CN112175874B - Complex enzyme and method for treating guar gum fracturing fluid flowback fluid by using same - Google Patents

Complex enzyme and method for treating guar gum fracturing fluid flowback fluid by using same Download PDF

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CN112175874B
CN112175874B CN202011085130.1A CN202011085130A CN112175874B CN 112175874 B CN112175874 B CN 112175874B CN 202011085130 A CN202011085130 A CN 202011085130A CN 112175874 B CN112175874 B CN 112175874B
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guar gum
fluid
flowback
treating
complex enzyme
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CN112175874A (en
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吴家全
郭丽梅
肖早早
张永康
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Tianjin University of Science and Technology
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Tianjin University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N1/00—Microorganisms, e.g. protozoa; Compositions thereof; Processes of propagating, maintaining or preserving microorganisms or compositions thereof; Processes of preparing or isolating a composition containing a microorganism; Culture media therefor
    • C12N1/20—Bacteria; Culture media therefor
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C02F3/342—Biological treatment of water, waste water, or sewage characterised by the microorganisms used characterised by the enzymes used
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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    • C12N1/14—Fungi; Culture media therefor
    • C12N1/16—Yeasts; Culture media therefor
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    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
    • C12N9/14—Hydrolases (3)
    • C12N9/24—Hydrolases (3) acting on glycosyl compounds (3.2)
    • C12N9/2402—Hydrolases (3) acting on glycosyl compounds (3.2) hydrolysing O- and S- glycosyl compounds (3.2.1)
    • C12N9/2477—Hemicellulases not provided in a preceding group
    • C12N9/2488—Mannanases
    • C12N9/2491—Beta-mannosidase (3.2.1.25), i.e. mannanase
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    • C12Y302/00—Hydrolases acting on glycosyl compounds, i.e. glycosylases (3.2)
    • C12Y302/01—Glycosidases, i.e. enzymes hydrolysing O- and S-glycosyl compounds (3.2.1)
    • C12Y302/01025—Beta-mannosidase (3.2.1.25), i.e. mannanase
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract

The invention discloses a complex enzyme and a method for treating guar gum fracturing fluid flowback fluid by using the same. The complex enzyme provided by the invention can realize the purpose of quickly degrading the residual thickening agent guar gum in the flowback fluid. Meanwhile, the invention also provides a method for treating the fracturing flow-back fluid by using the complex enzyme, and the method has the advantages of simple process, no requirement of special equipment, low treatment cost and realization of cyclic utilization.

Description

Complex enzyme and method for treating guar gum fracturing fluid flowback fluid by using same
Technical Field
The invention relates to a complex enzyme and a method for treating guar gum fracturing fluid flowback fluid by using the same, and belongs to the technical field of oil and gas field development and environmental protection.
Background
Fracturing is one of measures for improving oil and gas yield, and water-based fracturing fluid is most widely used at present due to the advantages of low cost, high safety and the like, and a large amount of fracturing flowback fluid is generated after fracturing is finished. Direct discharge not only pollutes the environment, but also wastes water resources, and the cost for concentrating to a treatment station for harmless treatment is high. The method is feasible and necessary, and can reduce waste water and water for liquid preparation, thereby achieving the effects of saving energy, reducing emission and reducing the fracturing cost.
In recent years, a large number of fracturing fluid recycling technical researches are carried out at home and abroad, CN110937669A discloses a treating agent and a treating method of fracturing flow-back fluid, a method of adding a bactericide is adopted to treat the flow-back fluid, and meanwhile, some inorganic ions are removed, so that the influence of various bacteria on recycling is eliminated;
CN107254305A discloses a treatment and recycling method of a guar gum cross-linked fracturing flow-back fluid, which is used for removing oil, scale and mechanical impurities from the flow-back fluid and then recycling the flow-back fluid; the oxidation degradation by adding an oxidizing agent is more common in the aspect of removing residual thickening agents, but the process needs special equipment and is high in cost.
Disclosure of Invention
Aiming at the prior art, the invention provides a complex enzyme and a method for treating guar gum fracturing fluid flowback fluid by using the complex enzyme, and the bacillus subtilis has strong environment adaptation capability and contains rich protease, lipase, amylase, cellulase and the like. It can strongly decompose carbon series, nitrogen series, phosphorus series and sulfur series pollutants, and decompose complex polysaccharide, protein and water-soluble organic matters; the beta-mannase efficiently degrades the specificity of macromolecular guar gum into micromolecular sugar in an acid environment, and accelerates the absorption and utilization of yeast and bacillus subtilis; the yeast has high propagation speed and low dependence on environmental temperature, the generated generation single-cell protein is easy to flocculate and separate, the three strongly cooperate with each other to efficiently and quickly decompose the residual thickening agent in the return liquid, thereby realizing the purpose of reducing the concentration of the thickening agent and achieving the recycling.
In order to achieve the purpose, the invention adopts the technical scheme that:
the complex enzyme for treating the guar gum fracturing flow-back fluid comprises the following components in percentage by mass: bacillus subtilis, beta-mannase, yeast, adhesive, wherein the adhesive is 2; the compound enzyme adhesive is one of Arabic gum or gelatin; the appearance of the complex enzyme is granular or powdery.
A complex enzyme, a preparation method thereof and a method for treating guar gum fracturing fluid flowback fluid, wherein the guar gum derivative is one or a mixture of hydroxypropyl guar gum, carboxymethyl hydroxypropyl guar gum or fenugreek gum. The method comprises the following steps:
(1) Proportionally adding Bacillus subtilis, beta-mannase and yeast, mixing, adding aqueous solution of adhesive, stirring, granulating, drying and packing.
(2) And settling and separating the flowback liquid to obtain a flowback liquid treatment liquid, wherein the flowback liquid is settled and separated to obtain the flowback liquid treatment liquid, the COD value of the flowback treatment liquid is 2356mg/L, the total sugar content is 18861mg/L, the mass ratio of the flowback liquid treatment to the complex enzyme is 0.05-1.0, the temperature is 10-30 ℃, the air aeration is carried out for 10-72 hours, and thalli and metabolites are separated by flotation or settlement.
The invention has the following excellent effects:
(1) The material is easy to obtain, the treatment process is simple, and the investment cost is low;
(2) The three enzymes are strongly combined, so that the guar gum polysaccharide is rapidly and efficiently degraded;
(3) The post-treatment process is simple, and the thalli and the protein metabolites can be separated by conventional flotation or sedimentation.
The present invention will be further described with reference to the following examples.
The instruments, reagents, materials and the like used in the following examples are, unless otherwise specified, conventional instruments, reagents, materials and the like known in the art, and are commercially available, and the experimental methods, detection methods and the like used in the following examples are, unless otherwise specified, conventional experimental methods, detection methods and the like known in the art.
EXAMPLE 1 Complex enzyme-1 preparation
Adding 20g of bacillus subtilis, 10g of beta-mannase (derived from aspergillus niger expression), 8g of yeast and 6g of 0.3% gelatin aqueous solution into a beaker, uniformly mixing, extruding by using a screw extruder, and drying by using a fluidized bed to obtain the complex enzyme-1.
EXAMPLE 2 Complex enzyme-2 preparation
Adding 20g of bacillus subtilis, 15g of beta-mannase (derived from aspergillus niger expression), 4g of yeast and 6g of 0.3% acacia gum aqueous solution into a beaker, uniformly mixing, extruding by using a screw extruder, and drying by using a fluidized bed to obtain the complex enzyme-2.
Example 3 degradation of flowback fluid
Taking 1L of flowback treatment liquid, adding 0.5g of the compound enzyme of the example 1, introducing air for 24 hours at 25 ℃, standing, adding a polyaluminium chloride flocculating agent, settling, taking supernatant for determination, wherein the COD value is 1072mg/L, the removal rate is 54.5%, the total sugar content is 858.1mg/L, and the removal rate is 57.8%.
Example 4 degradation of flowback fluid
Taking 1L of flowback treatment liquid, adding 1.0g of the compound enzyme of the example 1, introducing air for 24 hours at 25 ℃, standing, adding a polyaluminium chloride flocculating agent, settling, taking supernatant for determination, wherein the COD value is 676.2mg/L, the removal rate is 71.3%, the total sugar content is 541.3mg/L, and the removal rate is 80.6%.
Example 5 degradation of flowback liquid
Taking 1L of flowback treatment liquid, adding 1.0g of the compound enzyme of the embodiment 2, introducing air for 24 hours at 25 ℃, standing, adding a polyaluminium chloride flocculating agent, settling, taking supernatant for determination, wherein the COD value is 756.3mg/L, the removal rate is 67.9%, the total sugar content is 605.4mg/L, and the removal rate is 74.6%.
Example 6 degradation of flowback fluid
Taking 1L of flowback treatment liquid, adding 5.0g of the compound enzyme of the embodiment 2, introducing air for 24 hours at 25 ℃, standing, adding a polyaluminium chloride flocculating agent, settling, taking supernatant for determination, wherein the COD value is 508.9mg/L, the removal rate is 78.4%, the total sugar content is 407.4mg/L, and the removal rate is 84.7%.
Example 7 degradation of flowback liquid
Taking 1L of flowback treatment liquid, adding 1.0g of the compound enzyme of the example 1, introducing air for 72 hours at 25 ℃, standing, adding a polyaluminium chloride flocculating agent, settling, taking supernatant for determination, wherein the COD value is 699.7mg/L, the removal rate is 70.3%, the total sugar content is 560.1mg/L, and the removal rate is 83.3%.
Example 8
Taking 1L of the degradation flowback liquid, adding 1.0g of the composite enzyme of the embodiment 2, introducing air for 72 hours at 20 ℃, standing, adding a polyaluminum chloride flocculating agent, settling, taking supernatant for determination, wherein the COD value is 855.2mg/L, the removal rate is 63.7%, the total sugar content is 684.6mg/L, and the removal rate is 71.9%.
Comparative example degradation flowback fluid
Taking 1L of flowback treatment liquid, introducing air at 25 ℃ for 72 hours, standing, adding a polyaluminium chloride flocculant, settling, taking supernatant fluid for determination, wherein the COD value is 2101.5mg/L, the removal rate is 10.8%, the total sugar content is 1682.3mg/L, and the removal rate is 12.6%.
Although the specific embodiments of the present invention have been described with reference to the examples, the scope of the present invention is not limited thereto, and those skilled in the art will appreciate that various modifications and variations can be made without inventive effort by those skilled in the art based on the technical solution of the present invention.

Claims (7)

1. The complex enzyme for treating guar gum fracturing fluid flowback fluid is characterized in that: the composite enzyme comprises bacillus subtilis, beta-mannase, yeast and adhesive; the composite enzyme comprises the following components in percentage by mass: the bacillus subtilis, the beta-mannase, the yeast and the adhesive are 0.5-1.5.
2. The complex enzyme for treating guar gum fracturing fluid flowback fluid according to claim 1, which is characterized in that: the adhesive is one of acacia gum or gelatin.
3. The complex enzyme for treating guar gum fracturing fluid flowback fluid according to claim 1, which is characterized in that: the appearance of the complex enzyme is granular or powdery.
4. The preparation method of the complex enzyme for treating guar gum fracturing fluid flowback fluid according to any one of claims 1 to 3, characterized by comprising the following steps: proportionally adding Bacillus subtilis, beta-mannase and yeast, mixing, adding aqueous solution of adhesive, stirring, granulating, drying and packing.
5. The use of the complex enzyme for treating guar gum fracturing fluid flowback fluid according to claim 1 for treating guar gum derivative fracturing flowback fluid.
6. The method for treating the guar gum fracturing fluid flowback fluid by using the compound enzyme for treating the guar gum derivative fracturing flowback fluid as claimed in claim 5, is characterized by comprising the following steps of: the guar gum derivative is one or a mixture of hydroxypropyl guar gum, carboxymethyl hydroxypropyl guar gum or fenugreek gum.
7. The method for treating the guar gum fracturing fluid flowback fluid by using the compound enzyme for treating the guar gum derivative fracturing flowback fluid as claimed in claim 5, is characterized in that: the method for treating the fracturing flowback fluid comprises the following steps of: and settling the flowback liquid and separating oil to obtain a flowback liquid treatment liquid before adding the complex enzyme, wherein the mass ratio of the flowback liquid treatment to the complex enzyme is 100-0.05, the temperature is 10-30 ℃, and the air aeration is carried out for 10-72 hours.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0808388D0 (en) * 2007-05-11 2008-06-18 Clearwater Int Llc Apparatus, Compositions, and methods of breaking fracturing fluids
CN107794233A (en) * 2016-08-31 2018-03-13 中石化石油工程技术服务有限公司 A kind of processing method of composite bacteria preparation and preparation method thereof and well-drilling waste water

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2018227567B2 (en) * 2017-03-03 2022-12-01 Locus Solutions Ipco, Llc Compositions and methods for microbial enhanced digestion of polymers in fracking wells

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0808388D0 (en) * 2007-05-11 2008-06-18 Clearwater Int Llc Apparatus, Compositions, and methods of breaking fracturing fluids
CN107794233A (en) * 2016-08-31 2018-03-13 中石化石油工程技术服务有限公司 A kind of processing method of composite bacteria preparation and preparation method thereof and well-drilling waste water

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Performance of a new thermostable mannanase in breaking guar-based fracturing fluids at high temperatures with little premature degradation;Ke Hu等;《Appl Biochem Biotechnol》;20131024;第172卷(第3期);第1215-1226页 *
酶降解制备小分子瓜尔胶;王世彬等;《油田化学》;20140625;第31卷(第2期);摘要，第195页左栏第1段、右栏第2段，第197页右栏第4段 *

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