 201210555266 A CN201210555266 A CN 201210555266A CN 103087202 A CN103087202 A CN 103087202A
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etherifying agent
purified cotton
sodium hydroxide
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陈网根
朱国生
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HANGZHOU HONGBO CHEMICAL CO Ltd
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Abstract

The invention relates to the technical field of production of polyanionic cellulose, and discloses a preparation method of polyanionic cellulose with an ultrahigh viscosity for a water-based drilling fluid. The preparation method comprises the steps of: (1) uniformly mixing a sodium hydroxide aqueous solution with ethanol water solution to obtain an alcohol-alkali mixture with a temperature of 8-13 degrees centigrade; (2) after tearing up refined cotton with high degree of polymerization, putting into a kneader together with the alcohol-alkali mixture to alkalize the refined cotton at the low temperature; (3) after the alkalization is finished, adding an etherifying agent, adding the sodium hydroxide after the etherifying agent is completely added, and then raising the temperature to 75-80 DEG C for etherification reaction; and (4) after the etherification reaction is finished, neutralizing a product to the pH value of 7-7.5, and thereby obtaining the polyanionic cellulose with the ultrahigh viscosity for the water-based drilling fluid after washing, drying and crushing. The polyanionic cellulose prepared by the preparation method disclosed by the invention is ultrahigh in viscosity, low in production cost, and good in salt resistance, high in apparent viscosity and low in filter loss when being applied to water-based drilling fluid.

Description

The water-base drilling fluid preparation method of hyperviscosity Polyanionic Cellulose
Technical field
The present invention relates to the Polyanionic Cellulose production technical field, particularly a kind of water-base drilling fluid preparation method of hyperviscosity Polyanionic Cellulose.
Background technology
Drilling fluid is divided into oil base drilling fluid and water-base drilling fluid.Along with the more and more stricter environmental legislation in the whole world, water-base drilling fluid is because polluting the little main flow that becomes.And the fluid loss agent of cellulose family, rheology modifier have the advantages that the source is abundant, biodegradable, pollution is little, and main products is Xylo-Mucine (CMC-Na) and Polyanionic Cellulose (PAC).They are that consumption is maximum up to now, and purposes is the most extensive, eco-friendly filtrate reducer for drilling fluid, rheology modifier.
Along with petroleum prospecting develops under the stratum, ocean, the formation condition that spuds in is increasingly harsh, and drilling depth is increasing.Generally, 1000 meters of the downward every extensions of drilling depth, downhole temperature can raise 30 ℃, and when well depth reached 4000 meters, temperature can raise 120 ℃.So high temperature resistance, salt tolerant requirement for components of drilling liquid are more and more higher, to the also raising thereupon of anti-degraded requirement of filtration reduction and viscosity number and viscosity.Common CMC-Na and PAC can not meet the demands.Domestic CMC-Na and PAC manufacturer are owing to all adopting the simple technique of mediating, and low times amount ethanol is made solvent.Can only produce common CMC-Na and PAC product.These products can only satisfy on land the needs with the drilling fluid of shallow well mostly.Tracing it to its cause, is that area of dissipation is little because in domestic conversion unit and technique, conduct heat not rapid.When alkalization and interpolation Mono Chloro Acetic Acid, inevitably make material be in strong basicity and higher temperature; The local superheating of material causes etherification temperature also will inevitably raise.Its consequence is cellulosic cracking, and the reduction of viscosity also has the problems such as etherification reaction is inhomogeneous.So it is the PAC that the slurry process of solvent is produced that domestic PAC performance does not all reach the developed countries Virahol.In order to satisfy the offshore drilling that day by day increases and the drilling well of other complex stratum condition, to domestic existing main equipment and technique is improved and necessary additional be imperative.
The disclosure of the invention of notification number CN101838333A a kind of preparation method of PAC HV.This preparation method is take purified cotton as cellulosic material, and the step that comprises has cellulosic alkalization, cellulosic aftertreatment with etherifying agent mixing, cellulosic etherificate, neutralization washing, product; Described preparation method also comprises the crosslinking reaction step, described crosslinking reaction step be described cellulosic etherificate and described in and carry out between washing step, described crosslinking reaction step is with linking agent N, and N '-methylene-bisacrylamide joins and carries out crosslinking reaction in Polyanionic Cellulose.The weak point that wherein exists is: 1, before the alkalization, the raw material such as alkali, alcohol before advancing kneader without any processing, only carrying out the 10-30min short period of time in kneader gives mixed, (longer time is also impossible, because the long-staying of reactant in this equipment, can have a strong impact on the output of whole production line), like this, because starting temperature is high, Mierocrystalline cellulose is because alkaline bleach liquor cleavage is again thermopositive reaction, cause the alkalization starting temperature can be higher, the alkalization starting temperature be one of key factor that affects product viscosity, can cause like this decline of the finished product viscosity; 2, during whole alkalization, temperature is also higher, at 15-40 ℃, has affected largely the acquisition of high-viscosity products, and product viscosity is not high, causes filter loss higher when being used for water-base drilling fluid, and salt resistant character is relatively poor.3, etherifying agent still uses single Mono Chloro Acetic Acid, will inevitably make like this consumption of alkali very large, and the thermal discharge that reacts when alkalization, etherificate is larger, causes the viscosity of product that larger decline is arranged.Although when their product arrived 0.99-1.03 when substitution value, the Brookfield viscosity of 1% aqueous solution was that the PAC(of 6300-7000mpa.s namely replaces uniform CMC) product, the external high level of distance also has gap.
United States Patent (USP) 7,384, the patent of 892 B2 that is CN1989219A adopts the raw cotton linters to make raw material, make solvent with Virahol-methanol mixed solvent, prepared substitution value with slurry method and arrived at 1.18 o'clock, the Brookfield viscosity of 1% aqueous solution is that the PAC(of 9913 mpa.s namely replaces uniform CMC) product.But the production technique of external this high performance PAC product is slurry method, namely the high power solvent method.Preparation PAC cost is too high, and solvent for use is that the price of Virahol is again a times of domestic CMC producer alcohol solvent price used.PAC product obvious shortage on market with the slurry method preparation is striven power unexpectedly.
Summary of the invention
The object of the invention is to overcome the defects that exists on prior art, water-base drilling fluid that a kind of performance the is equivalent to external high performance PAC product preparation method with the hyperviscosity Polyanionic Cellulose is provided, prepared Polyanionic Cellulose has the viscosity of superelevation, when being used for water-base drilling fluid, salt resistant character is good, apparent viscosity is high, and filter loss is low.
The technical solution adopted for the present invention to solve the technical problems is:
A kind of water-base drilling fluid preparation method of hyperviscosity Polyanionic Cellulose, described preparation method's step is as follows:
(1) under water at low temperature is cooling, mass concentration 45-50% aqueous sodium hydroxide solution and the mass concentration 85-95% aqueous ethanolic solution weight ratio by 1:1.4-2.5 is mixed, obtain the alcohol-alkali mixed solution of 8-13 ℃.
This step is one of crucial inventive point of the present invention, the present invention breaks through routine, at first the alcohol that the uses-alkali raw material that will alkalize carries out subzero treatment outside kneader, and then advance kneader and purified cotton quaternization, can obviously reduce like this temperature when especially initial (temperature) of quaternization, can not have the generation of local superheating, the good uniformity of purified cotton alkalization, having reduced purified cotton is cellulosic cracking, thereby improves product viscosity.
(2) the high-polymerization degree purified cotton is torn up after, drop in kneader with alcohol-alkali mixed solution, in purified cotton and alcohol-alkali mixed solution, the mol ratio of alkali is 1:1.9-2.5, purified cotton is carried out low temperature alkalizes, alkalization temperature 8-13 ℃, alkalization time 30-60min.
Alkalization temperature, and the temperature of alkalization raw alcohol-alkali mixed solution control consistent, the good uniformity that the purified cotton that can guarantee to alkalize is alkalized, the quality of product is good.the temperature control of alkalization raw alcohol-alkali mixed solution and the control of alkalization temperature are extremely crucial on the impact of product viscosity, the contriver finds through long-term exploration practice, 13 ℃ of alkalization temperatures are threshold values, this is a non-obvious feature for the routine techniques personnel, alkalization temperature is over 13 ℃, rising along with temperature, the viscosity of product can obviously descend, therefore the present invention controls alkalization temperature below 13 ℃, temperature is low, and to have reduced purified cotton be cellulosic cracking, be beneficial to the raising product viscosity, but in commercial process, temperature is lower, the apparatus expensive that needs, and condition is harsh, production cost is high, therefore, consider with the balance of product performance (better performance) for satisfying suitability for industrialized production demand (lower production cost), control alkalization temperature, and the temperature of alkalization raw alcohol-alkali mixed solution is all at 8-13 ℃.
(3) after alkalization finishes, add etherifying agent, the mol ratio of etherifying agent and purified cotton is 1.4-2.0:1, after etherifying agent adds, add secondary sodium hydroxide, the mol ratio of sodium hydroxide and purified cotton is 0.1-0.2:1, then is warming up to 75-80 ℃ of etherification reaction 35-90min.
In prior art, usually be sodium hydroxide disposable adding when alkalization with alkali, certainly will cause like this thermal discharge of quaternization large, and in kneader, alkali concn is also larger, the also corresponding increase of demand that adds etherifying agent (conventional is Mono Chloro Acetic Acid), a large amount of acid and the heat release of alkali neutralization reaction when causing adding etherifying agent produces amount of heat, seriously reduces the viscosity of product.Therefore, the present invention takes that alkalization finishes, etherifying agent adds sodium hydroxide after adding again, and the original alkali that once adds is separated into present twice and adds alkali, and the thermal discharge that can effectively control like this reaction is excessive, guarantees that product has high viscosity.
(4) after etherification reaction finished, product was neutralized to pH to 7-7.5, obtained water-base drilling fluid hyperviscosity Polyanionic Cellulose through washing, oven dry, pulverizing.
As preferably, the described etherifying agent of step (3) is that sodium chloroacetate and Mono Chloro Acetic Acid are the mixture of 0.5-3:1 in molar ratio, and etherifying agent adds with the ethanolic soln form, and the mass percent that described etherifying agent accounts for ethanolic soln is 50-75%.Sodium chloroacetate adds with fine powder.
Adopting the combination etherifying agent is another crucial inventive point of the present invention, the contriver breaks through the pattern that routine adds single Mono Chloro Acetic Acid etherifying agent, develop a kind of novel combination etherifying agent, by adding of sodium chloroacetate, the alkali consumption in the time of can reducing alkalization, acid (Mono Chloro Acetic Acid) consumption in the time of reducing etherificate again, like this, no matter alkalize or etherificate, the heat release of reaction system is controlled to greatest extent to be reduced, can effectively reduce the viscosity loss of purified cotton like this, greatly improve product viscosity.
The purpose of alkalization is to obtain sodium cellulosate, goes back remainder alkali, and in next step etherificate, etherifying agent (Mono Chloro Acetic Acid) the remaining alkali of alkalization that can neutralize obtains sodium chloroacetate, and then sodium cellulosate and sodium chloroacetate react the acquisition Polyanionic Cellulose.And adopt combination etherifying agent of the present invention, sodium chloroacetate directly just has suitable share, need not a large amount of alkali (alkalization remainder alkali) obtains with chloroacetate reaction, can effectively reduce so the required alkali number of alkalization, also can reduce the required acid amount of etherificate, no matter alkalize or etherificate, the heat release of reaction system is controlled to greatest extent to be reduced, can effectively reduce the viscosity loss of purified cotton like this, greatly improve product viscosity.
As preferably, the joining day of the described etherifying agent of step (3) is controlled at 20-50min, and during etherifying agent adds, temperature is controlled at below 25 ℃.Be beneficial to the raising product viscosity.
As preferably, during adding, etherifying agent adds linking agent, and the consumption of linking agent is the 0.2-1.0% of purified cotton weight.As preferably, described linking agent is selected from a kind of in dichloro acetic acid, Epicholorohydrin, propylene chlorohydrin, and it is to add after 3%-5% that linking agent is diluted with ethanol to mass concentration again.
Use linking agent can greatly improve the viscosity of product, the contriver invents by practical exploration, and linking agent is selected from a kind of in dichloro acetic acid, Epicholorohydrin, propylene chlorohydrin, and result of use is best, improves effective to the viscosity of product.
As preferably, the polymerization degree of the described high-polymerization degree purified cotton of step (2) is more than 2600.The original viscosity of purified cotton is high like this, and products obtained therefrom viscosity is also secure.
As preferably, after step (2) is torn up the high-polymerization degree purified cotton, after dropping in kneader with alcohol-alkali mixed solution, be filled with nitrogen in the kneader and get rid of oxygen in kneader.It is cellulosic cracking that eliminating oxygen can reduce purified cotton, is beneficial to the raising product viscosity.
As preferably, it is that the form of chip solid or the aqueous solution adds that step (3) adds the sodium hydroxide of sodium hydroxide, and the sodium hydroxide mass concentration in the aqueous solution is 45-50%.
The invention has the beneficial effects as follows: prepared Polyanionic Cellulose has the viscosity of superelevation, and production cost is low, and when being used for water-base drilling fluid, salt resistant character is good, and apparent viscosity is high, and filter loss is low.
Embodiment
Below by specific embodiment, technical scheme of the present invention is described in further detail.
In the present invention, if not refer in particular to, the raw material that adopts and equipment etc. all can be buied from market or this area is commonly used.Method in following embodiment if no special instructions, is the ordinary method of this area.
Embodiment 1:
(1) under water at low temperature is cooling, mass concentration 45% aqueous sodium hydroxide solution and the mass concentration 95% aqueous ethanolic solution weight ratio by 1:1.4 is mixed, obtain the alcohol of 8 ℃ of left and right-alkali mixed solution;
(2) high-polymerization degree purified cotton (polymerization degree is more than 2600) is torn up after, after dropping in kneader with alcohol-alkali mixed solution, be filled with nitrogen in the kneader and get rid of oxygen in kneader; In purified cotton and alcohol-alkali mixed solution, the mol ratio of alkali is 1:1.9, and purified cotton is carried out the low temperature alkalization, and alkalization temperature is controlled 8 ℃ of left and right, alkalization time 60min;
(3) after alkalization finishes, add etherifying agent, the mol ratio of etherifying agent and purified cotton is 1.4:1, described etherifying agent is that sodium chloroacetate and Mono Chloro Acetic Acid are the mixture of 2.6:1 in molar ratio, Mono Chloro Acetic Acid in etherifying agent adds with the ethanolic soln form, and the mass percent that the Mono Chloro Acetic Acid in described etherifying agent accounts for ethanolic soln is 75%; Sodium chloroacetate adds with fine powder.The joining day of described etherifying agent is controlled at 20min, and during etherifying agent adds, temperature is controlled at below 25 ℃; Add linking agent during etherifying agent adds, the consumption of linking agent is 0.2% of purified cotton weight, and linking agent is dichloro acetic acid, and it is to add after 3% that linking agent is diluted with ethanol to mass concentration again; After etherifying agent adds, add sodium hydroxide, the mol ratio of sodium hydroxide and purified cotton is 0.1:1, then is warming up to 80 ℃ of etherification reaction 35min;
(4) after etherification reaction finished, product was neutralized to pH to 7-7.5, obtained water-base drilling fluid hyperviscosity Polyanionic Cellulose through washing, oven dry, pulverizing, detected data and saw Table 1.
Table 1
Figure 2012105552663100002DEST_PATH_IMAGE002
Embodiment 2:
(1) under water at low temperature is cooling, mass concentration 49% aqueous sodium hydroxide solution and the mass concentration 88% aqueous ethanolic solution weight ratio by 1:2.0 is mixed, obtain the alcohol of 13 ℃ of left and right-alkali mixed solution;
(2) high-polymerization degree purified cotton (polymerization degree is more than 2600) is torn up after, after dropping in kneader with alcohol-alkali mixed solution, be filled with nitrogen in the kneader and get rid of oxygen in kneader; In purified cotton and alcohol-alkali mixed solution, the mol ratio of alkali is 1:2.2, and purified cotton is carried out low temperature alkalization, alkalization temperature 13 ℃ of left and right, alkalization time 30min;
(3) after alkalization finishes, add etherifying agent, the mol ratio of etherifying agent and purified cotton is 1.6:1, described etherifying agent is that sodium chloroacetate and Mono Chloro Acetic Acid are the mixture of 0.4:1 in molar ratio, in etherifying agent, Mono Chloro Acetic Acid adds with the ethanolic soln form, the mass percent that Mono Chloro Acetic Acid accounts for ethanolic soln is 50%, and sodium chloroacetate adds with fine powder.The joining day of described etherifying agent is controlled at 50min, and during etherifying agent adds, temperature is controlled at below 25 ℃; Add linking agent during etherifying agent adds, the consumption of linking agent is 1.0% of purified cotton weight, and linking agent is Epicholorohydrin, and it is to add after 5% that linking agent is diluted with ethanol to mass concentration again; After etherifying agent adds, add sodium hydroxide, the mol ratio of sodium hydroxide and purified cotton is 0.2:1, then is warming up to 75 ℃ of etherification reaction 90min;
(4) after etherification reaction finished, product was neutralized to pH to 7-7.5, obtained water-base drilling fluid hyperviscosity Polyanionic Cellulose through washing, oven dry, pulverizing, detected data and saw Table 2.
 
Table 2
Figure DEST_PATH_IMAGE004
Embodiment 3:
(1) under water at low temperature is cooling, mass concentration 50% aqueous sodium hydroxide solution and the mass concentration 91% aqueous ethanolic solution weight ratio by 1:2.5 is mixed, obtain the alcohol of 10 ℃ of left and right-alkali mixed solution;
(2) high-polymerization degree purified cotton (polymerization degree is more than 2600) is torn up after, after dropping in kneader with alcohol-alkali mixed solution, be filled with nitrogen in the kneader and get rid of oxygen in kneader; In purified cotton and alcohol-alkali mixed solution, the mol ratio of alkali is 1:2.3, and purified cotton is carried out low temperature alkalization, alkalization temperature 10 ℃ of left and right, alkalization time 40min;
(3) after alkalization finishes, add etherifying agent, the mol ratio of etherifying agent and purified cotton is 1.7:1, and described etherifying agent is that sodium chloroacetate and Mono Chloro Acetic Acid are the mixture of 2:1 in molar ratio, in etherifying agent, Mono Chloro Acetic Acid adds with the ethanolic soln form, and the mass percent that described Mono Chloro Acetic Acid accounts for ethanolic soln is 60%; The joining day of described etherifying agent is controlled at 30min, and during etherifying agent adds, temperature is controlled at below 25 ℃; Add linking agent during etherifying agent adds, the consumption of linking agent is 0.5% of purified cotton weight, and linking agent is propylene chlorohydrin, and it is to add after 4% that linking agent is diluted with ethanol to mass concentration again; After etherifying agent adds, add sodium hydroxide, the mol ratio of sodium hydroxide and purified cotton is 0.2:1, then is warming up to 78 ℃ of etherification reaction 50min;
(4) after etherification reaction finished, product was neutralized to pH to 7-7.5, obtained water-base drilling fluid hyperviscosity Polyanionic Cellulose through washing, oven dry, pulverizing, detected data and saw Table 3.
Table 3
Figure DEST_PATH_IMAGE006
Comparative Examples 1:
Press the record of the inventive embodiments 2 of notification number CN101838333A and implement, detect data and see the following form.
Figure DEST_PATH_IMAGE008
Comparative Examples 2:
Be product [0086] table 1 of the invention slurry method technique preparation of CN1989219A by notification number US7384892B2, [0090] table 2, the record of [0095] table 3 detects data and sees the following form.
Figure DEST_PATH_IMAGE010
 
The method for analyzing performance of products obtained therefrom of the present invention:
The viscosimetric analysis of product, the aqueous solution of the mass fraction 1% of preparation PAC product is with its viscosity of Brookfield viscometer determining; Substitution value, pH value, CL -Content and moisture content are analyzed according to the GB1904-2005 testing standard.
Application performance is ISO13500-2008 according to international API API 13A-2010(; That is the drilling fluid materials standard P34-38 of the standard GB/T5005-2010 of the People's Republic of China (PRC) measures.Illustrate that in passing, the application data of application data of the present invention and US7384892B2 is all measured by this standard; And the application data of Comparative Examples 1CN101838333A is not measured by this standard, so its apparent viscosity and filter loss are not had a comparability.
Table 4 is above-mentioned table 1, table 2, and table 3, Comparative Examples 1, Comparative Examples 2 Data inductions are together as follows:
Figure DEST_PATH_IMAGE012
Find out effect of the present invention from three embodiment and two Comparative Examples.
1. method of the present invention is to improve the better simply production line of domestic system use, produces and the external more expensive suitable product of slurry method production line with cheaper one-tenth instinct, has the stronger market competitiveness.
2. without the high Virahol of valency, still adopt alcohol to do medium, low power solvent method, product cost is low, and the output of unit equipment is high.
3. excellent product performance.
Above-described embodiment is a kind of better scheme of the present invention, is not that the present invention is done any pro forma restriction, also has other variant and remodeling under the prerequisite that does not exceed the technical scheme that claim puts down in writing.

Claims (8)

1. a water-base drilling fluid is with the preparation method of hyperviscosity Polyanionic Cellulose, and it is characterized in that: described preparation method's step is as follows:
(1) under water at low temperature is cooling, mass concentration 45-50% aqueous sodium hydroxide solution and the mass concentration 85-95% aqueous ethanolic solution weight ratio by 1:1.3-2.5 is mixed, obtain the alcohol-alkali mixed solution of 8-13 ℃;
(2) the high-polymerization degree purified cotton is torn up after, drop in kneader with alcohol-alkali mixed solution, in purified cotton and alcohol-alkali mixed solution, the mol ratio of alkali is 1:1.9-2.5, purified cotton is carried out low temperature alkalizes, alkalization temperature 8-13 ℃, alkalization time 30-60min;
(3) after alkalization finishes, add etherifying agent, the mol ratio of etherifying agent and purified cotton is 1.3-3.5:1, after etherifying agent adds, adds sodium hydroxide, and the mol ratio of sodium hydroxide and purified cotton is 0.1-1.4:1, then is warming up to 75-80 ℃ of etherification reaction 35-90min;
(4) after etherification reaction finished, product was neutralized to pH to 7-7.5, obtained water-base drilling fluid hyperviscosity Polyanionic Cellulose through washing, oven dry, pulverizing.
2. preparation method according to claim 1, it is characterized in that: the described etherifying agent of step (3) is that sodium chloroacetate and Mono Chloro Acetic Acid are the mixture of 0.5-3:1 in molar ratio, etherifying agent adds with the ethanolic soln form, and the mass percent that described etherifying agent accounts for ethanolic soln is 50-75%.
3. preparation method according to claim 1 and 2, it is characterized in that: the joining day of the described etherifying agent of step (3) is controlled at 20-50min, and during etherifying agent adds, temperature is controlled at below 25 ℃.
4. preparation method according to claim 3, it is characterized in that: add linking agent during etherifying agent adds, the consumption of linking agent is the 0.2-1.0% of purified cotton weight.
5. preparation method according to claim 4 is characterized in that: described linking agent is selected from a kind of in dichloro acetic acid, Epicholorohydrin, propylene chlorohydrin, and it is to add after 3%-5% that linking agent is diluted with ethanol to mass concentration again.
6. preparation method according to claim 1 and 2, it is characterized in that: the polymerization degree of the described high-polymerization degree purified cotton of step (2) is more than 2600.
7. preparation method according to claim 1 and 2 is characterized in that: after step (2) is torn up the high-polymerization degree purified cotton, after dropping in kneader with alcohol-alkali mixed solution, be filled with nitrogen in the kneader and get rid of oxygen in kneader.
8. preparation method according to claim 1 and 2 is characterized in that: it is that the form of chip solid or the aqueous solution adds that step (3) adds the sodium hydroxide of sodium hydroxide, and the sodium hydroxide mass concentration in the aqueous solution is 45-50%.
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CN104558216A (en) * 2013-10-27 2015-04-29 中国石油化工集团公司 Kneading preparation method and application method of high-hydrophobicity modified starch
CN105199003A (en) * 2015-04-28 2015-12-30 杭州弘博新材料有限公司 Method for preparing high-viscosity and high-etherification-degree sodium carboxymethyl cellulose from jute
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CN109929041A (en) * 2019-03-29 2019-06-25 陕西国防工业职业技术学院 A kind of preparation method of polyanion cellulose
CN112661866A (en) * 2020-12-18 2021-04-16 重庆力宏精细化工有限公司 Heat-resistant salt-tolerant polyanionic cellulose and preparation method thereof
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