CN106366204B - Combed polysaccharide compound and preparation method thereof and application and water-base drilling fluid and its application as coating agent - Google Patents
Combed polysaccharide compound and preparation method thereof and application and water-base drilling fluid and its application as coating agent Download PDFInfo
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- CN106366204B CN106366204B CN201610729963.4A CN201610729963A CN106366204B CN 106366204 B CN106366204 B CN 106366204B CN 201610729963 A CN201610729963 A CN 201610729963A CN 106366204 B CN106366204 B CN 106366204B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B13/00—Preparation of cellulose ether-esters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B3/00—Preparation of cellulose esters of organic acids
- C08B3/16—Preparation of mixed organic cellulose esters, e.g. cellulose aceto-formate or cellulose aceto-propionate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
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Abstract
The present invention relates to the drilling applications of petroleum industry, in particular it relates to a kind of combed polysaccharide compound and preparation method thereof and the application as coating agent and water-base drilling fluid and its application.The main chain of the combed polysaccharide compound is provided by sulfonate polysaccharide class compound, the side chain of the combed polysaccharide compound is provided as the compound shown in the compound shown in following formula (1) and formula (2), wherein, the sulfonate polysaccharide class compound is starch, the cellulose compound of sulfonation or the xanthans of sulfonation of sulfonation.The combed polysaccharide compound that the present invention is provided, pass through the sulfonate polysaccharide class compound of main chain and the synergy of the acrylic compounds of side chain and acrylic amide unit, can in drilling fluid as coating agent when play good coating performance, and also there is excellent heat-resisting property and anti-salt property
Description
Technical field
The present invention relates to the drilling applications of petroleum industry, in particular it relates to a kind of combed polysaccharide compound and its preparation
Method and application and water-base drilling fluid and its application as coating agent.
Background technology
Coating agent is very important a kind of inorganic agent in water-base drilling fluid inorganic agent, and it can not only pass through suction-operated
Landwaste is coated with, prevents landwaste from disperseing, beneficial to the exclusion of landwaste during solid controlling, while coating agent has high inhibition work to mud shale etc.
With preventing its hydration swelling, be conducive to wellbore stability.In addition, in DWSW liquid system, coating agent can also play part and carry
Cut, lubrication, with multifunctionality.
High molecular weight polyacrylamide birdss of the same feather flock together compound as conventional coating agent, and coating, inhibition are protruded, but are existed always
The defects such as temperature resistance, salt-resistance deficiency.Because high molecular weight polyacrylamide strand is long flexible chain, it is in high shear forces
Under easily degrade, cause its molecular weight reduction, so as to lose coating performance.By heat-resistant salt-resistant monomer such as N- ethenyl pyrrolidones
It is more conventional polyacrylamide coating agent that ketone, 2- acrylamide-2-methylpro panesulfonic acids, which are grafted on polyacrylamide,
Method of modifying, but introduce the molecular weight of these monomer post-consumer polymers and can be greatly lowered, cause its to be coated with hydraulic performance decline.
The content of the invention
It is an object of the invention to be difficult to have concurrently preferably coating performance, heat-resisting property and salt resistance for existing coating agent
There is provided a kind of combed polysaccharide compound with excellent coating performance, heat-resisting property and anti-salt property for the defect of performance
And preparation method thereof and the application as coating agent and water-base drilling fluid and its application.
To achieve these goals, the present invention provides a kind of combed polysaccharide compound, the combed polysaccharide compound
Main chain by sulfonate polysaccharide class compound provide, the side chain of the combed polysaccharide compound is as the compound shown in following formula (1)
There is provided with the compound shown in formula (2), wherein, the sulfonate polysaccharide class compound is starch, the cellulose family of sulfonation of sulfonation
Compound or the xanthans of sulfonation：
Formula (1)Formula (2)
Wherein, R1、R1'、R2And R2' it is each independently selected from H and C1-C6 alkyl.
Present invention also offers a kind of preparation method of combed polysaccharide compound, this method includes：
(1) in aqueous solvent, polysaccharide compound and sulfonating agent is subjected to sulfonating reaction, sulfonate polysaccharide class chemical combination is obtained
Thing；
(2) in aqueous solvent, in the presence of graft copolymerization catalyst, by shown in sulfonate polysaccharide class compound, formula (1)
Compound shown in compound and formula (2) carries out graft copolymerization；
Wherein, the polysaccharide compound is the one or more in starch, cellulose compound and xanthans；
Formula (1)Formula (2)
Wherein, R1、R1'、R2And R2' it is each independently selected from H and C1-C6 alkyl.
Present invention also offers combed polysaccharide compound made from the above method.
Application present invention also offers above-mentioned combed polysaccharide compound in drilling fluid as coating agent.
The present invention, which is also provided, a kind of contains above-mentioned combed polysaccharide compound as the water-base drilling fluid of coating agent.
The present invention also provides application of the above-mentioned water-base drilling fluid in oil/gas drilling.
The combed polysaccharide compound that the present invention is provided, passes through the sulfonate polysaccharide class compound and the acrylic acid of side chain of main chain
The synergy of class and acrylic amide unit, can in drilling fluid as coating agent when play good coating performance, and
Also there is excellent heat-resisting property and anti-salt property.Particularly, the combed polysaccharide compound dissolubility obtained by the present invention is good, more
Suitable for water-base drilling fluid.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The present invention provides a kind of combed polysaccharide compound, and the main chain of the combed polysaccharide compound is by sulfonate polysaccharide class
Compound is provided, and the side chain of the combed polysaccharide compound is as the compound shown in the compound shown in following formula (1) and formula (2)
There is provided, wherein, the sulfonate polysaccharide class compound is starch, the cellulose compound of sulfonation or the xanthan of sulfonation of sulfonation
Glue：
Formula (1)Formula (2)
Wherein, R1、R1'、R2And R2' it is each independently selected from H and C1-C6 alkyl.
According to the present invention, the combed polysaccharide compound may be considered to be connect on the main chain of sulfonate polysaccharide class compound
The side chain provided on branch as the compound shown in the compound shown in formula (1) and formula (2), the side chain can be shown in formula (1)
Copolymer compound chain shown in compound and formula (2) or be respectively equal poly chain that the compound shown in formula (1) is provided and
With the equal poly chain of the compound shown in formula (2).The combed polysaccharide compound passes through when for drilling fluid as coating agent
Multiple spot suction-operated of the polar group to landwaste on strand, effectively turns into big particle diameter by the landwaste coalescence of high degree of dispersion
Grain is simultaneously removed during solid controlling, plays excellent encapsulation action, while above-mentioned combed polysaccharide compound can also ensure
Excellent temperature resistance and anti-salt property is obtained under preferable encapsulation action.Also, for linear polymer coating agent, this
The combed polysaccharide compound of invention can not only obtain higher coating performance, heat-resisting property and anti-salt property, additionally it is possible to obtain
Obtain preferably water-soluble, be so just more applicable for water-base drilling fluid.
According to the present invention, wherein, above-mentioned C1-C6 alkyl for example can be methyl, ethyl, n-propyl, isopropyl, positive fourth
Base, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, n-hexyl etc..
In order to preferably play the combed polysaccharide compound as the effect of coating agent, under preferable case, R1、
R1'、R2And R2' it is each independently selected from H, methyl, ethyl, n-propyl, isopropyl and normal-butyl.
Wherein, the instantiation of the compound shown in formula (1) can be for example one kind in the compound shown in following formula
Or it is a variety of：
In formula (1-1)：R1And R1' it is H (also referred to as acrylamide)；
In formula (1-2)：R1For methyl, R1' it is H (also referred to as Methacrylamide)；
In formula (1-3)：R1For ethyl, R1' it is H (also referred to as ethyl acrylamide)；
In formula (1-4)：R1For H, R1' it is methyl (also referred to as 2- crotonamides).
Wherein, the instantiation of the compound shown in formula (2) can be for example one kind in the compound shown in following formula
Or it is a variety of：
In formula (2-1)：R2And R2' it is H (also referred to as acrylic acid)；
In formula (2-2)：R2For methyl, R2' it is H (also referred to as methacrylic acid).
According to the present invention, the sulfonate polysaccharide class compound is starch, the cellulose compound or sulphur of sulfonation of sulfonation
The xanthans of change.The polysaccharide compound of these sulfonation can be commercially available product, it would however also be possible to employ mistake described below in the present invention
It is prepared by Cheng Jinhang.It is considered that the polysaccharide compound of sulfonation is that some sulfonic groups are formd on polysaccharide compound or other are contained
The structure of methylthio group, this is the conventional cognitive of this area, and the present invention will not be repeated here.
Wherein, the cellulose compound of the sulfonation be the carboxymethyl cellulose of sulfonation, the hydroxymethyl cellulose of sulfonation,
The carboxyethyl cellulose of sulfonation, the hydroxyethyl cellulose of sulfonation, the hydroxypropyl cellulose of sulfonation or the hydroxypropyl methyl of sulfonation are fine
Dimension element.
According to the present invention, although the present invention is to sulfur-containing group (such as sulfonic group, sulfuric acid on the polysaccharide compound after sulfonation
Ester group, mercapto etc.) content there is no particular limitation, but be able to obtain the combed polysaccharide for being more applicable for coating agent
Class compound, it is preferable that in the sulfonate polysaccharide class compound, the content of sulfur-containing group is 20-35 weight %, preferably 25-
30 weight %.
According to the present invention, the molecular weight of the combed polysaccharide compound can change in relative broad range, in order to
Obtain the combed polysaccharide compound for being more applicable for coating agent, it is preferable that the Weight-average molecular of the combed polysaccharide compound
Measure as 9,000,000-15,000,000g/mol, preferably 9,500,000-14,500,000g/mol, more preferably 10,000,
000-13,500,000g/mol, it is still more preferably 12,000,000-13,500,000g/mol.
In accordance with the present invention it is preferred that, in the combed polysaccharide compound, as the compound shown in formula (1) and formula (2) institute
The content for the construction unit that the compound shown is provided is 80-95 weight %, preferably 85-92 weight %, more preferably 88-92 weights
Measure %.When the construction unit and the sulphur of offer main chain that provide the compound shown in the formula (1) of side chain and the compound shown in formula (2)
The construction unit for changing polysaccharide compound is met under above-mentioned weight ratio, can preferably play each in combed polysaccharide compound
The synergy of group, obtains water-soluble high, and coating performance, heat-resisting property and anti-salt property more excellent combed polysaccharide
Compound.
According to the present invention, although construction unit that the compound shown in compound and formula (2) shown in formula (1) is provided rubs
You can change ratio in relative broad range, it is preferable that the compound shown in the compound and formula (2) shown in formula (1) is provided
Construction unit mol ratio be 1：0.2-1, preferably 1：0.2-0.5, more preferably 1：0.24-0.4 (such as 1：0.25-
0.33) it is still more preferably, 1：0.27-0.33.There is provided when the compound shown in the compound shown in formula (1) and formula (2)
The mol ratio of construction unit within the range when, result in be more beneficial for main chain coordinate play coating agent performance side chain,
As set forth above, it is possible to think that the side chain is the equal of the compound shown in equal poly chain and formula (2) that the compound shown in formula (1) is provided
Poly chain, but the copolymerization chain of the compound formation shown in compound and formula (2) more preferably shown in formula (1), it is particularly random
Linear copolymerization chain.Several side chain grafts form comb-type structure, namely form the comb of the present invention in sulfonate polysaccharide class compound
Type polysaccharide compound.
Present invention also offers a kind of preparation method of combed polysaccharide compound, this method includes：
(1) in aqueous solvent, polysaccharide compound and sulfonating agent is subjected to sulfonating reaction, sulfonate polysaccharide class chemical combination is obtained
Thing；
(2) in aqueous solvent, in the presence of graft copolymerization catalyst, by shown in sulfonate polysaccharide class compound, formula (1)
Compound shown in compound and formula (2) carries out graft copolymerization；
Wherein, the polysaccharide compound is the one or more in starch, cellulose compound and xanthans；
Formula (1)Formula (2)
Wherein, R1、R1'、R2And R2' it is each independently selected from H and C1-C6 alkyl.
Wherein, shown in formula (1) compound shown in compound and formula (2) and its group is as described above,
This is repeated no more.
According to the present invention, sulfonate polysaccharide class described above will be provided by the sulfonating reaction in step (1)
Compound, therefore, the polysaccharide compound can be selected according to required sulfonate polysaccharide class compound, as starch, fibre
Tie up the one or more in chlorins compound and xanthans.
According to the present invention, the number-average molecular weight of the starch is usually 20,000-200 ten thousand, and it can be each of this area routine
Kind of native starch, such as potato starch, green starch, starch from sweet potato, wheaten starch in one or more.Wherein, it is described
The optional catabolite containing it in acid of starch, for example, can contain dextrin, maltose and its more glucose of low molecule amount
In one or more.
Wherein, the cellulose compound is carboxymethyl cellulose, hydroxymethyl cellulose, carboxyethyl cellulose, hydroxyl second
One or more in base cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose.It should be understood that the polysaccharide
Compound is usually linear macromolecular, it is believed that the polysaccharide compound after the sulfonation of following gained is also linear big point
Minor structure.
According to the present invention, the molecular weight of the polysaccharide compound can be carried out according to required sulfonate polysaccharide class compound
Selection, for example in order to prepare weight average molecular weight for 9,000,000-15,000,000g/mol (be preferably 9,500,000-14,
500,000g/mol, more preferably 10,000,000-13,500,000g/mol, it is still more preferably 12,000,000-13,
500,000g/mol) combed polysaccharide compound, it is preferable that the weight average molecular weight of the polysaccharide compound is 100,000-
2,000,000g/mol, preferably 150,000-1,000,000g/mol, for example, 700,000-1,000,000g/mol.
According to the present invention, the aqueous solvent can be single water or miscible have some not influence the present invention
Reaction solvent (being, for example, the one or more in methanol, ethanol, ethylene glycol, propyl alcohol, isopropanol etc.) water mixture,
Certainly it is preferably water.It is applied to the required sulfonate polysaccharide class compound of the present invention in order to prepare, it is preferable that in step (1),
Relative to the polysaccharide compound of 100 parts by weight, the consumption of aqueous solvent is 1000-5000 parts by weight, preferably 2000-
4000 parts by weight.
According to the present invention, to the sulfonating agent, there is no particular limitation, as long as the sulfonate polysaccharide class of the present invention can be obtained
Compound, can be using the conventional various sulfonating agents in this area, it is preferable that the sulfonating agent be chlorosulfonic acid, sulfur trioxide,
One kind in PS and the concentrated sulfuric acid (concentration be, for example, more than 90 weight %, particularly the 98 weight % concentrated sulfuric acid)
Or it is a variety of.The consumption of the sulfonating agent can change in relative broad range, in order to which the content of sulfur-containing group is made for 20-35
Under weight % (being preferably 25-30 weight %) sulfonate polysaccharide class compound, preferable case, relative to described in 100 parts by weight
Polysaccharide compound, the consumption of the sulfonating agent is 20-40 parts by weight, preferably 25-35 parts by weight, for example, 28-30 weight
Part.
, according to the invention it is preferred in the case of, the condition of the sulfonating reaction includes：It (is preferably 55- that temperature, which is 50-70 DEG C,
65 DEG C), the time is 8-20h (being preferably 10-12h).
According to the present invention, in order to promote dissolubility of the polysaccharide compound in aqueous solvent, above-mentioned sulfonating reaction
Carried out also in the presence of cosolvent, the cosolvent for example can be one kind or many in formic acid, acetic acid, ethanedioic acid and malonic acid
Kind.Wherein it is preferred to, relative to the polysaccharide compound of 100 parts by weight, the consumption of the cosolvent is 8-20 weight
Part, preferably 10-15 parts by weight.
According to the present invention, above-mentioned steps (1) can mix the polysaccharide compound and aqueous solvent using first, then
Introduce sulfonating agent and optional cosolvent mixes and carries out the mode of the sulfonating reaction.
According to the present invention, although the product of the sulfonating reaction obtained by step (1) is without any further processing
For in step (2), but it is able to be more beneficial for the progress of the graft copolymerization, the step (1) is also included institute
The product for stating sulfonating reaction carries out separation of solid and liquid (for example with the mode of suction filtration) and dries gained solid phase, so that it is more to obtain sulfonation
The process of saccharide compound.
According to the present invention, by by the compound shown in sulfonate polysaccharide class compound, formula (1) and formula (2) institute in step (2)
The compound shown carries out graft copolymerization, you can the compound that is grafted in sulfonate polysaccharide class compound shown in above formula (1) and
The polymer lateral chain of compound formation shown in formula (2), it is believed that sulfonate polysaccharide class compound here does not occur herein
Self-polymerization react, be only on the basis of the sulfonate polysaccharide class compound obtained by step (1), using the sulfonate polysaccharide class compound as
Main chain is grafted the compound shown in above formula (1) by the graft copolymerization of step (2) again and the compound shown in formula (2) is formed
Polymer lateral chain.Although the consumption of the compound shown in compound and formula (2) shown in the formula (1) can be according to required
Side chain situation on combed polysaccharide compound is properly selected, under preferable case, relative to the sulphur of 100 parts by weight
Change polysaccharide compound, total consumption of the compound shown in compound and formula (2) shown in formula (1) is 500-1500 parts by weight,
Preferably 800-1000 parts by weight, more preferably 850-950 parts by weight.In order to obtain what can preferably be coordinated with main chain
Side chain, it is preferable that the mol ratio of the consumption of the compound shown in compound and formula (2) shown in formula (1) is 1：0.2-1, preferably
For 1：0.2-0.5, more preferably 1：0.24-0.4 (such as 1：0.25-0.33), it is still more preferably 1：0.27-0.33.
According to the present invention, the progress of aqueous solvent as described above in step (2) is selected, and applicable in order to prepare
In the required combed polysaccharide compound of the present invention, it is preferable that in step (2), relative to the sulfonate polysaccharide of 100 parts by weight
Class compound, the consumption of aqueous solvent is 5000-10000 parts by weight, preferably 6000-9000 parts by weight, more preferably 6500-
8000 parts by weight.
According to the present invention, the graft copolymerization catalyst can be using the conventional catalysis for graft copolymerization in this area
Agent, for the compound shown in the sulfonate polysaccharide class compound preferably suitable for the present invention, formula (1) and the change shown in formula (2)
Under the graft copolymerization that compound is carried out, preferable case, the graft copolymerization catalyst is high-valency metal compound and persulfuric acid
One or more in salt.Wherein, the high-valency metal compound for example can be the compound of quadrivalent cerium, cobaltous chemical combination
One or more in thing, the compound of pentavalent vanadium, ferric compound etc., preferably ammonium ceric nitrate, ferric trichloride, four
One or more in (4- carboxyl phenyls) Cob altporphyrin and vanadium acetylacetonate.Preferably, the persulfate is ammonium persulfate, mistake
One or more in sodium sulphate and potassium peroxydisulfate.The consumption of the graft copolymerization catalyst can be according to required combed polysaccharide
Class compound is adjusted, it is preferable that relative to the sulfonate polysaccharide class compound of 100 parts by weight, the graft copolymerization is urged
The consumption of agent is 0.1-2 parts by weight, preferably 0.2-1 parts by weight, more preferably 0.2-0.5 parts by weight.
, according to the invention it is preferred in the case of, in step (2), the condition of the graft copolymerization includes：Temperature is 10-
40 DEG C (being preferably 20-35 DEG C, for example, 25-35 DEG C), the time is 10-30h (being preferably 16-25h, for example, 20-24h).
According to the present invention, in order to keep the activity of catalyst etc., this method can also include：So that the grafting is altogether
Poly- reaction is carried out in an inert atmosphere, and the one or more such as nitrogen, helium, neon, argon gas being passed through into system are simultaneously
Replace atmosphere therein (process can for example carry out 5-300min, mainly deoxygenation).
According to the present invention, in order to substantially more react, step (2) can be used first by sulfonate polysaccharide class compound
With aqueous solvent mixing, then the compound shown in introduction-type (1) and the compound shown in formula (2) are mixed, and are being passed through
Nitrogen, helium, neon, argon gas etc. are one or more and replace after atmosphere therein, introduce the graft copolymerization catalyst and carry out
The graft copolymerization.
According to the present invention, this method can also include the product of the graft copolymerization being dried, so as to obtain
The combed polysaccharide compound.
Present invention also offers combed polysaccharide compound made from the above method.Although the present invention is not limited particularly
It is fixed, but the combed polysaccharide compound may be considered above described in combed polysaccharide compound in one kind, or
The mixture of a variety of combed polysaccharide compounds of person.However, it is to be understood that the combed polysaccharide prepared by the above method
Compound typically refers to direct product of the above method without purification, and the product of even now is probably a variety of combed polysaccharides
The mixture of compound, but such situation is also included within the scope of the invention by the present invention.
Application present invention also offers above-mentioned combed polysaccharide compound in drilling fluid as coating agent.
The present invention, which is also provided, a kind of contains above-mentioned combed polysaccharide compound as the water-base drilling fluid of coating agent.
The combed polysaccharide compound that the present invention is provided, passes through the sulfonate polysaccharide class compound and the acrylic acid of side chain of main chain
The synergy of class and acrylic amide unit, can in drilling fluid as coating agent when play good coating performance, and
Also there is excellent heat-resisting property and anti-salt property.Particularly, the combed polysaccharide compound dissolubility obtained by the present invention is good, more
Suitable for water-base drilling fluid.There is no particular limitation for content of the present invention to the combed polysaccharide compound, can be according to stratum
Situation is suitably adjusted, it is preferable that relative to the water in the water-base drilling fluid of 100 parts by weight, the combed polysaccharide
The content of compound is 0.2-2 parts by weight, preferably 0.3-1.5 parts by weight, such as 0.5-1 parts by weight.
According to the present invention, in addition to water and above-mentioned copolymer, the water-base drilling fluid can also contain as water base
Other additives of drilling fluid, for example, can be containing the one or more in bentonite, alkalinity regulator and heavy weight additive etc..
Wherein, the bentonite refers to the clay using montmorillonite as main mineral constituent, and it has imparting drilling fluid is viscous to cut
The effect of power and leak-off wave making machine, for example, can be sodium bentonite and/or calcium-base bentonite, preferably sodium bentonite.Phase
For the water in the drilling fluid of 100 parts by weight, it is preferable that the bentonitic content is 2-4 parts by weight, more preferably 3-
4 parts by weight.
Wherein, the alkalinity regulator has the effect for improving bentonite mud yield, adjusting drilling liquid pH value, for example can be with
For Na2CO3.Preferably, relative to the water in the water-base drilling fluid of 100 parts by weight, the content of the alkalinity regulator is
0.2-0.4 parts by weight.
Wherein, the density for acting as adjusting drilling fluid of the heavy weight additive reaches required density, for example, can be barite
(such as that can be barite of the barium sulfate content in more than 90 weight %).Preferably, relative to the brill of 100 parts by weight
Aqueous phase in well liquid, the consumption of the heavy weight additive is 200-300 parts by weight.
The various materials that above-mentioned additive is can be commercially available product, can also be made according to the conventional method in this area, this
In repeat no more.
Present invention also offers application of the above-mentioned water-base drilling fluid in oil/gas drilling.
The combed polysaccharide compound that the present invention is provided can be rapidly soluble in water, is particularly suitable for use in water-base drilling fluid,
And with excellent coating performance, heat-resisting property and anti-salt property.
The present invention will be described in detail by way of examples below.
In following examples and comparative example：
Referred to as the content for the construction unit that the compound shown in the compound shown in formula (1) and formula (2) is provided with combed
On the basis of the gross weight of polysaccharide compound, the construction unit that the compound shown in the compound and formula (2) shown in formula (1) is provided
Shared content, it is believed that be the percent by weight that side chain accounts for combed polysaccharide compound.
Embodiment 1
The present embodiment is used to illustrate combed polysaccharide compound of the present invention and preparation method thereof and coating agent.
(1) 100g starch (is purchased from Sa En chemical technologies (Shanghai) Co., Ltd., molecular weight is 1,000,000g/
Mol) it is dissolved in 3000g water, and adds 12g acetic acid and 30g chlorosulfonic acid, after stirring, in reacts 12h at 60 DEG C；
Products therefrom is subjected to suction filtration, and dries gained solid, so as to obtain sulfonated starch SS-1.Identified through infrared nuclear-magnetism, the sulfonation
The content of sulfur-containing group is 28.5 weight % in starch；
(2) 100g sulfonated starch SS-1 is dissolved in 7000g water, and add 700g acrylamide and 200g third
Olefin(e) acid, leads to nitrogen 15min after stirring, then add 0.2g ammonium ceric nitrate, and in reacting 24h at 25 DEG C, so that by institute
Obtain product to be dried, crush, obtain combed polysaccharide compound, as coating agent C1.The weight of the combed polysaccharide compound
Average molecular weight is 13,500,000g/mol, wherein, identified through infrared nuclear-magnetism, form the propylene of combed polysaccharide compound side chain
The mol ratio for the construction unit that acid amides and acrylic acid are provided is 1：0.27, the construction unit provided by acrylamide and acrylic acid
Content is 90 weight %.
Embodiment 2
The present embodiment is used to illustrate combed polysaccharide compound of the present invention and preparation method thereof and coating agent.
(1) by 100g carboxymethyl cellulose (be purchased from Sa En chemical technologies (Shanghai) Co., Ltd., molecular weight is 700,
000g/mol) it is dissolved in 2000g water, and adds 12g acetic acid and 30g chlorosulfonic acid, after stirring, in reaction at 55 DEG C
10h；Products therefrom is subjected to suction filtration, and dries gained solid, so as to obtain sulfonation carboxymethyl cellulose SC-1.Through infrared nuclear-magnetism
The content of sulfur-containing group is 29.1 weight % in identification, the sulfonation carboxymethyl cellulose；
(2) 100g sulfonation carboxymethyl cellulose SC-1 is dissolved in 8000g water, and add 710g acrylamide and
240g acrylic acid, leads to nitrogen 20min after stirring, then add 0.5g ammonium persulfate, and in reacting 22h at 25 DEG C,
So as to be dried, crush by products therefrom, combed polysaccharide compound, as coating agent C2 are obtained.The combed polysaccharide
The weight average molecular weight of compound is 12,500,000g/mol, wherein, identified through infrared nuclear-magnetism, form combed polysaccharide compound side
The mol ratio for the construction unit that the acrylamide and acrylic acid of chain are provided is 1：0.3, the knot provided by acrylamide and acrylic acid
The content of structure unit is 90.5 weight %.
Embodiment 3
The present embodiment is used to illustrate combed polysaccharide compound of the present invention and preparation method thereof and coating agent.
(1) 100g hydroxypropyl methyl cellulose (is purchased from Sa En chemical technologies (Shanghai) Co., Ltd., molecular weight is
150,000g/mol) it is dissolved in 2000g water, and adds 15g acetic acid and 28g sulfur trioxide, after stirring, in 55 DEG C
Lower reaction 10h；Products therefrom is subjected to suction filtration, and dries gained solid, so as to obtain sulfonation hydroxypropyl methyl cellulose SC-2.
Identified through infrared nuclear-magnetism, the content of sulfur-containing group is 25.6 weight % in the sulfonation hydroxypropyl methyl cellulose；
(2) 100g sulfonation hydroxypropyl methyl cellulose SC-2 is dissolved in 6500g water, and adds 720g methyl-prop
The methacrylic acid of acrylamide and 230g, leads to nitrogen 10min after stirring, then add 0.5g ammonium persulfate, and in 30
20h is reacted at DEG C, so that products therefrom is dried, crushed, combed polysaccharide compound, as coating agent C3 is obtained.Should
The weight average molecular weight of combed polysaccharide compound is 12,000,000g/mol, wherein, identified through infrared nuclear-magnetism, form combed many
The mol ratio for the construction unit that the Methacrylamide and methacrylic acid of saccharide compound side chain are provided is 1：0.31, by methyl
The content for the construction unit that acrylamide and methacrylic acid are provided is 90.5 weight %.
Embodiment 4
The present embodiment is used to illustrate combed polysaccharide compound of the present invention and preparation method thereof and coating agent.
(1) (1) prepares sulfonated starch SS-1 according to the step of embodiment 1；
(2) according to the step of embodiment 1 (2), unlike, the consumption of the acrylamide used for 620g, acrylic acid
Consumption is 180g, so that combed polysaccharide compound is finally given, as coating agent C4.The weight of the combed polysaccharide compound is equal
Molecular weight is 9,500,000g/mol, wherein, identified through infrared nuclear-magnetism, form the acrylamide of combed polysaccharide compound side chain
The mol ratio of the construction unit provided with acrylic acid is 1：0.26, the content of the construction unit provided by acrylamide and acrylic acid
For 88.9 weight %.
Embodiment 5
The present embodiment is used to illustrate combed polysaccharide compound of the present invention and preparation method thereof and coating agent.
(1) (1) prepares sulfonated starch SS-1 according to the step of embodiment 1；
(2) according to the step of embodiment 1 (2), unlike, the consumption of the acrylamide used for 880g, acrylic acid
Consumption is 220g, so that combed polysaccharide compound is finally given, as coating agent C5.The weight of the combed polysaccharide compound is equal
Molecular weight is 14,500,000g/mol, wherein, identified through infrared nuclear-magnetism, form the acryloyl of combed polysaccharide compound side chain
The mol ratio for the construction unit that amine and acrylic acid are provided is 1：0.24, the construction unit that is provided by acrylamide and acrylic acid contains
Measure as 91.7 weight %.
Comparative example 1
It regard the sulfonated starch SS-1 obtained by (1) the step of embodiment 1 as coating agent DC1.
Comparative example 2
(1) (1) prepares sulfonated starch SS-1 according to the step of embodiment 1；
(2) according to the step of embodiment 1 (2), unlike, acrylic acid is not used, and the consumption of acrylamide is increased
To 900g, so that combed polysaccharide compound is finally given, as coating agent DC2.The combed polysaccharide compound is divided equally again
Son amount is 14,000,000g/mol, wherein, identified through infrared nuclear-magnetism, the side chain in the combed polysaccharide compound is only by propylene
Acid amides is provided, and the content of the construction unit provided by acrylamide is 90 weight %.
Comparative example 3
(1) (1) prepares sulfonated starch SS-1 according to the step of embodiment 1；
(2) according to the step of embodiment 1 (2), unlike, acrylamide is not used, and the consumption of acrylic acid is increased
To 900g, so that combed polysaccharide compound is finally given, as coating agent DC3.The combed polysaccharide compound is divided equally again
Son amount is 4,200,000g/mol, wherein, identified through infrared nuclear-magnetism, the side chain in the combed polysaccharide compound is only by acrylic acid
There is provided, and the content of the construction unit provided by acrylic acid is 90 weight %.
Comparative example 4
By purchased from the polyacrylamide that the weight average molecular weight of the Tian Run chemical companies AB1000 trades mark is 10,600,000g/mol
It is used as coating agent DC4.
Test case 1
This test case is used for the drilling fluid for illustrating the present invention.
Base drilling fluid Y：The water of 100 parts by weight, the sodium bentonite of 3 parts by weight is (purchased from Weifang China dimension bentonite technology
Research center), the Na of 0.3 parts by weight2CO3。
Under room temperature (about 25 DEG C), the above-mentioned coating agent C1-C5 and DC1-DC4 of 0.4 parts by weight is dissolved in respectively above-mentioned
In base drilling fluid Y, so that drilling fluid Y1-Y5 and drilling fluid DY1-DY4 is made, wherein, above-mentioned coating agent C1-C5's and DC4
Dissolving is time-consuming as shown in table 1 below：
Table 1
It can be seen from Table 1 that, coating agent C1-C5 of the invention dissolution time is not introduced into poly- the third of sulfonate polysaccharide on year-on-year basis
Acrylamide coating agent DC4 at least reduces 5min, illustrates the coating agent of the present invention and has faster dissolution velocity.
Test case 2
The rheological property heat-resisting property of above-mentioned drilling fluid is tested respectively, i.e., measures above-mentioned wellbore fluid respectively and ties up to
Apparent viscosity (AV), plastic viscosity (PV) before aging and after 150 DEG C of aging 16h at room temperature, yield value (YP), first egress
(G10”/10’)；It the results are shown in Table shown in 2, wherein：
Apparent viscosity (AV) is using the fast viscosimeter of normal form six side according to specified in standard GB/T/T29170-2012
What method was measured, unit is mPas,
Plastic viscosity (PV) is using the fast viscosimeter of normal form six side according to specified in standard GB/T/T29170-2012
What method was measured, unit is mPas, PV=θ600-θ300
Yield value (YP) is using the fast viscosimeter method according to specified in standard GB/T/T29170-2012 of normal form six
Measure, YP=0.511 × (2 × φ 300- φ 600), unit is Pa.
First egress (G10 "/10 ') is to be provided according to the fast viscosimeter of normal form six according in standard GB/T/T29170-2012
Method measure, unit is Pa/Pa.
Table 2
It can be seen from Table 2 that, coating agent of the invention has good thickening, carries and cut effect, adds the bag of the present invention
Rised appreciably by apparent viscosity, yield value and gel strength of the drilling fluid of agent in table 2, and after 150 DEG C of heat rollings, drilling well
Liquid can still maintain preferable viscosity and shear force, illustrate the coating agent of the present invention and have good heat-resisting property, combination property is excellent
In comparative example.
Test case 3
Salt solution Y'：The water of 100 parts by weight, the NaCl of 10 parts by weight.
The above-mentioned coating agent C1-C5 and DC1-DC4 of 0.4 parts by weight is dissolved in above-mentioned salt solution Y' respectively, so as to be made
Drilling fluid Y'1-Y'5 and drilling fluid DY'1-DY'4.
Method according to test case 2, measures above-mentioned drilling fluid Y'1-Y'5 and drilling fluid DY'1-DY'4 table respectively
See viscosity (AV), plastic viscosity (PV), yield value (YP), first egress (G10 "/10 ')；It the results are shown in Table shown in 3, wherein：
Table 3
It can be seen from Table 3 that, coating agent C1-C5 of the invention still has in salt solution significantly to be viscosified, proposes the effect of cutting,
Illustrate that the influence by salt is smaller, compared to having more preferable anti-salt property for comparative example.
Test case 4
Heat roll back yield key step it is as follows：It (is water, water and above coating respectively to add 350mL test solutions in ageing can
The mixed liquor of agent, water here uses running water), 5-10 mesh mud shale landwaste 50g are weighed, in 120 DEG C of roller furnace,
Roll scattered 16h；Then sieved and washed with 40 mesh sieves by rock sample is reclaimed in water totally, rock sample will be tailed over and be put into surface plate, 105
Dried in DEG C baking oven to constant weight；Weigh, calculating heat by following formula rolls back yield (the results are shown in Table 4)：
S=M/50 × 100%
In formula：The rate of recovery after the mesh sieves of S -40, %；The screen over-size of the mesh sieves of M -40, g.
Table 4
It can be seen from Table 4 that, embodiment can effectively play encapsulation action under 0.5% dosage, increase landwaste
Rolling rate of recovery, effect is better than comparative example；After dosage is promoted into 1%, rolling rate of recovery of the landwaste in the embodiment aqueous solution
74%, even as high as 81.1% can be reached, and linear polyacrylamide coating agent DC4 rolling rate of recovery is only 68%, can
Seeing the coating agent of the present invention has excellent coating performance.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (39)
1. a kind of combed polysaccharide compound, it is characterised in that the main chain of the combed polysaccharide compound is by sulfonate polysaccharide class
Compound is provided, and the side chain of the combed polysaccharide compound is as the compound shown in the compound shown in following formula (1) and formula (2)
There is provided, wherein, the sulfonate polysaccharide class compound is starch, the cellulose compound of sulfonation or the xanthan of sulfonation of sulfonation
Glue；The weight average molecular weight of the combed polysaccharide compound is 9,000,000-15,000,000g/mol；As shown in formula (1)
The content for the construction unit that compound shown in compound and formula (2) is provided is 80-95 weight %；
Formula (1)Formula (2)
Wherein, R1、R1'、R2And R2'It is each independently selected from H and C1-C6 alkyl.
2. combed polysaccharide compound according to claim 1, wherein, R1、R1'、R2And R2'It is each independently selected from H, first
Base, ethyl, n-propyl, isopropyl and normal-butyl.
3. combed polysaccharide compound according to claim 1 or 2, wherein, the weight of the combed polysaccharide compound is equal
Molecular weight is 9,500,000-14,500,000g/mol.
4. combed polysaccharide compound according to claim 3, wherein, the Weight-average molecular of the combed polysaccharide compound
Measure as 10,000,000-13,500,000g/mol.
5. the combed polysaccharide compound according to claim 1 or 4, wherein, in the combed polysaccharide compound, by formula
(1) content for the construction unit that the compound shown in the compound and formula (2) shown in is provided is 85-92 weight %.
6. combed polysaccharide compound according to claim 1, wherein, shown in the compound and formula (2) shown in formula (1)
The mol ratio for the construction unit that compound is provided is 1：0.2-1.
7. combed polysaccharide compound according to claim 6, wherein, shown in the compound and formula (2) shown in formula (1)
The mol ratio for the construction unit that compound is provided is 1：0.2-0.5.
8. combed polysaccharide compound according to claim 7, wherein, shown in the compound and formula (2) shown in formula (1)
The mol ratio for the construction unit that compound is provided is 1：0.24-0.4.
9. combed polysaccharide compound according to claim 1, wherein, the cellulose compound of the sulfonation is sulfonation
Carboxymethyl cellulose, the hydroxymethyl cellulose of sulfonation, the carboxyethyl cellulose of sulfonation, the hydroxyethyl cellulose of sulfonation, sulfonation
Hydroxypropyl cellulose or sulfonation hydroxypropyl methyl cellulose.
10. a kind of preparation method of combed polysaccharide compound, it is characterised in that this method includes：
(1) in aqueous solvent, polysaccharide compound and sulfonating agent is subjected to sulfonating reaction, sulfonate polysaccharide class compound is obtained；
(2) in aqueous solvent, in the presence of graft copolymerization catalyst, by the chemical combination shown in sulfonate polysaccharide class compound, formula (1)
Compound shown in thing and formula (2) carries out graft copolymerization；Relative to the sulfonate polysaccharide class compound of 100 parts by weight,
Total consumption of the compound shown in compound and formula (2) shown in formula (1) is 500-1500 parts by weight；Relative to 100 parts by weight
The sulfonate polysaccharide class compound, the consumption of the graft copolymerization catalyst is 0.1-2 parts by weight；
Wherein, the polysaccharide compound is the one or more in starch, cellulose compound and xanthans；
Formula (1)Formula (2)
Wherein, R1、R1'、R2And R2'It is each independently selected from H and C1-C6 alkyl.
11. method according to claim 10, wherein, the cellulose compound is carboxymethyl cellulose, methylol
One kind or many in cellulose, carboxyethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose
Kind.
12. method according to claim 11, wherein, the sulfonating agent is in chlorosulfonic acid, sulfur trioxide, 1,3-N-morpholinopropanesulfonic acid
One or more in ester and the concentrated sulfuric acid.
13. method according to claim 11, wherein, relative to the polysaccharide compound of 100 parts by weight, the sulphur
The consumption of agent is 20-40 parts by weight.
14. method according to claim 13, wherein, relative to the polysaccharide compound of 100 parts by weight, the sulphur
The consumption of agent is 25-35 parts by weight.
15. the method according to any one in claim 10-14, wherein, in step (1), relative to 100 parts by weight
The polysaccharide compound, the consumption of aqueous solvent is 1000-5000 parts by weight.
16. method according to claim 15, wherein, in step (1), relative to the polysaccharide of 100 parts by weight
Compound, the consumption of aqueous solvent is 2000-4000 parts by weight.
17. method according to claim 15, wherein, the condition of the sulfonating reaction includes：Temperature is 50-70 DEG C；When
Between be 8-20h.
18. method according to claim 17, wherein, the condition of the sulfonating reaction includes：Temperature is 55-65 DEG C；When
Between be 10-12h.
19. method according to claim 10, wherein, relative to the sulfonate polysaccharide class compound of 100 parts by weight, formula
(1) total consumption of the compound shown in compound and formula (2) shown in is 800-1000 parts by weight.
20. method according to claim 19, wherein, relative to the sulfonate polysaccharide class compound of 100 parts by weight, formula
(1) total consumption of the compound shown in compound and formula (2) shown in is 850-950 parts by weight.
21. method according to claim 10, wherein, the use of the compound shown in compound and formula (2) shown in formula (1)
The mol ratio of amount is 1：0.2-1.
22. method according to claim 21, wherein, the use of the compound shown in compound and formula (2) shown in formula (1)
The mol ratio of amount is 1：0.2-0.5.
23. method according to claim 22, wherein, the use of the compound shown in compound and formula (2) shown in formula (1)
The mol ratio of amount is 1：0.24-0.4.
24. method according to claim 10, wherein, R1、R1'、R2And R2'It is each independently selected from H, methyl, ethyl, just
Propyl group, isopropyl and normal-butyl.
25. the method according to any one in claim 10 and 19-24, wherein, the graft copolymerization catalyst is height
One or more in divalent metal compound and persulfate.
26. method according to claim 25, wherein, the high-valency metal compound is ammonium ceric nitrate, ferric trichloride, four
One or more in (4- carboxyl phenyls) Cob altporphyrin and vanadium acetylacetonate；The persulfate is ammonium persulfate, sodium peroxydisulfate
With the one or more in potassium peroxydisulfate.
27. method according to claim 25, wherein, relative to the sulfonate polysaccharide class compound of 100 parts by weight, institute
The consumption for stating graft copolymerization catalyst is 0.1-2 parts by weight.
28. method according to claim 27, wherein, relative to the sulfonate polysaccharide class compound of 100 parts by weight, institute
The consumption for stating graft copolymerization catalyst is 0.2-1 parts by weight.
29. method according to claim 28, wherein, relative to the sulfonate polysaccharide class compound of 100 parts by weight, institute
The consumption for stating graft copolymerization catalyst is 0.2-0.5 parts by weight.
30. the method according to any one in claim 10-14,16-24 and 26-29, wherein, in step (2), relatively
In the sulfonate polysaccharide class compound of 100 parts by weight, the consumption of aqueous solvent is 5000-10000 parts by weight.
31. method according to claim 30, wherein, in step (2), relative to the sulfonate polysaccharide of 100 parts by weight
Class compound, the consumption of aqueous solvent is 6000-9000 parts by weight.
32. the method according to any one in claim 10-14,16-24,26-29 and 31, wherein, in step (2),
The condition of the graft copolymerization includes：Temperature is 10-40 DEG C；Time is 10-30h.
33. method according to claim 32, wherein, in step (2), the condition of the graft copolymerization includes：Temperature
Spend for 20-35 DEG C；Time is 16-25h.
34. the combed polysaccharide compound as made from the method described in any one in claim 10-33.
35. the combed polysaccharide compound in claim 1-9 and 34 described in any one is used as coating agent in drilling fluid
Using.
36. a kind of combed polysaccharide compound contained in claim 1-9 and 34 described in any one is used as the water of coating agent
Base drilling fluid.
37. water-base drilling fluid according to claim 36, wherein, relative to the water in the water-base drilling fluid of 100 parts by weight,
The content of the combed polysaccharide compound is 0.2-2 parts by weight.
38. the water-base drilling fluid according to claim 37, wherein, relative to the water in the water-base drilling fluid of 100 parts by weight,
The content of the combed polysaccharide compound is 0.3-1.5 parts by weight.
39. application of the water-base drilling fluid in claim 36-38 described in any one in oil/gas drilling.
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| CN109837074B (en) * | 2019-03-27 | 2021-03-09 | 中国石油大学(华东) | Fluid loss additive composition and application thereof, water-based drilling fluid and application thereof |
| CN110079294A (en) * | 2019-05-30 | 2019-08-02 | 四川格鑫拓科技有限公司 | A kind of high temperature resistant weighted fracture fluid and preparation method thereof |
| CN113248665B (en) * | 2021-05-11 | 2023-05-05 | 黑龙江吉地油田服务股份有限公司 | Sewage-resistant polymer for oil extraction and preparation method thereof |
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