CN115125064A - Environment-friendly cleaning agent and application thereof in oil sludge treatment - Google Patents
Environment-friendly cleaning agent and application thereof in oil sludge treatment Download PDFInfo
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- CN115125064A CN115125064A CN202110331422.7A CN202110331422A CN115125064A CN 115125064 A CN115125064 A CN 115125064A CN 202110331422 A CN202110331422 A CN 202110331422A CN 115125064 A CN115125064 A CN 115125064A
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- sophorolipid
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- 239000010802 sludge Substances 0.000 title claims abstract description 85
- 239000012459 cleaning agent Substances 0.000 title claims abstract description 43
- 239000003876 biosurfactant Substances 0.000 claims abstract description 65
- 150000001875 compounds Chemical class 0.000 claims abstract description 50
- 239000004094 surface-active agent Substances 0.000 claims abstract description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 27
- 238000004140 cleaning Methods 0.000 claims abstract description 23
- 229930186217 Glycolipid Natural products 0.000 claims abstract description 7
- 150000001413 amino acids Chemical class 0.000 claims abstract description 7
- 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 group 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 claims abstract description 6
- 238000000855 fermentation Methods 0.000 claims description 116
- 230000004151 fermentation Effects 0.000 claims description 116
- 108010028921 Lipopeptides Proteins 0.000 claims description 63
- ZTOKUMPYMPKCFX-CZNUEWPDSA-N (E)-17-[(2R,3R,4S,5S,6R)-6-(acetyloxymethyl)-3-[(2S,3R,4S,5S,6R)-6-(acetyloxymethyl)-3,4,5-trihydroxyoxan-2-yl]oxy-4,5-dihydroxyoxan-2-yl]oxyoctadec-9-enoic acid Chemical compound OC(=O)CCCCCCC/C=C/CCCCCCC(C)O[C@@H]1O[C@H](COC(C)=O)[C@@H](O)[C@H](O)[C@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](COC(C)=O)O1 ZTOKUMPYMPKCFX-CZNUEWPDSA-N 0.000 claims description 62
- FCBUKWWQSZQDDI-UHFFFAOYSA-N rhamnolipid Chemical group 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 description 62
- 238000005406 washing Methods 0.000 claims description 28
- 244000063299 Bacillus subtilis Species 0.000 claims description 10
- 235000014469 Bacillus subtilis Nutrition 0.000 claims description 10
- 241000589517 Pseudomonas aeruginosa Species 0.000 claims description 10
- 230000010355 oscillation Effects 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 7
- 241000222120 Candida <Saccharomycetales> Species 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 2
- 244000005700 microbiome Species 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 30
- 239000000126 substance Substances 0.000 abstract description 26
- 238000000034 method Methods 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- 238000005067 remediation Methods 0.000 abstract description 2
- 239000003921 oil Substances 0.000 description 114
- 239000002699 waste material Substances 0.000 description 15
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- 239000006228 supernatant Substances 0.000 description 11
- 239000002689 soil Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
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- 238000000638 solvent extraction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 241001052560 Thallis Species 0.000 description 5
- 241000235646 Cyberlindnera jadinii Species 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
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- 238000007865 diluting Methods 0.000 description 3
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- 239000003945 anionic surfactant Substances 0.000 description 2
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- 241000894006 Bacteria Species 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/10—Amino carboxylic acids; Imino carboxylic acids; Fatty acid condensates thereof
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/662—Carbohydrates or derivatives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention belongs to the technical field of environmental remediation, and particularly relates to an environment-friendly cleaning agent and application thereof in treatment of oily sludge. The cleaning agent contains a compound biosurfactant, wherein the compound biosurfactant is a glycolipid biosurfactant and an amino acid biosurfactant, and the mass fraction of the surfactant is (2-20): 1, and regulating the PH value to 8-9 by NaOH. The compound cleaning agent in the method can achieve a better oil sludge cleaning effect under a lower concentration condition, under different temperature conditions, the compound cleaning agent has a stable cleaning effect on different oil field oil sludge, the content of the residual oil of the sludge is lower than that of a chemical surfactant and a single biological surfactant with the same concentration after being cleaned, and the components of the environment-friendly cleaning agent are all biodegradable surfactants, so that the compound cleaning agent has the characteristics of low dosage, environment friendliness, stable performance and the like.
Description
Technical Field
The invention belongs to the technical field of environmental remediation, and particularly relates to an environment-friendly cleaning agent and application thereof in treatment of oily sludge.
Background
The oil sludge is usually generated in the processes of oil exploitation, processing, storage and transportation, the waste oil sludge contains a large amount of carcinogenic toxic and harmful substances such as benzene, the waste oil sludge can cause harm to ecological environment and human health by random stacking, the waste oil sludge is listed as one of national hazardous wastes in China, and the waste oil sludge needs to be treated and can be backfilled into soil after the oil content of the waste oil sludge reaches the standard.
At present, the thermochemical oil washing mainly uses a chemical surfactant, is efficient and quick, but has high operation cost and is accompanied with the problem of secondary pollution, and has adverse effect on subsequent advanced treatment such as biodegradation, and the biosurfactant is used as a nontoxic degradable green product, and the treated oily sludge has the characteristics of small using amount, high crude oil recovery rate, economy and environmental protection, and is a novel environment-friendly oil washing agent.
Sophorolipid, rhamnolipid and lipopeptide are biosurfactants which are most researched in the field of oil-containing solid waste treatment at the present stage, but a single biosurfactant component usually has an advantage only for a certain petroleum component, so that the problem of poor effect can occur when complex oil sludge and aged oil sludge are treated, and the treatment cost of the biosurfactant is higher than that of a chemical surfactant, so that the use amount of the biosurfactant in the oil sludge treatment process is reduced, the oil sludge cleaning efficiency is improved, and the biosurfactant has important significance for realizing the recycling and harmless treatment of the oil sludge.
Disclosure of Invention
In order to improve the washing efficiency of the oil-containing sludge and reduce the oil content of the oil sludge, the invention provides an environment-friendly cleaning agent and application thereof in treating the oil-containing sludge.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
an environment-friendly cleaning agent comprises a compound biosurfactant, wherein the compound biosurfactant is a glycolipid biosurfactant and an amino acid biosurfactant, and the mass fractions of the biosurfactant are (2-20): 1, and regulating the PH value to 8-9 by NaOH.
The glycolipid biosurfactant is rhamnolipid and/or sophorolipid; the amino acid biosurfactant is lipopeptide; wherein the rhamnolipid, sophorolipid and lipopeptide are obtained or purified by fermentation of corresponding strains.
The rhamnolipid is obtained by fermenting pseudomonas aeruginosa, and the preservation number of pseudomonas aeruginosa strains is CGMCC NO.19110, and the rhamnolipid is purchased from commercial approaches; the sophorolipid is obtained by fermenting candida, the preservation number of candida is CCTCC NO: M2014349, and the sophorolipid is purchased from a commercial way; the lipopeptide is obtained by fermenting Bacillus subtilis, and the Bacillus subtilis (PL-10) is sent to a common microorganism center of China Committee for culture Collection of microorganisms in 2019, 3 months and 4 days by a laboratory, wherein the addresses are as follows: no. 3 of Xilu No.1 of Beijing, Chaoyang, and the preservation number of the strain is CGMCC NO. 17302.
The cleaning agent is prepared from the following components in percentage by mass (1-20): 1 or the rhamnolipid and the lipopeptide in a mass ratio of (2-20): 1, or the mass ratio of sophorolipid to lipopeptide is (1-10): (1-10): 1, the cleaning agent is a weakly alkaline cleaning agent (PH 8-9).
An application of the cleaning agent and an application of the cleaning agent in cleaning oil sludge.
And mixing the oily sludge with the cleaning agent, and oscillating, centrifuging and air-drying to finish the cleaning of the oily sludge.
The oil sludge and the cleaning agent are mixed according to the mass volume ratio of 1: (2-20) adding a cleaning solution into the oily sludge, wherein the washing temperature is 20-80 ℃, the oscillation speed is 100-350 r/min, and the oscillation time is 10-90 min.
In the washing step, the washing temperature may be 50 ℃, the oscillation speed may be 150r/min, and the oscillation time may be 30 min.
The invention has the following advantages:
according to the cleaning agent, the specific nonionic and the anionic surfactant are compounded, and a compounded system has smaller critical micelle concentration and lower surface/interface tension, can reduce the steric hindrance of the nonionic and effectively reduce the electrostatic repulsion of the anionic surfactant, and has a synergistic effect on oil sludge cleaning; specifically, the waste oil sludge is cleaned by adopting a compound solution of glycolipids and amino acid biosurfactant, and the best cleaning effect can be achieved under the condition of 0.1% of mass concentration, so that the oil content of the oil sludge is reduced to below 2%, the cleaning efficiency is not influenced by the temperature condition, and the stability is good. Compared with a single biological surfactant, the compound biological surfactant has higher efficiency for cleaning oil sludge, and compared with a chemical surfactant with the same concentration, the compound biological surfactant has higher cleaning efficiency for different oil sludge under different temperature conditions.
Drawings
FIG. 1 is a comparative graph of the effects of the compound cleaning agent, the single biosurfactant and the chemical surfactant on degradation of sludge under the same concentration condition.
FIG. 2 is a comparison graph of the effects of three compound detergents with different mass ratios on degradation of oil sludge.
FIG. 3 is a graph comparing the effect of the compound cleaning agent and the chemical surfactant in degrading sludge under different temperature conditions.
FIG. 4 is a graph comparing the effect of the compounded biosurfactant on degrading sludge at different concentrations.
Fig. 5 is a graph comparing the effect of chemical surfactant degrading sludge at different concentrations according to the present invention.
FIG. 6 is a comparison graph of the degradation effects of the compound cleaning agent and the chemical surfactant on different oil field oil sludge.
FIG. 7 is a graph showing the effect of three complex biosurfactants and two complex biosurfactants on washing waste oil sludge in Xinjiang, Daqing and Hongkong oil fields
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
The materials used in the following examples are commercially available without specific reference.
Example 1:
the waste oil sludge in the embodiment is from an oil field in Xinjiang, and an oil sludge soil sample is dried in the shade, crushed, sieved by a sieve with the aperture of 2mm, removed of impurities, and packaged in a sealed bag for storage and standby.
The rhamnolipid is obtained by fermenting pseudomonas aeruginosa CGMCC NO.19110 for 7 days according to the prior mode, the sophorolipid is obtained by fermenting candida utilis CCTCC NO. M2014349 for 5 days, and the lipopeptide is obtained by fermenting bacillus subtilis CGMCC NO.17302 for 7 days.
Preparation of biosurfactant solution: after the thalli are removed by centrifugation of rhamnolipid, sophorolipid and lipopeptide fermentation liquor at 5000r/min, the pH of supernatant is adjusted to 8.5 by NaOH solution, and the concentration of the obtained fermentation liquor is 40g/L of rhamnolipid, 100g/L of sophorolipid and 20g/L of lipopeptide.
The biosurfactant solutions obtained above were prepared as follows:
compound liquid 1: adding 160mL of sophorolipid fermentation liquor and 200mL of lipopeptide fermentation liquor to a constant volume of 1.0L (mass ratio of 4: 1); compound liquid 2: adding rhamnolipid fermentation liquor and lipopeptide fermentation liquor (mass ratio is 4:1), namely taking 400mL of rhamnolipid fermentation liquor and 200mL of lipopeptide fermentation liquor to fix the volume to 1L; compound liquid 3: taking 80mL of sophorolipid fermentation liquor, 200mL of rhamnolipid fermentation liquor and 200mL of lipopeptide fermentation liquor to fix the volume to 1L (mass ratio of 2:2: 1); control 1: sodium dodecyl sulfate solution (chemical surfactant), i.e. 20g of sodium dodecyl sulfate was taken to be constant volume to 1.0L, control 2: preparing sophorolipid solution fermentation liquor, namely taking 200mL of sophorolipid fermentation liquor and fixing the volume to 1.0L; control 3: the volume of rhamnolipid solution fermentation liquor is set to 1.0L, wherein 500mL of rhamnolipid fermentation liquor is taken; control 4: lipopeptide fermentation broth. The total mass fraction of the biosurfactant in the solutions of the above groups is 0.2%.
Placing 5g of oil sludge into a conical flask, respectively adding more than 15mL of surfactant solutions into each group, arranging three parallel samples in each group, hot washing at 50 ℃ for 30min, stirring at 150rpm, standing, centrifuging at 5000r/min for 30min to separate oil liquid from solid, and decanting to remove oil slick and supernatant.
And (4) after drying the residual solid matters, determining the residual oil quantity of the oil sludge by using an organic solvent extraction method.
The result is shown in figure 1, after the compound cleaning agent cleans the oil sludge, the content of the oil sludge residual oil is lower than that of a single type of biosurfactant and a chemical surfactant, namely the washing efficiency of the compound cleaning agent containing the glycolipid biosurfactant and the amino acid biosurfactant is higher than that of the single biosurfactant and the chemical surfactant, wherein the compound of the three biosurfactants has the best oil sludge washing effect.
Example 2:
the waste oil sludge in the embodiment is from an oil field in Xinjiang, and an oil sludge soil sample is dried in the shade, crushed, sieved by a sieve with the aperture of 2mm, removed of impurities, and packaged in a sealed bag for storage and standby.
The rhamnolipid is obtained by fermenting pseudomonas aeruginosa CGMCC NO.19110 for 7 days according to the prior art, the sophorolipid is obtained by fermenting candida utilis CCTCC NO. M2014349 for 5 days, the lipopeptide is obtained by fermenting bacillus subtilis CGMCC NO.17302 for 7 days, the rhamnolipid, sophorolipid and lipopeptide fermentation liquor are centrifuged at 5000r/min to remove thalli, the PH of the supernatant is adjusted to 8.5 by NaOH, and the concentration of the obtained fermentation liquor is 40g/L of rhamnolipid, 100g/L of sophorolipid and 20g/L of lipopeptide.
The biosurfactant solutions obtained above were prepared as follows:
the compound cleaning agent is prepared according to the following different mass ratios, i.e. sophorolipid fermentation liquor, rhamnolipid fermentation liquor and lipopeptide fermentation liquor, 1: taking 50mL of sophorolipid fermentation liquor, 250mL of rhamnolipid fermentation liquor and 250mL of lipopeptide fermentation liquor, and carrying out constant volume treatment on the fermentation liquor to obtain a solution with the volume of 1L (1:2:1), 2: taking 80mL of sophorolipid fermentation liquor, 200mL of rhamnolipid fermentation liquor and 200mL of lipopeptide fermentation liquor to constant volume of 1L (2:2:1), 3: taking 100mL of sophorolipid fermentation liquor, 166.7mL of rhamnolipid fermentation liquor and 166.7mL of lipopeptide fermentation liquor to be constant volume to 1L (3:2:1), 4: taking 114.3mL of sophorolipid fermentation liquor, 142.9mL of rhamnolipid fermentation liquor and 142.9mL of lipopeptide fermentation liquor, and carrying out volume metering to 1L (4:2:1), 5: taking 125mL of sophorolipid fermentation liquor, 125mL of rhamnolipid fermentation liquor and 125mL of lipopeptide fermentation liquor to constant volume of 1L (5:2:1), 6: taking 133.3mL of sophorolipid fermentation liquid, 111.1mL of rhamnolipid fermentation liquid and 111.1mL of lipopeptide fermentation liquid, and diluting to 1L (6:2:1), 7: taking 66.7mL of sophorolipid fermentation liquor, 166.7mL of rhamnolipid fermentation liquor and 333.3mL of lipopeptide fermentation liquor, and diluting to 1L (1:1:1), 8: taking 66.7mL of sophorolipid fermentation liquor, 250mL of rhamnolipid fermentation liquor and 166.7mL of lipopeptide fermentation liquor, and carrying out volume fixing on the fermentation liquor to 1L (2:3:1) and 9: taking 57.1mL of sophorolipid fermentation liquor, 285.7mL of rhamnolipid fermentation liquor and 142.9mL of lipopeptide fermentation liquor, and diluting to 1L (2:4:1), 10: taking 50mL of sophorolipid fermentation liquor, 312.5mL of rhamnolipid fermentation liquor and 125mL of lipopeptide fermentation liquor, and carrying out volume fixing to 1L (2:5:1), 11: taking 44.4mL of sophorolipid fermentation liquor, 333.3mL of rhamnolipid fermentation liquor and 111.1mL of lipopeptide fermentation liquor, and fixing the volume to 1L (2:6:1), wherein the mass fractions of the groups are 0.2%.
Placing 5g of oil sludge into a conical flask, respectively adding more than 15mL of biosurfactant solution, arranging three parallel samples in each group, respectively hot washing for 30min at the temperature of 50 ℃, stirring at 150rpm, standing, centrifuging at 5000r/min for 30min to separate oil liquid from solid and three phases, and pouring floating oil and supernate.
And after the residual solid matters are dried, determining the residual oil quantity of the oil sludge by using an organic solvent extraction method, and comparing the oil sludge cleaning effects of the compounded biosurfactants in different proportions.
The result is shown in the attached figure 2, and the compound cleaning agent of rhamnolipid, sophorolipid and lipopeptide is prepared in the following steps: 2:1 has the best cleaning effect on the oil sludge.
Example 3:
the waste oil sludge in the embodiment is from an oil field in Xinjiang, and an oil sludge soil sample is dried in the shade, crushed, sieved by a sieve with the aperture of 2mm, removed of impurities, and packaged in a sealed bag for storage and standby.
The rhamnolipid is obtained by fermenting pseudomonas aeruginosa CGMCC NO.19110 for 7 days according to the existing mode, the sophorolipid is obtained by fermenting candida utilis CCTCC NO. M2014349 for 5 days, and the lipopeptide is obtained by fermenting bacillus subtilis CGMCC NO.17302 for 7 days.
Preparing each solution in the compound biosurfactant: after the thalli are removed by centrifugation of rhamnolipid, sophorolipid and lipopeptide fermentation liquor at 5000r/min, the PH of supernatant is adjusted to 8.5 by NaOH, and the concentration of the obtained fermentation liquor is 40g/L of rhamnolipid, 100g/L of sophorolipid and 20g/L of lipopeptide.
The biosurfactant solutions obtained above were prepared as follows:
compounding a biosurfactant: the compound biosurfactant is prepared according to the mass fraction ratio, and comprises the following components: 80mL of sophorolipid fermentation liquor, 200mL of rhamnolipid fermentation liquor and 200mL of lipopeptide fermentation liquor are taken to be constant volume to 1L (mass ratio is 2:2: 1); chemical surfactant group: 20g of sodium dodecyl sulfate solution is taken, the constant volume is 1L, and the mass fractions of the compound biological surfactant and the chemical surfactant are both 0.2 percent.
Putting 5g of oil sludge into a conical flask, respectively adding more than 15mL of compound biological surfactant group or chemical surfactant group solution, arranging three parallel samples in each group, respectively hot washing at 40 ℃, 50 ℃, 60 ℃, 70 ℃ and 80 ℃ for 30min at a stirring speed of 150rpm, standing, centrifuging at 5000r/min for 30min, separating oil liquid from solid phase, and decanting off floating oil and supernatant.
And after drying the residual solid matters, determining the residual oil quantity of the oil sludge by using an organic solvent extraction method, and comparing the oil sludge cleaning efficiency and stability of the compound biosurfactant and the chemical surfactant under different temperature conditions.
The result is shown in figure 3, under the temperature condition of 40-80 ℃, after the compound cleaning agent containing rhamnolipid, sophorolipid and lipopeptide is washed, the content of oil sludge and residual oil is lower than that of the chemical surfactant, the washing effect is stable under different temperature conditions, the washing effect of the chemical surfactant is influenced by the temperature conditions, and the stability is poor, so that the hot washing effect of the compound biosurfactant is better than that of the chemically synthesized surfactant.
Example 4:
the waste oil sludge in the embodiment is from an oil field in Xinjiang, and an oil sludge soil sample is dried in the shade, crushed, sieved by a sieve with the aperture of 2mm, removed of impurities, and packaged in a sealed bag for storage and standby.
The rhamnolipid is obtained by fermenting pseudomonas aeruginosa CGMCC NO.19110 for 7 days according to the existing mode, the sophorolipid is obtained by fermenting candida utilis CCTCC NO. M2014349 for 5 days, and the lipopeptide is obtained by fermenting bacillus subtilis CGMCC NO.17302 for 7 days.
Preparing various solutions in the compound biological surfactant: after the thalli are removed by centrifugation of rhamnolipid, sophorolipid and lipopeptide fermentation liquor at 5000r/min, the PH of supernatant is adjusted to 8.5 by NaOH, and the concentration of the obtained fermentation liquor is 40g/L of rhamnolipid, 100g/L of sophorolipid and 20g/L of lipopeptide.
The biosurfactant solutions obtained above were prepared as follows:
compounding a biosurfactant: the compound biosurfactant is prepared according to the mass fraction ratio, and comprises the following components: sophorolipid fermentation liquor, rhamnolipid fermentation liquor and lipopeptide fermentation liquor (mass ratio is 2:2:1), wherein the mass fractions are respectively 0.05% (20 mL of sophorolipid fermentation liquor, 50mL of rhamnolipid fermentation liquor and 50mL of lipopeptide fermentation liquor are taken for constant volume of 1L), 0.1% (40 mL of sophorolipid fermentation liquor, 100mL of rhamnolipid fermentation liquor and 100mL of lipopeptide fermentation liquor are taken for constant volume of 1L), 0.15% (60 mL of sophorolipid fermentation liquor, 150mL of rhamnolipid fermentation liquor and 150mL of lipopeptide fermentation liquor are taken for constant volume of 1L), 0.2% (80 mL of sophorolipid fermentation liquor, 200mL of rhamnolipid fermentation liquor and 200mL of lipopeptide fermentation liquor are taken for constant volume of 1L), 0.25% (100 mL of sophorolipid fermentation liquor, 250mL of rhamnolipid fermentation liquor and 250mL of lipopeptide fermentation liquor are taken for constant volume of 1L), 0.3% (120 mL of sophorolipid fermentation liquor, 300mL of rhamnolipid fermentation liquor and 300mL of lipopeptide fermentation liquor are taken for constant volume of 1L), 0.35% (taking 140mL of sophorolipid fermentation liquor, 350mL of rhamnolipid fermentation liquor and 350mL of lipopeptide fermentation liquor to make the volume of 1L).
Chemical surfactant: the mass fractions are respectively 0.5% (taking 5g of sodium dodecyl sulfate to fix the volume to 1L), 1% (taking 10g of sodium dodecyl sulfate to fix the volume to 1L), 1.5% (taking 15g of sodium dodecyl sulfate to fix the volume to 1L), 2% (taking 20g of sodium dodecyl sulfate to fix the volume to 1L), 2.5% (taking 25g of sodium dodecyl sulfate to fix the volume to 1L), 3% (taking 30g of sodium dodecyl sulfate to fix the volume to 1L), 3.5% (taking 35g of sodium dodecyl sulfate to fix the volume to 1L), and 4% (taking 40g of sodium dodecyl sulfate to fix the volume to 1L). .
Placing 5g of oil sludge into a conical flask, adding 15mL of compound biological surfactant solution, taking a chemically synthesized surfactant as a control, arranging three parallel samples in each group, respectively carrying out hot washing at 50 ℃ for 30min at a stirring speed of 150rpm, standing, centrifuging at 5000r/min for 30min, separating oil liquid from solid and three phases, and pouring floating oil and supernatant.
And after drying the residual solid matters, determining the residual oil quantity of the oil sludge by using an organic solvent extraction method, and comparing the cleaning effects of the compound biosurfactant and the chemical surfactant with different concentrations on the oil sludge of the oil field.
The results are shown in figures 4 and 5, the best oil washing effect can be achieved by the compound biosurfactant with the mass fraction of 0.15%, the washing effect is not obviously improved by increasing the dosage of the surfactant, and the use concentration of the chemical surfactant is 4% and the dosage of the chemical surfactant is far higher than that of the compound cleaning agent to achieve the same washing effect.
Example 5:
the waste oil sludge in the embodiment is from Xinjiang oil fields, Daqing oil fields and Hongkong oil fields, and the oil sludge soil sample is dried and crushed in the shade, then passes through a sieve with the aperture of 2mm, is removed of impurities, and is packaged in a sealing bag for storage and standby.
The rhamnolipid is obtained by fermenting pseudomonas aeruginosa CGMCC NO.19110 for 7 days according to the prior art, the sophorolipid is obtained by fermenting candida CCTCC NO. M2014349 for 5 days, and the lipopeptide is obtained by fermenting bacillus subtilis CGMCC NO.17302 for 7 days.
Preparing various solutions in the compound biological surfactant: after bacteria are removed by centrifugation of rhamnolipid, sophorolipid and lipopeptide fermentation liquor at 5000r/min, the PH of supernatant is adjusted to 8.5 by NaOH, and the concentration of the obtained fermentation liquor is 40g/L of rhamnolipid, 100g/L of sophorolipid and 20g/L of lipopeptide.
The biosurfactant solutions obtained above were prepared as follows:
compounding a biosurfactant: the composite biosurfactant is prepared according to the mass fraction ratio, and the composite biosurfactant of the three components comprises the following components: sophorolipid fermentation liquor, rhamnolipid fermentation liquor and lipopeptide fermentation liquor (mass ratio is 2:2:1) (60 mL of sophorolipid fermentation liquor, 150mL of rhamnolipid fermentation liquor and 150mL of lipopeptide fermentation liquor are taken to be constant volume to 1L); chemical surfactant group: the sodium dodecyl sulfate solution (15 g of sodium dodecyl sulfate is taken to fix the volume to 1L), and the total mass fraction of the solutions is 0.15 percent.
Placing 5g of oil sludge into a conical flask, adding 15mL of compound biological surfactant solution, taking a chemically synthesized surfactant as a control group, arranging three parallel samples in each group, respectively carrying out hot washing at 50 ℃ for 30min at a stirring speed of 150rpm, standing, centrifuging at 5000r/min for 30min, separating oil liquid from solid and three phases, and pouring floating oil and supernatant.
And after the residual solid matters are dried, determining the residual oil quantity of the oil sludge by using an organic solvent extraction method, and comparing the cleaning effects of the compound biosurfactant and the chemical surfactant on different oil field oil sludge.
The results are shown in figure 6, and the hot washing effect of the compound biosurfactant on the waste oil sludge of Xinjiang, Daqing and Dagang oil fields is better than that of the chemical surfactant with the same concentration.
Example 6:
the waste oil sludge in the embodiment is from Xinjiang oil fields, Daqing oil fields and Hongkong oil fields, and the oil sludge soil sample is dried and crushed in the shade, then passes through a sieve with the aperture of 2mm, is removed of impurities, and is packaged in a sealing bag for storage and standby.
The rhamnolipid is obtained by fermenting pseudomonas aeruginosa CGMCC NO.19110 for 7 days according to the prior art, the sophorolipid is obtained by fermenting candida CCTCC NO. M2014349 for 5 days, and the lipopeptide is obtained by fermenting bacillus subtilis CGMCC NO.17302 for 7 days.
Preparing various solutions in the compound biological surfactant: and centrifuging the rhamnolipid, sophorolipid and lipopeptide fermentation liquor at 5000r/min to remove thalli, and regulating the pH of the supernatant to 8.5 by using NaOH.
The biosurfactant solutions obtained above were prepared as follows:
compounding a biosurfactant: preparing rhamnolipid fermentation liquor and lipopeptide fermentation liquor according to the mass fraction ratio (the mass ratio is 4:1, namely 300mL of rhamnolipid fermentation liquor and 150mL of lipopeptide fermentation liquor are taken to fix the volume to 1L); the sophorolipid fermentation liquor and the lipopeptide fermentation liquor are mixed in a mass ratio of 4:1, namely, 120mL of sophorolipid fermentation liquor and 150mL of lipopeptide fermentation liquor are subjected to constant volume treatment to 1L, the sophorolipid fermentation liquor and the rhamnolipid fermentation liquor are mixed in a mass ratio of 4:1, namely, 120mL of sophorolipid fermentation liquor and 75mL of rhamnolipid fermentation liquor are subjected to constant volume treatment to 1L, the sophorolipid fermentation liquor, the rhamnolipid fermentation liquor and the lipopeptide fermentation liquor are mixed in a mass ratio of 2:2:1, namely, 60mL of sophorolipid fermentation liquor, 150mL of rhamnolipid fermentation liquor and 150mL of lipopeptide fermentation liquor are subjected to constant volume treatment to 1L, and the mass fractions of the solutions are 0.15%.
Placing 5g of oil sludge into a conical flask, adding 15mL of compound biological surfactant solution, taking a chemically synthesized surfactant as a control group, arranging three parallel samples in each group, respectively carrying out hot washing at 50 ℃ for 30min at a stirring speed of 150rpm, standing, centrifuging at 5000r/min for 30min, separating oil liquid from solid and three phases, and pouring floating oil and supernatant.
And after the residual solid matters are dried, determining the residual oil quantity of the oil sludge by using an organic solvent extraction method, and comparing the cleaning effects of the compound biosurfactant and the chemical surfactant on different oil field oil sludge.
The result is shown in figure 7, the hot washing effect of the three compound biosurfactants on the waste oil sludge of Xinjiang, Daqing and Dagang oil fields is better than that of the two compound biosurfactants with the same concentration, and the compound cleaning agent has more outstanding cleaning effect on the oil sludge of the Daqing oil field with higher heavy petroleum content.
From the above, the compound cleaning agent containing three biosurfactants has better cleaning effect on oil sludge than a single biosurfactant, and achieves the same oil sludge cleaning effect, the dosage of the compound cleaning agent containing three biosurfactants is far lower than that of a chemically synthesized surfactant, the washing effect of the compound biosurfactant on different oil field oil sludge is stable under different temperature conditions, and the content of oil sludge residual oil is lower than that of the chemically synthesized surfactant after washing.
Claims (8)
1. An environment-friendly cleaning agent is characterized in that: the cleaning agent contains a compound biosurfactant, wherein the compound biosurfactant is a glycolipid biosurfactant and an amino acid biosurfactant, and the mass fractions of the surfactants are (2-20): 1, and adjusting the PH to 8-9 by NaOH.
2. The environmentally friendly cleaning agent as claimed in claim 1, wherein: the glycolipid biosurfactant is rhamnolipid and/or sophorolipid; the amino acid biosurfactant is lipopeptide; wherein the rhamnolipid, sophorolipid and lipopeptide are obtained or purified by fermentation of corresponding strains.
3. The environmentally friendly cleaning agent as claimed in claim 2, wherein: the rhamnolipid is obtained by fermenting pseudomonas aeruginosa, and the preservation number of a pseudomonas aeruginosa strain is CGMCC NO. 19110; the sophorolipid is obtained by fermenting candida, and the preservation number of candida is CCTCC NO: M2014349; the lipopeptide is obtained by fermenting bacillus subtilis, the bacillus subtilis strain is sent to the common microorganism center of China Committee for culture Collection of microorganisms in the laboratory for preservation, and the strain preservation number is CGMCC NO. 17302.
4. The environmentally friendly cleaning agent according to any one of claims 1 to 3, wherein:
the cleaning agent is prepared from the following components in percentage by mass (1-20): 1, or the mass ratio of (2-20): 1, or the mass ratio of sophorolipid to lipopeptide is (1-10): (1-10): 1, the cleaning agent is a weakly alkaline cleaning agent (PH 8-9).
5. The use of the cleaning agent according to claim 1, wherein: the cleaning agent is applied to cleaning oil sludge.
6. Use according to claim 5, characterized in that: mixing the oily sludge with the cleaning agent as claimed in claim 1, and performing oscillation, centrifugation and air drying to finish the cleaning of the oily sludge.
7. Use according to claim 6, characterized in that: the mass volume ratio of the oil sludge to the cleaning agent is 1: (2-20) adding a cleaning solution into the oily sludge, wherein the washing temperature is 20-80 ℃, the oscillation speed is 100-350 r/min, and the oscillation time is 10-90 min.
8. Use according to claim 7, characterized in that: in the washing step, the washing temperature may be 50 ℃, the oscillation speed may be 150r/min, and the oscillation time may be 30 min.
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| CN105753283A (en) * | 2016-03-14 | 2016-07-13 | 北京华纳斯科技有限公司 | Method of utilizing biosurfactant and microbial agent to treat oil-containing sediment |
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| CN111115991A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Environment-friendly efficient oily sludge cleaning agent and preparation and use methods thereof |
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| CN105753283A (en) * | 2016-03-14 | 2016-07-13 | 北京华纳斯科技有限公司 | Method of utilizing biosurfactant and microbial agent to treat oil-containing sediment |
| CN106811313A (en) * | 2016-12-08 | 2017-06-09 | 中海石油环保服务（天津）有限公司 | A kind of environmentally friendly oil sludge and sand cleaning agent and its preparation and application |
| CN111115991A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Environment-friendly efficient oily sludge cleaning agent and preparation and use methods thereof |
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