CN113845894B - Low-pyruvyl xanthan gum-based temperature-resistant polymer and application thereof - Google Patents
Low-pyruvyl xanthan gum-based temperature-resistant polymer and application thereof Download PDFInfo
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Abstract
The invention relates to a temperature resistant polymer and application of the polymer. Xanthan gum is a biological gum integrating thickening, suspending, emulsifying and stabilizing into a whole and having excellent performance, and is widely used in the oil extraction field at present. However, the conventional xanthan gum has the defect of insufficient stability under a high-temperature operation environment. In order to overcome the technical defect, the invention provides a temperature-resistant polymer, which comprises low-pyruvyl xanthan gum, a stabilizer and an antioxidant protective agent. Proved by verification, the temperature-resistant polymer provided by the invention can effectively prolong the stability of the xanthan gum under the high temperature condition, has obviously improved viscosity retention rate compared with the traditional xanthan gum, effectively overcomes the defect of insufficient thermal stability of the traditional xanthan gum, has improved rheological property, can effectively reduce the operation difficulty when being applied to the oil extraction field as a completion fluid, and can also be used as a tertiary oil extraction auxiliary agent.
Description
Technical Field
The invention belongs to the technical field of microbial high molecular materials, and particularly relates to a low-pyruvate-based xanthan gum temperature-resistant polymer and application of the polymer.
Background
The disclosure of this background section is only intended to increase the understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art already known to those of ordinary skill in the art.
Xanthan gum is an acidic extracellular heteropolysaccharide produced by Xanthomonas campestris (Xanthomonas campestris), the main chain of the acidic extracellular heteropolysaccharide is formed by D-glucose connected by beta-1, 4 glycosidic bonds, the trisaccharide side chain is formed by D-mannose, D-glucuronic acid and D-mannose connected to glucose residues on the main chain through alpha-1, 3 glycosidic bonds, the mannose residues at the tail ends of the side chain distribute acetogenins, most of the internal mannose residues are acetylated, the level of substitution of pyruvic acid and acetyl groups is changed due to the difference of strains and metabolic environments of the strains, and based on the structure, the xanthan gum molecule can form more complex secondary and tertiary structures. The unique structure of the xanthan gum molecule enables the aqueous solution to have unique shearing dilution performance, good thickening property, emulsion stability, acid and alkali environment resistance and temperature resistance, so the xanthan gum is widely applied to various industries such as petroleum exploitation, food, medicine, chemical industry and the like, and is a microbial polysaccharide with important commercial value.
At present, along with the expansion of application fields, higher requirements are put forward on the properties of xanthan gum, such as the requirements on the temperature resistance and salt resistance of the xanthan gum in the petroleum exploitation field are higher and higher, the viscosity of an aqueous solution of the traditional xanthan gum is easy to be rapidly attenuated due to oxidative degradation, hydrolysis and the like of the traditional xanthan gum at high temperature, the application is greatly limited, the high-temperature and salt-resistant oil reservoir reserve ratio of China is high, and the xanthan gum with the temperature resistance and salt resistance is urgently needed to reduce the oil extraction cost, so that the development of the low-cost and high-temperature-resistant xanthan gum is particularly important for promoting the petroleum exploitation of China, in particular the petroleum exploitation of the high-temperature and salt oil reservoir.
The main method for solving the problem of temperature resistance of xanthan gum in the prior art is as follows: high temperature resistant polysaccharide producing strain mutagenesis screening (CN 201010132122.8), genetic engineering (CN 201811359138.5); or post-fermentation product crosslinking treatment (CN2009102366651. X; liu Ru "preparation of crosslinked xanthan gum and its solution rheology"). The workload of screening strains by mutagenesis is large, and the mutation recovery rate is high; the genetic engineering transformation breeding needs to transform a plurality of genes, so that the research cost is greatly increased, the activity of the strain is reduced due to genetic transformation, and the production and fermentation process is complex and high in cost; and the steps of the fermentation or product crosslinking process are complicated, a large amount of energy is consumed, and the application cost of the xanthan gum product is obviously increased.
Disclosure of Invention
Based on the above technical background, the present invention aims to provide an ideal high temperature resistant xanthan gum product, wherein a stabilizer is introduced to improve the temperature resistance of xanthan gum by providing a xanthan gum polymer form. Further, the research of the invention proves that the xanthan gum substituted by the low pyruvate group can obtain better temperature resistance than the common product, and therefore, the invention provides the temperature resistant polymer based on the low pyruvate group xanthan gum.
Specifically, the invention provides the following technical scheme:
in a first aspect of the present invention, a temperature resistant polymer is provided, wherein the temperature resistant polymer at least comprises low pyruvyl xanthan gum, a stabilizer and a protective agent;
the stabilizer is selected from one or a combination of more of glutaraldehyde, glyoxal, succinic acid and butanedione;
the protective agent is an antioxidant.
As is well known in the art, the xanthan gum molecule is a "pentasaccharide repeating unit" structural polymer composed of D-glucose, D-mannose, D-glucuronic acid, acetyl and pyruvate, and in the above heat-resistant polymer, the low pyruvate xanthan gum represents that the pyruvic acid content in the xanthan gum molecule is significantly lower than that in normal xanthan gum; in a preferred embodiment, the amount of pyruvate in the xanthan gum is less than 0.1% (w/w) of the total amount.
In one embodiment of the invention, the low pyruvyl xanthan is derived from a fermentation product of an engineering strain of xanthomonas (Xanthomonas campestris Δgull-3) or a commercially available product.
The construction and screening process of the further engineering strain Xanthomonas campestris delta gull-3 is as follows:
(1) The method comprises the steps of amplifying and obtaining upstream and downstream homologous arm genes of gumL from a genome of a synthetic common xanthan strain Xanthomonas campestris NRRL B-1459, obtaining a pK18mobSacB linearization vector through double digestion, inserting the upper and lower homologous arm fragments of gumL into a multiple cloning site on a plasmid by using T5 DNA ligase, and constructing a knockout plasmid pK18 mobSacB-delta gumL of pyruvyltransferase.
(2) Transforming the knockout plasmid pK18 mobSacB-delta gulL into DH-5 alpha strain to obtain transformant, obtaining recombinant strain DH-5 alpha/pK 18 mobSacB-delta gulL;
(3) Plasmids extracted from recombinant strain DH-5α/pK18mobSacB- ΔgulL were transferred by means of shock transformation (CN 201210379735.0) to Xanthomonas campestris NRRL B-1459, and Kanamycin plates were screened for single-crossover strains, and sucrose-lethal plates were screened for double-crossover bacteria from which gulL had been knocked out and designated Xanthomonas campestris ΔgulL-3.
(4) Fermenting by using a strain Xanthomonas campestris delta gull-3 to obtain a low-pyruvyl xanthan gum product.
In a preferred technical scheme of the first aspect, the protective agent is an antioxidant, and is further a sulfurous acid antioxidant, and in a specific embodiment, the protective agent is one or a combination of several of sodium thiosulfate, sodium hyposulfite, sodium sulfite and sodium bisulfite.
Preferably, in the heat-resistant polymer according to the first aspect, the raw materials and mass percentages are: 50-80% of low pyruvoyl xanthan gum, 10-35% of stabilizing agent and 10-20% of protecting agent.
In one embodiment of the above preferred technology, the components and mass fractions of the temperature resistant polymer are as follows: low pyruvate xanthan gum 72%, glyoxal 18% and sodium sulfite 10%.
In still another embodiment of the foregoing preferred embodiment, the components and mass fractions of the temperature-resistant polymer are as follows: low pyruvyl xanthan gum 60%, succinic acid 20% and sodium thiosulfate 20%.
In still another embodiment of the foregoing preferred embodiment, the components and mass fractions of the temperature-resistant polymer are as follows: 51% of low pyruvoyl xanthan gum, 34% of butanedione and 15% of low sodium sulfite.
Preferably, the preparation method of the temperature resistant polymer comprises the following steps: weighing the components in proper mass ratio, and uniformly mixing.
In a second aspect, the invention provides the use of the temperature resistant polymer of the first aspect in the oil recovery field.
Xanthan gum has good suspending effect on insoluble solids and oil drops, and has high viscosity under static action, so that the xanthan gum can be used as a displacement agent in oil extraction operation for improving liquid fluidity so as to increase the recovery ratio of crude oil. The defects are mainly that: poor heat-resistant stability, is easy to degrade under the conditions of high temperature and high salt, and cannot meet the operation requirement of high-temperature stratum. In addition, xanthan gum is easily affected by factors such as microorganisms, and needs to be added with preservative and the like for use, and the solution state can be preserved for about one week.
Proved by verification, the heat-resistant polymer provided by the first aspect of the invention can effectively improve the stability of xanthan gum, in particular the heat-resistant stability under high temperature condition, and the solution storage time is prolonged to 2 months or more. In addition, the temperature-resistant polymer has better rheological property compared with the temperature-resistant polymer, and the operation convenience is effectively improved.
Preferably, the oil recovery field includes, but is not limited to, the application of the above temperature resistant polymers in mud treatment, tertiary oil recovery and other fields.
In a third aspect of the present invention, a completion fluid is provided that includes the temperature resistant polymer of the first aspect.
Preferably, the completion fluid is one of an oil displacement agent, a drilling fluid thickener, a cuttings suspension agent, a filtrate reducer, an oil displacement agent, a profile control agent or a water shutoff agent, which comprises but is not limited to medium and low permeability reservoir tertiary oil recovery.
Further, the oil displacement agent, the profile control agent or the water shutoff agent is a weak gel preparation, and the gel preparation is formed by the heat-resistant polymer in the first aspect under the action of the cross-linking agent.
The cross-linking agent is selected from one of aluminum chloride, chromium chloride, potassium dichromate/sodium sulfite, chromium formate, chromium lactate, chromium acetate, chromium propionate, chromium butyrate, chromium oxalate, chromium malonate, aluminum citrate, oligomeric phenolic resin, formaldehyde, glyoxal, glutaraldehyde, melamine formaldehyde resin, phenol, catechol, resorcinol, hydroquinone and hexamethylenetetramine.
Further, the oil displacement agent also comprises a surfactant, wherein the surfactant comprises an anionic surfactant, a cationic surfactant or a nonionic surfactant; examples of such anionic surfactants are C 8-16 Sodium alkylbenzenesulfonate or C 8-16 Sodium alkyl sulfate; examples of the cationic surfactant are C 8-16 Alkyl trimethyl bromides or ammonium chloride; examples of the nonionic surfactant are C 8-16 Alkyl dimethyl ammonium oxide or C 8-16 At least one of alkylphenol ethoxylates.
The beneficial effects of the above technical scheme are:
(1) The stability of the high-temperature state of the xanthan gum aqueous solution is obviously improved, the viscosity retention rate of the xanthan gum aqueous solution reaches more than 74% at 90 ℃ for 30 days, and the viscosity retention rate reaches more than 40% at 60 days;
(2) Compared with the prior art, the rheological property of the xanthan gum aqueous solution is provided, the tackifying effect is better at low shear, the viscosity is lower at high shear, and the injection property is better;
(3) Compared with the prior art, the method can be directly completed in the application process, the process operation is simple, and the energy is saved.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a comparison of the temperature resistance of different types of xanthan gum and its temperature resistant polymers in example 1 and comparative example 1;
fig. 2 is a comparison of the shear resistance of different types of xanthan gum and its temperature resistant polymers in example 1 and comparative example 1.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
As described in the background art, the xanthan gum also has the defects of insufficient temperature resistance and insufficient stability when being applied to oil extraction operation, and in order to solve the technical problems, the invention provides a temperature-resistant polymer.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1 a temperature resistant xanthan polymer comprising the following components in mass fraction:
low pyruvoyl xanthan gum 72%
Stabilizer 18%
10% of protective agent
The low pyruvoyl xanthan gum product (L-3) has a pyruvoyl content of 0.087%; the stabilizer is succinyl aldehyde; the protective agent is sodium sulfite.
The preparation method of the temperature-resistant xanthan polymer (L-3) comprises the following steps: 720g of low-pyruvoyl xanthan gum (L-3), 180g of glyoxal and 100g of sodium sulfite are respectively weighed and fully and uniformly mixed to obtain 1000g of temperature-resistant xanthan gum temperature-resistant polymer (L-3 x), and the mixture is sealed for standby.
Example 2 a temperature resistant xanthan polymer comprising the following components in mass fraction:
low pyruvoyl xanthan gum 60%
The low pyruvate xanthan gum product (L-3-2) has a pyruvate content of 0.057%; the stabilizer is succinic acid; the protective agent is sodium thiosulfate.
The preparation method of the temperature-resistant xanthan polymer (L-3-2) comprises the following steps: 720g of low-pyruvyl xanthan gum (L-3-2), 180g of oxalic acid and 100g of sodium thiosulfate are weighed respectively, fully and uniformly mixed to obtain 1000g of temperature-resistant xanthan gum polymer (L-3-2 x), and sealed for later use.
Comparative example 1 a general xanthan gum temperature resistant polymer comprises the following components in percentage by mass:
ordinary xanthan gum product (commercially available) 72%
Stabilizer 18%
10% of protective agent
The pyruvyl group content of the ordinary xanthan gum product (H-1) is 2.52%; the stabilizer is succinyl aldehyde; the protective agent is sodium sulfite.
The preparation method of the ordinary xanthan gum temperature resistant polymer (H-1) comprises the following steps: 720g of ordinary xanthan gum (H-1), 180g of glyoxal and 100g of sodium sulfite are respectively weighed and fully and uniformly mixed to obtain 1000g of temperature-resistant xanthan gum temperature-resistant polymer (H-1 x), and the mixture is sealed for standby.
Effect verification
The different xanthan gum products (L-3, H-1) and their temperature resistant polymers (L-3, H-1) of example 1 and comparative example 1 were weighed separately to prepare 3000ppm aqueous solutions, and after sufficient dissolution, the viscosity change over time at 90℃was measured using a Brookfield DV2T rotational viscometer (62 # spindle, 60 r/min).
The measurement result is shown in figure 1, and the result shows that the temperature-resistant xanthan gum temperature-resistant polymer has obvious high temperature resistance, the viscosity retention rate can reach 74% after the temperature is kept for 30 days at 90 ℃, the viscosity retention rate is still more than 40% after 60 days, the combined viscosity retention rate of a common xanthan gum product is lower than 10%, and the non-compounded xanthan gum product can be only stabilized for about one week.
Test 2 comparison of shear resistance of different xanthan gum products and temperature resistant polymers thereof
The different xanthan products (L-3, H-1) and their temperature resistant polymers (L-3, H-1) of example 1 and comparative example 1 were weighed separately and formulated into 3000ppm aqueous solutions, and after sufficient dissolution, the viscoelasticity of the samples at different shear rates was measured using an Anton Paar MCR302 rheometer.
The measurement result is shown in figure 2, and the result shows that the temperature-resistant xanthan gum temperature-resistant polymer has better tackifying effect in low shear, lower viscosity in high shear and better injection characteristic, and is an ideal auxiliary material in the field of tertiary oil recovery in oil fields.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. The heat-resistant polymer is characterized by comprising the following raw materials in percentage by mass: 50-80% of low-pyruvyl xanthan gum, 10-35% of stabilizer and 10-20% of protective agent;
the stabilizer is selected from one or a combination of more of glutaraldehyde, glyoxal, succinic acid and butanedione;
the protective agent is one or a combination of more of sodium thiosulfate, sodium hyposulfite, sodium sulfite and sodium bisulfite;
in the low-pyruvate xanthan gum, the total amount of pyruvate is less than 0.1%;
the low-pyruvate xanthan gum is derived from a fermentation product of a xanthomonas engineering strain or a commercial product.
2. The temperature-resistant polymer according to claim 1, wherein the temperature-resistant polymer comprises the following components in percentage by mass: low pyruvate xanthan gum 72%, glyoxal 18% and sodium sulfite 10%.
3. The temperature-resistant polymer according to claim 1, wherein the temperature-resistant polymer comprises the following components in percentage by mass: low pyruvyl xanthan gum 60%, succinic acid 20% and sodium thiosulfate 20%.
4. The temperature-resistant polymer according to claim 1, wherein the temperature-resistant polymer comprises the following components in percentage by mass: 51% of low pyruvoyl xanthan gum, 34% of butanedione and 15% of low sodium sulfite.
5. The temperature-resistant polymer according to claim 1, wherein the preparation method of the temperature-resistant polymer comprises the following steps: weighing the components in proper mass ratio, and uniformly mixing.
6. Use of the temperature resistant polymer of any one of claims 1-5 in the field of oil recovery; the application of the oil extraction field comprises the application of the temperature-resistant polymer in the fields of slurry treatment and tertiary oil extraction.
7. A completion fluid comprising the temperature resistant polymer of any one of claims 1-5.
8. The completion fluid of claim 7, wherein the completion fluid is one of an oil displacement agent, a drilling fluid thickener, a cuttings suspension agent, a fluid loss additive, an oil displacement agent, a profile control agent, or a water shutoff agent comprising tertiary oil recovery of medium and low permeability reservoirs.
9. The completion fluid of claim 8, wherein the oil displacement agent, profile control agent or water shutoff agent is a weak gel formulation formed by the heat resistant polymer of any one of claims 1-5 under the action of a cross-linking agent;
the cross-linking agent is selected from one of aluminum chloride, chromium chloride, potassium dichromate/sodium sulfite, chromium formate, chromium lactate, chromium acetate, chromium propionate, chromium butyrate, chromium oxalate, chromium malonate, aluminum citrate, oligomeric phenolic resin, formaldehyde, glyoxal, glutaraldehyde, melamine formaldehyde resin, phenol, catechol, resorcinol, hydroquinone and hexamethylenetetramine.
10. The completion fluid of claim 8, further comprising a surfactant in the oil-displacing agent, the surfactant comprising an anionic surfactant, a cationic surfactant, or a nonionic surfactant.
11. The completion fluid of claim 10, wherein said anionic surfactant is C 8-16 Sodium or C alkylbenzene sulfonate 8-16 Sodium alkyl sulfate.
12. The completion fluid of claim 10, wherein said cationic surfactant is C 8-16 Alkyl trimethyl bromide or ammonium chloride.
13. The completion fluid of claim 10, wherein said nonionic surfactant is C 8-16 Alkyl dimethyl ammonium oxides or C 8-16 Alkylphenol ethoxylates.
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| CN113845894A (en) | 2021-12-28 |
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