CN114634804A - Bio-based thickened oil viscosity reducer and preparation method and application thereof - Google Patents
Bio-based thickened oil viscosity reducer and preparation method and application thereof Download PDFInfo
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- CN114634804A CN114634804A CN202210163650.2A CN202210163650A CN114634804A CN 114634804 A CN114634804 A CN 114634804A CN 202210163650 A CN202210163650 A CN 202210163650A CN 114634804 A CN114634804 A CN 114634804A
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- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical compound CCCCCCCC(CC(O)=O)OC(=O)CC(CCCCCCC)OC1OC(C)C(O)C(O)C1OC1C(O)C(O)C(O)C(C)O1 FCBUKWWQSZQDDI-UHFFFAOYSA-N 0.000 claims abstract description 39
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- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- 238000010795 Steam Flooding Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
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- 238000004780 2D liquid chromatography Methods 0.000 description 1
- HVCOBJNICQPDBP-UHFFFAOYSA-N 3-[3-[3,5-dihydroxy-6-methyl-4-(3,4,5-trihydroxy-6-methyloxan-2-yl)oxyoxan-2-yl]oxydecanoyloxy]decanoic acid;hydrate Chemical compound O.OC1C(OC(CC(=O)OC(CCCCCCC)CC(O)=O)CCCCCCC)OC(C)C(O)C1OC1C(O)C(O)C(O)C(C)O1 HVCOBJNICQPDBP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
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- 239000007836 KH2PO4 Substances 0.000 description 1
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 1
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- 125000000129 anionic group Chemical group 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
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- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
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- 239000002888 zwitterionic surfactant Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
- C09K8/604—Polymeric surfactants
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Abstract
The invention discloses a bio-based thickened oil viscosity reducer and a preparation method and application thereof, wherein the viscosity reducer consists of viscosity reducing components and a preservative; the viscosity reducing component comprises 80-95% of rhamnolipid fermentation broth supernatant and 5-20% of biological emulsifier fermentation broth by mass percentage; the rhamnolipid concentration in the supernatant of rhamnolipid fermentation liquor is 2-5%, wherein the structural component of the dirhamnolipid is more than or equal to 65%; the rhamnolipid fermentation liquor contains a vegetable oil hydrolysate sodium aliphatate; the biological emulsifier fermentation broth is a fermentation broth of a recombinant bacterium containing an emulsifying functional protein. The bio-based thickened oil viscosity reducer disclosed by the invention obtains rhamnolipid as a surfactant component through microbial fermentation, and is prepared by compounding a biological emulsifier, compared with the existing chemical viscosity reducer, the bio-based thickened oil viscosity reducer has the characteristics of stronger salt resistance and high temperature resistance, capability of effectively reducing the oil-water interfacial tension and the surface tension, safety and environmental friendliness, and the viscosity reducing effect on thickened oil can reach 80-99%, and the cost can be effectively reduced.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a bio-based thickened oil viscosity reducer and a preparation method and application thereof.
Background
The reserve of the thick oil in China is large and is mainly distributed in oil fields such as Liaohe, Xinjiang, Shengli, Nanyang, Hongkong, Jilin and North China, and the geological reserve of the thick oil accounts for about 17 percent of the total reserve. In recent years, with the increasing demand of petroleum and the decreasing exploitation of crude oil from conventional oil reservoirs, the development of heavy oil is more and more emphasized.
The high content of colloids and asphaltenes in the heavy oil results in high viscosity and poor fluidity, which undoubtedly greatly increases the costs of heavy oil recovery and transportation. Therefore, the key point in the process of thick oil recovery is to reduce viscosity of thick oil so as to improve the fluidity problem of the thick oil. In order to improve the recovery efficiency of the thickened oil, a thermal recovery viscosity reduction technology represented by steam flooding has become a large-scale applied thickened oil recovery technology abroad; the heavy oil reservoir in China is deep, the gas injection pressure is high, the formation temperature is high, the dryness is low, the reservoir thickness is thin, the edge bottom water is active, and the heavy oil steam flooding exploitation efficiency is seriously influenced.
In recent years, the emulsification viscosity-reducing technology is popular in oil fields due to the characteristics of good viscosity-reducing effect, simple process and low economic cost; the basic principle is that the viscosity of crude oil is reduced by using the viscosity-reducing oil displacement agent, and the fluidity of the crude oil is improved, so that the recovery rate of thick oil is improved. In the process, the emulsification viscosity-reducing method is simple and convenient to operate, active water containing surfactant is injected into a thick oil layer, and the thick oil is emulsified by stirring with a certain external force and is converted into oil-in-water (O/W) emulsion with a continuous phase as a water phase, so that the viscosity and the flow friction of the thick oil are obviously reduced, and the exploitation capacity of the thick oil is effectively improved.
At present, the emulsifying viscosity-reducing agent reported in research is a compound preparation with a chemical surfactant as a main body. Generally speaking, the performance of a single chemical surfactant is difficult to achieve the expected target, and the combination of multiple surfactants is a universal solution, and the temperature-resistant and salt-resistant thick oil emulsifying viscosity reducer with multiple anionic and nonionic characteristics is obtained through the combination of the surfactants. Chemical surfactants such as nonionic surfactant AEO-15, OP-10, Tween, unsaturated fatty alkyl amide, lauryl zwitterionic surfactant imidazoline, anionic surfactant Sodium Dodecyl Sulfate (SDS), self-made sulfonic acid type surfactant, fatty alcohol sulfate, etc. have been used in the literature or patents.
The biosurfactant is easy to dissolve in water, has lower Critical Micelle Concentration (CMC) and has good surface interfacial activity on an oil-water interface; the wettability of the oil-bearing rock can be increased, residual oil in rock holes is easy to desorb, and the emulsion viscosity-reducing effect on crude oil is stronger. Compared with chemical surfactants, the biological surfactant is easy to biodegrade, does not damage the stratum and has great application potential in tertiary oil recovery and oil transportation. In patent CN108130064A, lipopeptide products are obtained by microbial fermentation and are used as surfactant components, and a thickened oil viscosity reducer is prepared by compounding chemical surfactants, wherein the thickened oil viscosity reducer comprises lipopeptide alcoholic solutions prepared by fermentation and extraction and chemical surfactants (anionic surfactants and nonionic surfactants).
Currently, with the development of technologies, varieties such as biological surfactant lipopeptide and glycolipid enter the industrialization stage, and the development of a bio-based emulsifying viscosity reducer taking a biological surfactant as a functional main body has important significance for promoting the greening of oil field chemicals.
Disclosure of Invention
The invention provides a bio-based thickened oil viscosity reducer, a preparation method and application thereof for overcoming the defects of the prior art.
The bio-based thick oil viscosity reducer is prepared by using a microbial surfactant and consists of viscosity reducing components and a preservative; the viscosity reducing component comprises 80-95% of rhamnolipid fermentation broth supernatant and 5-20% of biological emulsifier fermentation broth by mass percentage;
wherein the concentration of the rhamnolipid in the supernatant of the rhamnolipid fermentation liquor is 2-5% (mass percent), wherein the structural component of the dirhamnolipid is more than or equal to 65%; the rhamnolipid fermentation liquor contains a vegetable oil hydrolysate sodium aliphatate;
the biological emulsifier fermentation broth is a fermentation broth of a recombinant bacterium containing an emulsifying functional protein.
As a preferred embodiment, the content of the sodium fatty acid is 0.1-1% of the weight of the rhamnolipid fermentation broth.
In a preferred embodiment, the recombinant bacterium containing the lactonized functional protein is a recombinant bacterium containing acetylxylan esterase AXE protein.
As a preferred embodiment, the content of the emulsified functional protein in the biological emulsifier fermentation broth is 1500-2300 mg/L.
As a preferred embodiment, the preservative is added in an amount of 0.05% by mass of the viscosity reducing component.
As a preferred embodiment, the preservative is preferably bronopol.
The preparation method of the bio-based thickened oil viscosity reducer comprises the following steps:
fermenting a rhamnolipid fermentation strain to prepare rhamnolipid fermentation liquor, centrifuging to obtain fermentation liquor supernatant, adjusting the pH to be alkaline, and then performing bacterial activity removal treatment to obtain a first viscosity-reducing component;
taking a recombinant bacterium containing the emulsified functional protein, fermenting the recombinant bacterium to obtain a fermentation liquid, adjusting the pH value to be alkaline, and obtaining a second viscosity-reducing component;
and mixing the first viscosity reducing component and the second viscosity reducing component in proportion, adding a preservative, uniformly stirring, and standing to obtain a finished product of the bio-based thick oil viscosity reducer.
As a preferred embodiment, the first and second viscosity reducing components are mixed at 25-50 ℃.
As a preferred embodiment, the bacterial viability removing treatment is: and (4) preserving the temperature of the fermentation liquid supernatant fluid after the pH is adjusted to be alkaline at high temperature.
The application of the bio-based thickened oil viscosity reducer comprises the application of the bio-based thickened oil viscosity reducer in crude oil degradation.
The invention relates to a bio-based viscosity reducer for thick oil, which is prepared by taking a rhamnolipid product synthesized by microbial fermentation of oil as a main component of a biosurfactant, simultaneously containing a sodium fatty acid component with a surface active component generated by microbial degradation of oil and compounding a bio-emulsifier. Compared with the existing chemical viscosity reducer, the viscosity reducer has the characteristics of stronger salt resistance and high temperature resistance, can effectively reduce the oil-water interfacial tension and the surface tension, and has the viscosity reducing effect on the thickened oil of 70-99%.
The product is composed of all biological-based components, and is safe and environment-friendly; and because the fermentation liquor is directly used for compounding, a refined product does not need to be extracted from the fermentation liquor, and the cost can be effectively reduced.
Drawings
FIG. 1 is a standard curve of rhamnolipid concentration quantified by anthrone-sulfuric acid method.
FIG. 2 shows the peak appearance and component structure of rhamnolipid analyzed by ELSD-HPLC-MS.
Detailed Description
The technical scheme of the invention is further explained by combining the description of the attached drawings and the detailed description.
In the examples, the rhamnolipid is prepared according to the invention patent of ZL201711014867.2, namely 'a pseudomonas aeruginosa strain and application thereof'.
In the examples, the biological emulsifier is prepared according to the patent of invention 'application of acetylxylan esterase AXE as emulsifier' granted by the applicant of patent No. 201610814319.7.
Example 1
This example illustrates the method for the quantification of rhamnolipids, the structural characterization and the method for the quantification of sodium aliphatate.
The rhamnolipid yield measured by a sulfuric acid-anthrone method is as follows: after fermentation is finished, 1mL of fermentation liquor is centrifuged (12000r/min, 2min) to remove thalli, supernatant of the fermentation liquor is obtained, deionized water is added to dilute by a proper multiple and then is fully and uniformly oscillated, 1mL of the fermentation liquor is added into a 10mL glass test tube with a plug, 5mL of 75% sulfuric acid-anthrone reagent (0.20g of anthrone is dissolved in 100mL of 75% sulfuric acid) is immediately added, the mixture is uniformly oscillated and then is placed into an electromagnetic oven to be boiled and heated for 10min, then the mixture is taken out and is rapidly immersed into crushed ice for 10min, and the light absorption value is measured at 625 nm. And (3) calculating the content of the rhamnolipid in the fermentation liquor by utilizing a standard curve drawn by the reaction of the rhamnolipid standard substance and a 75% sulfuric acid-anthrone solution. Rhamnolipid profiles are shown in figure 1.
The rhamnolipid homolog high performance liquid chromatography-mass spectrometry (HPLC-MS) analysis method comprises the following steps: after fermentation is finished, centrifuging (12000r/min, 2min) 1mL of fermentation liquor to remove thalli to obtain fermentation liquor supernatant, adding 100 mu L of fermentation liquor supernatant into 900 mu L of ethanol solution, performing vortex oscillation for 1min, and centrifuging (12000r/min, 5min) to remove precipitates; the supernatant was filtered through a 0.22 μm organic filter membrane and used as a sample for liquid chromatography. The analytical column used was Sepax HP-C18 (4.6X 150mm, 5 μm); the mobile phase was 0.05% formic acid solution (a), 100% acetonitrile (B). The column oven temperature was 30 deg.C, the drift temperature of the Evaporative Light Scattering Detector (ELSD) was 60 deg.C, and the nebulizer flow rate was 1.5L/min. Elution gradient is 0-5 min, 30-70% of B; 5-30 min, 70% -90% B; 30-40 min, 100% B. The flow rate was 1 mL/min. Two-dimensional liquid chromatography/quadrupole-time of flight mass spectrometry (2DLC/6520Q-TOF) analysis was used to provide information on rhamnolipid structure, mass spectrometry conditions: the atomizing gas and the drying gas are N2The HPLC/Q-TOF-MS system uses an ESI ion source with an ion source temperature of 350 ℃, an ion source gas flow rate of 10L/min, a spray voltage of 45P, a mass spectrometry scan mass range: 200 to 1000 m/Z. The peak profile of the rhamnolipid homolog component is shown in figure 2.
The detection method of the residual oil component in the rhamnolipid fermentation liquor comprises the following steps: taking 1mL of fermentation liquor in a centrifugal tube, centrifuging for 10min-15min at 10,000rpm to ensure sufficient demulsification, demixing residual grease, adding n-hexane with the same volume, slightly oscillating, standing for demixing, transferring the n-hexane phase of the extracted grease into a new centrifugal tube weighed in advance, placing the centrifugal tube in an oven, drying to constant weight, cooling and weighing. To the white solid in the centrifuge tube, NaOH solution (1%) was added dropwise and the white solid was immediately dissolved, indicating that the lipid fraction extract was a fatty acid.
Example 2
This example illustrates the expression of Pseudomonas aeruginosa CCTCC NO: m2017494 various fermentation systems for preparing rhamnolipid by soybean oil/glycerol fermentation, wherein the rhamnolipid content, structural components and sodium aliphatate content in the fermentation liquid.
Seed medium (LB medium): 10.0g/L of peptone, 5.0g/L of yeast powder and 10.0g/L of NaCl.
Fermentation medium: soybean oil 0-60g/L, glycerin 0-30g/L, sodium nitrate 6-10g/L, K2HPO4·3H2O 4g/L、KH2PO4 4g/L、NaCl 1g/L、KCl 1g/L、MgSO4·7H20.2g/L of O and anhydrous CaCl20.1g/L, 1g/L yeast powder and 2mL trace elements (FeCl)3 0.16g/L、CuSO4 0.15g/L、ZnSO4·7H2O 1.5g/L、MnSO4·H2O1.5 g/L), pH7, inoculum size 3% (v/v).
Pseudomonas aeruginosa CCTCC NO: m2017494 is firstly activated by a flat plate at 37 ℃ for strain activation, a loop of well-grown thalli is inoculated into 50mL LB culture medium after 20h, the culture is carried out at 37 ℃ and 200rpm for 24h, then the strain is inoculated into a groove triangular flask with the liquid loading amount of 50mL fermentation liquid/250 mL according to the inoculation amount of 3% (v/v), the culture is carried out at 37 ℃ and the rotating speed of 200rpm, and the fermentation is carried out for 72-96 h. After fermentation is finished, the fermentation liquor is centrifuged to remove thalli, NaOH solution is added into the clear liquid of the fermentation liquor for stirring, the pH value of the fermentation liquor is adjusted to 8.5, and the fermentation liquor is subjected to heat preservation at 90 ℃ for 10min, so that the fermentation liquor can be used for preparing the subsequent biodegradable viscosity reducer.
The content of rhamnolipid, the proportion of dirhamnolipid components and the content of fatty acid sodium in grease residue in the supernatant of rhamnolipid fermentation liquor for preparing the biological viscosity reducer are shown in table 1, and based on the adjustment of the components and the concentration of fermentation raw materials, the content of rhamnolipid in the supernatant of fermentation liquor for standby use is 2-5%, the proportion of dirhamnolipid components is 66-90%, and the proportion of fatty acid sodium is about 0-1%.
TABLE 1 rhamnolipid fermentation broth preparation and functional components
Example 3
This example illustrates the preparation and detection of the bio-emulsifier.
The specific scheme of utilizing the recombinant gene engineering bacteria to induce and express the emulsifying functional protein AXE is as follows:
(1) starting strains: escherichia coli (Escherichia coli) BL21-pET28 a-Cah.
(2) The seed culture medium is LB culture medium, its composition is: 5g/L of yeast powder, 10g/L of peptone and 10g/L of sodium chloride;
the culture conditions are as follows: a 250mL triangular flask, the liquid loading amount is 50mL, the culture temperature is 37 ℃, the rotating speed of a shaking table is 200r/min, and the culture is carried out for 12 h;
(3) the fermentation medium is composed of a self-induction medium and comprises the following components: 25g/L of yeast powder, 15g/L of tryptone, 10g/L of sodium chloride, 0.1% of glycerol (v/v), 0.2% of glucose (w/v) and 0.2% of lactose (w/v);
the culture conditions are as follows: 3L of liquid loading amount, 3.3 percent (v/v) of inoculation amount, 30 ℃ of fermentation temperature, 7.5 of pHs, 200r/min of stirring rotation speed and 1.5vvm of ventilation volume for fermentation for 16 h. And adding NaOH solution into the fermentation broth after the fermentation is stopped, stirring, and adjusting the pH of the fermentation broth to 8.5, so that the fermentation broth can be used for preparing the subsequent biological viscosity reducer.
Analytical detection of biological emulsifier protein: sampling the prepared fermentation liquor, determining the total protein content of the fermentation liquor by using a Brandford method, and analyzing the proportion of the target protein AXE in the total protein by using SDS-PAGE electrophoresis. The result shows that the total protein content in the fermentation liquor for standby is about 2.5-3.2g/L, wherein the proportion of the emulsifying functional protein AXE in the total protein is about 60-72%, and the content of the emulsifying functional protein AXE is about 1500-.
Example 4
This example illustrates the preparation of a bio-based viscosity reducer.
At room temperature to 50 ℃, as shown in table 2, mixing a biological surfactant rhamnolipid fermentation broth and a biological emulsifier fermentation broth according to a certain proportion, adding 0.05% preservative bronopol (bronopol), stirring and uniformly mixing for 60-120 min, and standing for 2-3h to obtain a finished product of the bio-based thick oil viscosity reducer. A comparative example 4 group was set, wherein the first viscosity-reducing component used in comparative examples 3 and 4 was a commercial rhamnolipid standard, and was prepared as a 4.0% solution by mass with a 30% proportion of the dirhamnolipid component.
TABLE 2 Bio-based thickened oil viscosity reducer finished product component table (mass ratio)
Example 5
This example illustrates the viscosity reducing effect of various bio-based viscosity reducing agents on crude oil.
4 crudes were selected and their ground viscosities (measured at 50 ℃) are shown in Table 3. The viscosity reducer of example 4 and the finished product of the comparative example were diluted with tap water at a ratio of 1:12 to prepare 8.5% active water, and 30g of the active water was added to 70g of crude oil. Crude oil and active water used in an experiment are respectively placed in an incubator at 50 ℃ and heated for 2 hours, then the crude oil and the active water are rapidly stirred uniformly, the viscosity of the crude oil is measured, then the mixed solution is placed at room temperature and stood overnight, the viscosity of the crude oil is measured again, the stability of the bio-based heavy oil viscosity reducer on the viscosity reduction of various crude oils is investigated, the results are shown in table 3, the viscosity reduction rate can reach 70-99% after 4 kinds of crude oil and active water are uniformly mixed according to the ratio of 7:3 at 50 ℃, the viscosity reduction rate of the compound viscosity reducer can still reach 80-95% after standing overnight at room temperature, and the compound viscosity reducer has good stability. The viscosity reducing effects of comparative examples 1 to 4 have a problem of poor system stability.
TABLE 3 viscosity reducing effect of bio-based viscosity reducing agent on 4 crude oils
Example 6
This example illustrates the selectivity of bio-based viscosity depressants for thick oil.
Taking the bio-based thick oil viscosity reducer 6 with good performance in example 4 as a research object, selecting two kinds of thick oil with different components as an action object, diluting the viscosity reducer 6 with tap water according to a ratio of 1:12 to prepare active water with the content of 8.5%, adding 30g of the active water into 70g of crude oil, respectively placing the crude oil and the active water used in the experiment in an incubator at 50 ℃ for heating for 2 hours, rapidly and uniformly stirring, measuring the viscosity of the crude oil, then placing the mixed solution at room temperature for standing overnight, measuring the viscosity of the crude oil again, and calculating the viscosity reduction stability of the bio-based thick oil viscosity reducer on the two kinds of thick oil materials, wherein the results are shown in table 4. The bio-based thickened oil viscosity reducer has excellent viscosity reducing performance on thickened oil with more colloid and less wax crystals, but has poorer effect performance on high-pour-point oil (with less wax crystal and more colloid) and has the phenomenon of wax crystal precipitation.
TABLE 4 viscosity reducing effect of bio-based heavy oil viscosity reducer on two crude oils with different physical properties
Example 7
This example is used to illustrate that the bio-based heavy oil viscosity reducer has better temperature resistance and salt tolerance.
The bio-based thickened oil viscosity reducer 6 with good performance in example 4 is taken as a research object, the viscosity reducer 6 is diluted with deionized water and simulated water respectively to prepare 1% active water according to a ratio of 1:100, and an interfacial tension meter is utilized to test the change of oil-water dynamic interfacial tension of crude oil at 60 ℃. And (3) placing the 1% active water in a constant temperature box at 80 ℃ for 10 days, testing the interfacial tension with the crude oil after the completion, and inspecting the temperature resistance of the biological viscosity reducer. The crude oil is common thick oil provided by a certain oil field, and the ground viscosity is 9028mPa.s (measured at 50 ℃); the simulated water is produced by mixing the oil well output liquid provided by a certain oil field with the injected water according to the proportion of 1:1, and the produced liquid is subjected to oil-water layering and filtering treatment in advance. The detection shows that the produced liquid and the injected water belong to highly mineralized water, the mineralization degree of the produced liquid is 55920mg/L, the mineralization degree of the injected water is 64525mg/L, wherein the Ca content2+、Mg2+The content reaches 3200 mg/L.
The results of the influence of the mineralization degree and the high temperature on the interfacial activity of the bio-based thick oil viscosity reducer are shown in table 5. Under the conditions of high salinity simulation water and heat preservation at 80 ℃ for 10 days, the bio-based thickened oil viscosity reducer can still reduce the oil-water interfacial tension to 0.1mN/m, which shows that the emulsification and viscosity reduction capability is still stable.
TABLE 5 influence of degree of mineralization and high temperature on oil-water interfacial activity of bio-based heavy oil viscosity reducer
| Active water numbering | Diluting water | The dosage of viscosity reducing agent | Heat preservation at 80 deg.C | Interfacial tension mN/m |
| Activated water 1 | Deionized water | 1％ | - | 0.085 |
| Activated water 2 | Simulated water | 1％ | - | 0.068 |
| Activated water 3 | Deionized water | 1％ | 10d | 0.102 |
| Activated water 4 | Simulated water | 1％ | 10d | 0.104 |
Claims (10)
1. A bio-based thickened oil viscosity reducer is characterized by comprising viscosity reducing components and a preservative; the viscosity reducing component comprises 80-95% of rhamnolipid fermentation broth supernatant and 5-20% of biological emulsifier fermentation broth by mass percentage;
wherein the concentration of the rhamnolipid in the rhamnolipid fermentation liquor supernatant is 2-5%, and the structural component of the dirhamnolipid is more than or equal to 65%; the rhamnolipid fermentation liquor contains a vegetable oil hydrolysate sodium aliphatate;
the biological emulsifier fermentation broth is a fermentation broth of a recombinant bacterium containing an emulsifying functional protein.
2. The bio-based heavy oil viscosity reducer according to claim 1, wherein the content of the sodium fatty acid is 0.1-1% of the weight of the rhamnolipid fermentation broth.
3. The bio-based heavy oil viscosity reducer according to claim 1, wherein the recombinant bacteria containing the emulsifying functional protein is a recombinant bacteria containing acetyl xylan esterase AXE protein.
4. The bio-based heavy oil viscosity reducer according to claim 1, wherein the content of the emulsification functional protein in the bio-emulsifier fermentation broth is 1500-2300 mg/L.
5. The bio-based heavy oil viscosity reducer according to claim 1, wherein the preservative is added in an amount of 0.05% by mass of the viscosity reducing component.
6. The bio-based heavy oil viscosity reducer according to claim 1, wherein the preservative is bronopol.
7. The method for preparing the bio-based thickened oil viscosity reducer according to any one of claims 1 to 6, which comprises the following steps:
fermenting a rhamnolipid fermentation strain to prepare rhamnolipid fermentation liquor, centrifuging to obtain fermentation liquor supernatant, adjusting the pH to be alkaline, and then performing bacterial activity removal treatment to obtain a first viscosity reducing component;
taking a recombinant bacterium containing the emulsified functional protein, fermenting the recombinant bacterium to obtain a fermentation liquid, adjusting the pH value to be alkaline, and obtaining a second viscosity-reducing component;
and mixing the first viscosity reducing component and the second viscosity reducing component in proportion, adding a preservative, uniformly stirring, and standing to obtain a finished product of the bio-based thick oil viscosity reducer.
8. The method of claim 7, wherein the first and second viscosity reducing components are mixed at 25-50 ℃.
9. The method for preparing a bacterial suspension according to claim 7, wherein the bacterial viability removing treatment is: and (4) preserving the temperature of the fermentation liquid supernatant fluid after the pH is adjusted to be alkaline at high temperature.
10. Use of the bio-based heavy oil viscosity reducer of any one of claims 1 to 6 in crude oil degradation.
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| US5866376A (en) * | 1997-02-25 | 1999-02-02 | Universidad Simon Bolivar | Production of oily emulsions mediated by a microbial tenso-active agent |
| CN107556993A (en) * | 2016-07-01 | 2018-01-09 | 中国石油化工股份有限公司 | A kind of biological emulsifying pour depressor of resisting high temperature, high salt and preparation method thereof |
| CN110643339A (en) * | 2019-10-22 | 2020-01-03 | 中国石油化工股份有限公司 | Biological enzyme composite preparation for oil extraction and preparation method and application thereof |
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