CN1546612A - Crude oil dewatering method using biological demulsifying agent - Google Patents

Crude oil dewatering method using biological demulsifying agent Download PDF

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CN1546612A
CN1546612A CNA2003101073124A CN200310107312A CN1546612A CN 1546612 A CN1546612 A CN 1546612A CN A2003101073124 A CNA2003101073124 A CN A2003101073124A CN 200310107312 A CN200310107312 A CN 200310107312A CN 1546612 A CN1546612 A CN 1546612A
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crude oil
demulsifying agent
biological demulsifying
lipopeptid
emulsion
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CNA2003101073124A
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CN1216132C (en
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梁凤来
刘如林
奚艳伟
张晶
马建芳
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Nankai University
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Nankai University
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Abstract

The invention relates to a crude oil dewatering method using biological demulsifying agent which comprises, ventilating culture of Bacillus sp.X3 strain 36-48 hours in culture medium whose principal raw material is carbohydrate at the temperature of 33-37 deg. C, forming a lipopeptide biological demulsifying agent, mixing the total culture liquid with oil by the volumetric ratio of 0.5-1:5-8, heat preserving 5-8 hours at 50-60 deg. C to remove the water in the crude oil.

Description

A kind of method of carrying out dehydrating of crude oil with biological demulsifying agent
Technical field
The claimed technical scheme of the present invention relates to the decomposition emulsion, specifically carries out the method for dehydrating of crude oil with biological demulsifying agent.
Background technology
Contain too much moisture in the crude oil, in the course of processing, not only can increase heat energy consumption, also can influence the catalyst action effect, and since at high temperature water and oil vaporize simultaneously, volume expands rapidly, can cause towards accidents such as towers; Owing to contain inorganic salts in the water in the crude oil, can cause corrosion again, reduce the life-span of refining equipment refining equipment; In addition, what of water-content directly influence oil field accumulating load and pipeline corrosion in the crude oil, and water-content also can reduce its calorific value when acting as a fuel, and simultaneously, also can bring error to crude oil measurement.Therefore, when oil transportation and refining, the water content that necessarily requires crude oil is below 0.5%, so the breaking emulsion and dewatering of crude oil emulsion is one of important link in the petroleum refining process.Seeking effective breakdown of emulsion ground method is the problem that people generally are concerned about.
At present, industrial the most frequently used crude oil demulsification method is still the adding chemical demulsifier.Because the complicacy of crude oil emulsion, though the de-emulsification speed of chemical demulsifier is very fast, consumption is big, and specificity is too strong, can not generally be applicable to the crude oil extraction liquid of various character, but also can cause the pollution to environment.
The mechanism of carrying out dehydrating of crude oil with biological demulsifying agent is, some microorganism can produce in its growth metabolism process has surface-active material, these surfactants are called as bio-surfactant, its molecular weight is little, have good surfactivity, be penetrated into water-oil interface easily, insert the space of water-oil interface, thereby make the interfacial film instability, its mechanism is identical with chemical demulsifier.It also can modification bacterium somatocyte surface and solids in addition, change its wettability, make it be suitable for breakdown of emulsion.Though to the breakdown of emulsion capability studys of various microorganisms from the last century eighties just, abroad, nineteen eighty-two Cairns etc., Gray in 1984 etc., Kosaric in 1987 etc., Stewart in 1996 etc., Madhusweta Das in 1999, Shin Hye Park in 2000 etc., NalinaNadarajah in 2002 etc. all carried out research to the breakdown of emulsion ability of different bacterial classifications, obtain similar conclusion, promptly the breakdown of emulsion ability of microorganism comes from somatic cells.But, be emulsion splitter as if the bacterial classification of studying employing with them, need thalline is separated from nutrient solution, production cost is very big.Therefore, up to the present, the biological demulsifying agent that is actually used in industrial crude oil oily water separation seldom, the report that carries out dehydrating of crude oil with biological demulsifying agent is also very limited.US 4,432,887 have reported a kind of emulsion splitter of microorganism origin, the microorganism of selecting for use has Nocardia, Rhodococcus, Arthrobacter, Corynebacterium or Mycobacterium, the wherein actual emulsion splitter that is used as is Nocardia amarae, Rhodococcus aurantiacus and Rhodococcus rubropertinctus; JP 09-173704 introduces with containing and belongs to the inoculum that replaces unicellular bacterium (Alteromonas) and come the separating oil water miscible liquid; 1998, people such as the Xu Yuan of China Hebei Environmental Monitoring Central Station spring write articles---biological demulsifying agent performance study (environment protection, 1998, (6)), also studied the demulsification performance of Nocardia amarae bacterial classification.In general, existing to carry out the breakdown of emulsion efficient of crude oil dehydration method with biological demulsifying agent not high, and de-emulsification speed is slow.
Summary of the invention
Technical problem to be solved by this invention is: the invention provides a kind of method of carrying out dehydrating of crude oil with biological demulsifying agent, it is to utilize the lipopeptid tensio-active agent of microorganisms to reach the breakdown of emulsion purpose, the full nutrient solution of microbial fermentation that will contain lipopeptid directly mixes with crude oil realizes breakdown of emulsion, overcome that existing to carry out the breakdown of emulsion efficient of crude oil dehydration method with biological demulsifying agent not high, shortcoming that de-emulsification speed is slow.
The present invention solves this technical problem the technical scheme that is adopted: with bacillus sp.X 3Bacterial strain is being in the substratum of main raw material with the carbohydrate, under 33~37 ℃ of temperature, ventilate and cultivated 36~48 hours, promptly form lipopeptid biological demulsifying agent---the full nutrient solution of lipopeptid biological demulsifying agent of lipopeptid tensio-active agent contained, will this full nutrient solution: crude oil=0.5~1: 5~8 volume ratio mixing be incubated the water that can deviate from the crude oil in 5~8 hours under 50~60 ℃ of temperature.
The invention has the beneficial effects as follows: through the again and again screening experiment to the microorganism of the biological demulsifying agent that is used for dehydrating of crude oil, the present invention screens the bacterial classification with fine breakdown of emulsion ability---bacillus sp.X finally first 3Bacterial strain, and be separated to activeconstituents with breakdown of emulsion ability---the lipopeptid biological tensio-active agent, find first that again this lipopeptid biological tensio-active agent has good breakdown of emulsion ability, by experiment many times, just prove again, do not need to separate, directly use bacillus sp.X 3Bacterial strain is being that the full nutrient solution that forms in the substratum of main raw material can carry out dehydrating of crude oil fast and efficiently with the carbohydrate.Following embodiment 1~4 proof, breakdown of emulsion efficient and the de-emulsification speed that carries out crude oil dehydration method with lipopeptid biological demulsifying agent of the present invention all is better than chemical demulsifier and prior biological emulsion splitter.
Embodiment
Embodiment 1
The method of lipopeptid biological demulsifying agent of the present invention being carried out dehydrating of crude oil is applied to water/oily model emulsion breakdown dehydration:
A. prepare water/oily model milk sap: will contain the kerosin of 1.67%Span80 and distilled water with 90: 60 mixed, and with 10000r/min high-speed stirring 1 minute, can form milky white liquid with stirrer.Dyed method is accredited as water/oil type milk sap.
B. purchasing of the full nutrient solution of lipopeptid biological demulsifying agent: with 5~10 ml concns is 1~3 * 10 8The bacillus sp X of individual/milliliter 3It is 500~1000 milliliters of substratum of main raw material that bacterial strain places with corn, starch or sucrose, ventilates under 33~37 ℃ of temperature and cultivates 36~48 hours, promptly makes the full nutrient solution of lipopeptid biological demulsifying agent.The collocation method of substratum is that those skilled in the art are known.
C. carry out dehydrating of crude oil: get 0.5~1 milliliter of the full nutrient solution of the lipopeptid biological demulsifying agent of producing among the above-mentioned B, join being with in the graduated rub oral examination tube of 5~8 milliliters in the water produced among the above-mentioned A/oil type model milk sap is housed, being placed on vibrates on the vortex mixer made their mixings in 15 seconds, place 55 ℃ of water-bath last 8 hours, carry out breakdown of emulsion, test to such an extent that demulsification efficiency is 99%.
D. control experiment: 1. under the situation identical, carry out the dehydrating of crude oil experiment, test to such an extent that demulsification efficiency is 97% with chemical demulsifier DGF-01 with above-mentioned conditionally complete; 2. under the situation identical,, test to such an extent that demulsification efficiency is 0 with being that the substratum of main raw material adds water/oil type model milk sap of producing among the above-mentioned A for 0.5~1 milliliter and carries out parallel laboratory test for 5~8 milliliters with corn, starch or sucrose among the above-mentioned B with above-mentioned conditionally complete; 3. under the situation identical with above-mentioned conditionally complete, only carry out parallel laboratory test with water/oil type model milk sap of 5.5~9 milliliters, test to such an extent that demulsification efficiency is 0.
The method of calculation of demulsification efficiency are:
Demulsification efficiency=(the residue milk sap volume behind initial milk sap volume-breakdown of emulsion certain hour) * 100/ initial emulsion liquid product
Embodiment 2
The method of lipopeptid biological demulsifying agent of the present invention being carried out dehydrating of crude oil is applied to the dehydration of crude oil model emulsion breakdown:
A. the preparation of crude oil model milk sap: 90 milliliters and 60 milliliters hot distilled waters of J9-19 crude oil of getting Dagang Oilfield, stirred 2 minutes with 10000r/min with stirrer, can form chocolate milk sap, dyed method is accredited as water/oil type milk sap, surveying its water content is 40%, can stablize the several months long, as crude oil model milk sap;
B. purchasing of the full nutrient solution of lipopeptid biological demulsifying agent: with embodiment 1;
C. carry out dehydrating of crude oil: get 5 milliliters of the full nutrient solutions of the lipopeptid biological demulsifying agent of producing among the above-mentioned B, join in the Boiling tube that 25 milliliters of the crude oil model milk sap produced among the above-mentioned A are housed, seal with rubbery stopper, be placed on the vortex mixer and vibrated 30 seconds, make their mixings, place 55 ℃ of water-bath last 5 hours, carry out breakdown of emulsion, test to such an extent that demulsification efficiency is 99%.
D. control experiment: 1. under the situation identical with above-mentioned conditionally complete, carry out the dehydrating of crude oil experiment with chemical demulsifier DGF-01, demulsification efficiency is 77%; 2. under the situation identical,, test to such an extent that demulsification efficiency is 0 with being that the substratum of main raw material adds the crude oil model milk sap of producing among the above-mentioned A for 5 milliliters and carries out parallel laboratory test for 25 milliliters with corn, starch or sucrose among the above-mentioned B with above-mentioned conditionally complete; 3. under the situation identical with above-mentioned conditionally complete, only carry out parallel laboratory test with 30 milliliters crude oil model milk sap, test to such an extent that demulsification efficiency is 0.
The demulsification efficiency method of calculation are with embodiment 1.
Embodiment 3
The method that lipopeptid biological demulsifying agent of the present invention is carried out dehydrating of crude oil is applied to the model emulsion breakdown dehydration of crude oil extraction liquid:
A. the preparation of crude oil extraction liquid: get water content and reach two kinds of crude oil of 30~40% No. 1 and No. 2, stir separately, profit is mixed, again they are mixed the model milk sap of crude oil extraction liquid;
B. purchasing of the full nutrient solution of lipopeptid biological demulsifying agent: with embodiment 1;
C. carry out dehydrating of crude oil: get 1 milliliter of the full nutrient solution of the lipopeptid biological demulsifying agent of producing among the above-mentioned B, join being with in the graduated rub oral examination tube of 15 milliliters of model milk sap that the crude oil extraction liquid of producing among the above-mentioned A is housed, being placed on vibrates on the vortex mixer made their mixings in 15 seconds, place 55 ℃ of water-bath last 8 hours, carry out breakdown of emulsion, test to such an extent that demulsification efficiency is 99%.
D. control experiment: 1. under the situation identical, carry out the dehydrating of crude oil experiment, test to such an extent that demulsification efficiency is 97% with chemical demulsifier DGF-01 with above-mentioned conditionally complete; 2. under the situation identical,, test to such an extent that demulsification efficiency is 0 with being that the model milk sap that the substratum of main raw material adds the crude oil extraction liquid of producing among the above-mentioned A for 1 milliliter carries out parallel laboratory test for 15 milliliters with corn, starch or sucrose among the above-mentioned B with above-mentioned conditionally complete; 3. under the situation identical with above-mentioned conditionally complete, only the model milk sap liquid with 16 milliliters crude oil extraction liquid carries out parallel laboratory test, tests to such an extent that demulsification efficiency is 0.
The demulsification efficiency method of calculation are with embodiment 1.
Embodiment 4
The method of carrying out dehydrating of crude oil with lipopeptid biological demulsifying agent of the present invention compares experiment with the method for having reported of carrying out dehydrating of crude oil with biological demulsifying agent;
It is the demulsification activity composition that the biological demulsifying agent of bibliographical information adopts the somatic cells of Nocardia bacteria Nocardia more, and the biological table of the lipopeptid class agent alive that is bacillus produces of the present invention is the demulsification activity composition.Though both are called biological demulsifying agent, but there is difference in essence, they also have difference to the demulsification of milk sap, and lipopeptid class biological demulsifying agent of the present invention is more more excellent than the demulsification of existing Nocardia bacteria biological demulsifying agent, and experiment comparative result under the same conditions sees the following form.
Agent alive of lipopeptid biological table and Nocardia bacteria are to the emulsion breakdown effect relatively
The breakdown of emulsion time (hour) Lipopeptid biological table agent demulsification efficiency (%) alive Nocardia bacteria demulsification efficiency (%)
????0.5 ????58 ????43
????1.0 ????86 ????74
????5.0 ????99 ????88
????10 ????100 ????95
????15 ????100 ????96

Claims (2)

1. a method of carrying out dehydrating of crude oil with biological demulsifying agent is characterized in that: with bacillus sp.X 3Bacterial strain is being in the substratum of main raw material with the carbohydrate, under 33~37 ℃ of temperature, ventilate and cultivated 36~48 hours, promptly form lipopeptid biological demulsifying agent---the full nutrient solution of lipopeptid biological demulsifying agent of lipopeptid tensio-active agent contained, will this full nutrient solution: crude oil=0.5~1: 5~8 volume ratio mixing be incubated the water that can deviate from the crude oil in 5~8 hours under 50~60 ℃ of temperature.
2. according to the described a kind of method of carrying out dehydrating of crude oil with biological demulsifying agent of claim 1, it is characterized in that: with 5~10 ml concns is 1~3 * 10 8The bacillus sp.X of individual/milliliter 3It is 500~1000 milliliters of substratum of main raw material that bacterial strain places with corn, starch or sucrose, ventilates under 33~37 ℃ of temperature and cultivates 36~48 hours, promptly makes the full nutrient solution of lipopeptid biological demulsifying agent.
CN 200310107312 2003-12-12 2003-12-12 Crude oil dewatering method using biological demulsifying agent Expired - Fee Related CN1216132C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100363468C (en) * 2005-08-10 2008-01-23 中国石油天然气股份有限公司 Production equipment for dewater and desolvent of lubricating oil additive and its technological method
CN107937020A (en) * 2017-11-24 2018-04-20 南京理工大学 A kind of efficient breaking method of the two-step method of lipopeptid
CN112830650A (en) * 2021-03-04 2021-05-25 榕知(杭州)信息技术有限公司 Process for treating oily sludge generated in crude oil exploitation process by microorganisms
CN115785940A (en) * 2022-12-01 2023-03-14 克拉玛依中科恒信科技有限责任公司 Demulsification cleanup additive for fracture acidizing and preparation method and use method thereof
CN116694541A (en) * 2023-08-08 2023-09-05 季华实验室 Biological demulsification microbial inoculum for ton barrels and screening method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100363468C (en) * 2005-08-10 2008-01-23 中国石油天然气股份有限公司 Production equipment for dewater and desolvent of lubricating oil additive and its technological method
CN107937020A (en) * 2017-11-24 2018-04-20 南京理工大学 A kind of efficient breaking method of the two-step method of lipopeptid
CN107937020B (en) * 2017-11-24 2020-05-12 南京理工大学 Two-step efficient demulsification method for lipopeptide
CN112830650A (en) * 2021-03-04 2021-05-25 榕知(杭州)信息技术有限公司 Process for treating oily sludge generated in crude oil exploitation process by microorganisms
CN115785940A (en) * 2022-12-01 2023-03-14 克拉玛依中科恒信科技有限责任公司 Demulsification cleanup additive for fracture acidizing and preparation method and use method thereof
CN116694541A (en) * 2023-08-08 2023-09-05 季华实验室 Biological demulsification microbial inoculum for ton barrels and screening method thereof

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