CN101457155B - Method for microbial decalcification and co-production of hydrogen in crude oil - Google Patents

Method for microbial decalcification and co-production of hydrogen in crude oil Download PDF

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Publication number
CN101457155B
CN101457155B CN2007101792718A CN200710179271A CN101457155B CN 101457155 B CN101457155 B CN 101457155B CN 2007101792718 A CN2007101792718 A CN 2007101792718A CN 200710179271 A CN200710179271 A CN 200710179271A CN 101457155 B CN101457155 B CN 101457155B
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crude oil
mikrobe
microbial fermentation
decalcification
fermentation solution
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CN101457155A (en
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罗来龙
方新湘
刘江华
于娟
陈爱华
海日古丽
朱海霞
陈永立
马天玲
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Petrochina Co Ltd
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Petrochina Co Ltd
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Abstract

The invention relates to a method for the combined production of hydrogen by crude oil microbial decalcification, which comprises the steps of carrying out amplification culture on various microbial strains by adopting a conventional microbial amplification culture mode, mixing the amplified strains and fermentation products according to any proportion, and enabling the concentration of the strains to be 108~1010Adding a microorganism mixed bacterium and a fermentation product which account for 1-10% of the weight of tap water or oilfield injection water and 1-6% of a culture medium into the tap water or oilfield injection water to prepare a microorganism fermentation liquid, adding the microorganism fermentation liquid and crude oil into a closed container according to the weight ratio of 0.1: 1-0.5: 1, carrying out full mixing reaction at the temperature of 25-55 ℃ for 1-5 days under the condition of no air, collecting gas generated in the reaction process, wherein the decalcification rate of the crude oil reaches 97.8%, and the yield of hydrogen reaches 1mol-1The purity of the hydrogen in the culture medium reaches 93.2 percent.

Description

A kind of method of crude oil mikrobe decalcification co-producing hydrogen
Technical field
The present invention relates to a kind ofly in the crude oil upgrading process, utilize microbial fermentation solution to carry out the method for former oil refining co-producing hydrogen.
Background technology
Along with the continuous increase and the external heavy crude of a large amount of import of China's BO output, the metal content in the crude oil increases progressively gradually.The increase of metal content in the crude oil; Not only bring many disadvantageous effects,, cause the serious fouling of furnace tubing as the poisoning of catalyst deactivation phenomenom in secondary processing process, occurring to Crude Oil Processing; Influence the quiet run of crude production device; And can reduce the postorder quality product, and increase the crude oil tooling cost, reduce the processing benefit of crude oil.
CN1431276, CN1521239, CN1760338, CN1657594, CN1657593, CN1245201, CN1472282, CN1611571, CN1611570, CN1611569, CN1611567, CN1611568, CN1267707, CN1865403, CN1657596 have all described a kind of chemical method and have particularly removed the metal process in the crude oil with organic acid or mineral acid; It is two point defects below main the existence in practical application: the one, utilize the electric desalting system of oil refining apparatus; For assurance device reaches decalcification desalting effect preferably; Need to inject the excessive organic acid and the bigger water yield; Thereby cause the unreacted organic acid of part to remain in the crude oil; Cause the corrosion of distillation plant even postorder processing units, influence oil refining apparatus safety, smooth running; The 2nd, the organic acid consumption is big, makes crude oil demetalization cost increase, because the sewage of demetalization process discharging contains part organic acid or organic acid salt, makes COD content up to tens thousand of mg/L, directly impacts the industrial sewage treatment system.
CN1865404 discloses the biological demetallated method of a kind of hydrocarbon ils, and this method is only applicable to the crude oil demetalization, does not relate to the method that microbiological crude oil takes off while co-producing hydrogen in the demetalization process; CN1958618A discloses the biological decalcification method in a kind of process for preparing chitin, and what relate generally to is agricultural byproducts decalcification technical field; CN101007682, CN1918079, CN1858213, CN1858197, CN1850582, CN1772877, CN1618980, CN1506465, CN1328158, CN1276430 provide the relevant method of utilizing mikrobe to come hydrogen manufacturing respectively; But all do not relate to when utilizing mikrobe hydrogen manufacturing, also be used for removing the content of the calcium metal of crude oil.
Summary of the invention
The object of the invention be to provide a kind of utilize mikrobe and tunning thereof under the amphimicrobian condition to the crude oil effect; Make mikrobe in the growth metabolism process, produce acid, aerogenesis, product surfactant; When crude oil was carried out decalcification, the microbial fermentation of fermentation generation hydrogen carried out the method for crude oil demetalization co-producing hydrogen.
The present invention realizes through following measure: with each bacterial classification of required mikrobe; Adopt the conventional mikrobe mode of spreading cultivation to spread cultivation; Above-mentioned bacterium and tunning thereof after will spreading cultivation respectively mix by arbitrary proportion again, obtain mikrobe mixed bacterium and tunning thereof, and after making its bacterium index reach certain requirement; Add mentioned microorganism mixed bacterium and tunning thereof and substratum in tap water or the oilfield injection water to certain concentration then; Be mixed with microbial fermentation solution, microbial fermentation solution and the crude oil with preparation joins in the encloses container in proportion then, under certain temperature and obstructed air conditions, carries out the thorough mixing reaction; Keep the amphimicrobian state in the entire reaction course, collect the gas that reaction process produces simultaneously.After cultivating the reaction certain hour, the calcium contents of assay determination crude oil, hydrogen output and hydrogen purity.
Described microbe-derived in oil field mining liquid or oil field soil sample, be subtilis (Bacillus subtilis), its preserving number is 1.942; Bacillus cereus (Bacillus cereus); Its preserving number is 1.1626, Bacillus licheniformis (Bacillus licheniformis), and its preserving number is 1.807; Pseudomonas aeruginosa (Pseudomonas aeruginosa), its preserving number are one or more the bacterial classification in 1.922.Said bacterial classification all can be provided by China Committee for Culture Collection of Microorganisms common micro-organisms center, and this mikrobe mixed bacterium can be mixed by arbitrary proportion mutually.
The material of one or more that the said substratum that microorganism growth is provided is waste molasses, beef extract or inorganic salt micronutrient element.
Keep in the substratum of microorganism growth; The waste molasses add-on accounts for 1~6% of microbial fermentation solution weight; The beef extract add-on accounts for 0~0.5% of microbial fermentation solution weight; In the inorganic salt micronutrient element, the ammonium salt add-on account for microbial fermentation solution weight 0~0.5%, the sodium salt add-on account for microbial fermentation solution weight 0~0.5%, the sylvite add-on account for microbial fermentation solution weight 0~0.5%, the magnesium salts add-on accounts for 0~0.05% of microbial fermentation solution weight.
Said waste molasses is the beet waste molasses; Beef extract is that one or both combination of components in Carnis Bovis seu Bubali cream or the peptone form, and ammonium salt is an ammonium nitrate or ammonium sulfate, and sodium salt is Sodium phosphate, dibasic or SODIUM PHOSPHATE, MONOBASIC; Sylvite is potassium primary phosphate or potassium hydrogenphosphate, and magnesium salts is a sal epsom.
The method that spreads cultivation of said mikrobe mixed bacterium spreads cultivation according to the conventional training method of mikrobe, makes the concentration of microbial fermentation product reach 10 8~10 10Individual/the ml mixed bacterium, the pH value is 5~7, and surviving rate is 85~99%.
Said cultured mikrobe and tunning thereof account for tap water or oilfield injection water weight 1~10%, cultivation fiduciary point tap water that adds in cultured mikrobe and the tunning thereof or oilfield injection water weight 1~6%.
In the microbial fermentation solution of said preparation and the crude oil hybrid reaction process, the weight ratio of microbial fermentation solution and crude oil effect is 0.1: 1~0.5: 1, and operative temperature is 25~55 ℃, and cultivating the reaction times is 1~5 day.
In the microbial fermentation solution of said preparation and the crude oil hybrid reaction process, microbial inoculum and crude oil operative temperature are 30~45 ℃, and cultivating the reaction times is 2~3 days.
Compared with prior art, the present invention has following effect:
Disclosed crude oil decalcifying technology of prior art or process for making hydrogen are independent process; Technique effect is single, and the present invention utilizes mikrobe and tunning thereof, and crude oil decalcifying technology and co-producing hydrogen process are organically combined; Improved the economic benefit of biological decalcification technology largely; And the crude oil decalcifying rate is reached more than 85%, purity reaches more than 90%, has that technology is simple, energy consumption is low, the safety and environmental protection characteristics.
Embodiment
Below in conjunction with embodiment the present invention is made further detailed description.
Embodiment 1
Subtilis, bacillus cereus, Bacillus licheniformis and pseudomonas aeruginosa bacterial classification that experiment is required; Adopt the conventional mikrobe mode of spreading cultivation to spread cultivation; Above-mentioned bacterium after will spreading cultivation respectively again and tunning thereof were by weight 1: 1: 1: 1 mixes; Obtain mikrobe mixed bacterium and tunning thereof, and make its bacteria concentration reach 6.8 * 10 9Individual/ml, pH5.0, survival rate 90%; Then mentioned microorganism mixed bacterium and tunning thereof with account for tap water or oilfield injection water weight 10%, the beet waste molasses culture medium adds in tap water or the oilfield injection water with the concentration that accounts for tap water or oilfield injection water weight 6%; Be mixed with microbial fermentation solution, again microbial fermentation solution and crude oil added in the encloses container by weight 0.1: 1, under 25 ℃ of temperature of reaction and obstructed air conditions, carry out the thorough mixing reaction; Keep the amphimicrobian state in the entire reaction course; Collect the gas that reaction process produces simultaneously, through cultivating reaction 5 days, the calcium contents that records crude oil is reduced to 21 μ g/g by 248 μ g/g; The decalcification rate is 91.5%, and the output of hydrogen is 0.7mol.mol -1Substratum, the purity of hydrogen are 91.2%.
Embodiment 2
Subtilis, bacillus cereus, Bacillus licheniformis and pseudomonas aeruginosa bacterial classification that experiment is required; Adopt the conventional mikrobe mode of spreading cultivation to spread cultivation; Above-mentioned bacterium after will spreading cultivation respectively again and tunning thereof were by weight 1: 0: 1: 0 mixes; Obtain mikrobe mixed bacterium and tunning thereof, and make its bacteria concentration reach 1 * 10 10Individual/ml, pH is 6.5, survival rate 95%; Then mentioned microorganism mixed bacterium and tunning thereof to account for tap water or oilfield injection water weight 5%, the beet waste molasses in the substratum, potassium hydrogenphosphate, sal epsom add in tap water or the oilfield injection water with the concentration that accounts for tap water or oilfield injection water weight 3%, 0.5% and 0.05% respectively, are mixed with microbial fermentation solution; Again microbial fermentation solution and crude oil were added in the encloses container by weight 0.5: 1; Under 40 ℃ of temperature of reaction and obstructed air conditions, carry out the thorough mixing reaction, keep the amphimicrobian state in the entire reaction course, collect the gas that reaction process produces simultaneously; Through cultivating reaction 1 day; The calcium contents that records crude oil is reduced to 19 μ g/g by 928 μ g/g, and the decalcification rate is 97.8%, and the output of hydrogen is 1mol.mol -1Substratum, the purity of hydrogen are 90.4%.
Embodiment 3
Subtilis, bacillus cereus, Bacillus licheniformis and pseudomonas aeruginosa bacterial classification that experiment is required; Adopt the conventional mikrobe mode of spreading cultivation to spread cultivation; Above-mentioned bacterium after will spreading cultivation respectively again and tunning thereof were by weight 2: 1: 2: 1 mixes; Obtain mikrobe mixed bacterium and tunning thereof, and make its bacteria concentration reach 1.0 * 10 8Individual/ml, pH is 7.0, survival rate 99%; Then mentioned microorganism mixed bacterium and tunning thereof to account for tap water or oilfield injection water weight 1.7%; Beet waste molasses in the substratum, Carnis Bovis seu Bubali cream, potassium hydrogenphosphate, SODIUM PHOSPHATE, MONOBASIC, sal epsom add in tap water or the oilfield injection water with the concentration that accounts for tap water or oilfield injection water weight 1%, 0.5%, 0.5%, 0.5% and 0.05% respectively; Be mixed with microbial fermentation solution, again microbial fermentation solution and crude oil added in the encloses container by weight 0.3: 1, under 55 ℃ of temperature of reaction and obstructed air conditions, carry out the thorough mixing reaction; Keep the amphimicrobian state in the entire reaction course; Collect the gas that reaction process produces simultaneously, through cultivating reaction 3 days, the calcium contents of crude oil is reduced to 17 μ g/g by 164 μ g/g; The decalcification rate is 89.6%, and the output of hydrogen is 1mol.mol -1Substratum, the purity of hydrogen are 92.6%.
Embodiment 4
Subtilis, bacillus cereus, Bacillus licheniformis and pseudomonas aeruginosa bacterial classification that experiment is required; Adopt the conventional mikrobe mode of spreading cultivation to spread cultivation; Above-mentioned bacterium after will spreading cultivation respectively again and tunning thereof were by weight 1: 0: 0: 0 mixes; Obtain mikrobe mixed bacterium and tunning thereof, and make its bacteria concentration reach 9.2 * 10 9Individual/ml, pH is 6.2, survival rate 85%; Then mentioned microorganism mixed bacterium and tunning thereof to account for tap water or oilfield injection water weight 2.0%, the beet waste molasses in the substratum accounts for the concentration of tap water or oilfield injection water weight 1% to be added in tap water or the oilfield injection water, is mixed with microbial fermentation solution; Again microbial fermentation solution and crude oil were added in the encloses container by weight 0.3: 1; Under 40 ℃ of temperature of reaction and obstructed air conditions, carry out the thorough mixing reaction, keep the amphimicrobian state in the entire reaction course, collect the gas that reaction process produces simultaneously; Through cultivating reaction 5 days; The calcium contents of crude oil is reduced to 25 μ g/g by 196 μ g/g, and the decalcification rate is 87.2%, and the output of hydrogen is 0.9mol.mol -1Substratum, the purity of hydrogen are 93.2%.
Embodiment 5
Subtilis, bacillus cereus, Bacillus licheniformis and pseudomonas aeruginosa bacterial classification that experiment is required; Adopt the conventional mikrobe mode of spreading cultivation to spread cultivation; Above-mentioned bacterium after will spreading cultivation respectively again and tunning thereof were by weight 0: 1: 1: 1 mixes; Obtain mikrobe mixed bacterium and tunning thereof, and make its bacteria concentration reach 6.2 * 10 9Individual/ml, pH is 5.2, survival rate 95%; Then mentioned microorganism mixed bacterium and tunning thereof to account for tap water or oilfield injection water weight 3.5%; Beet waste molasses in the substratum, peptone, potassium hydrogenphosphate, SODIUM PHOSPHATE, MONOBASIC, sal epsom add in tap water or the oilfield injection water with the concentration that accounts for tap water or oilfield injection water weight 2%, 0.5%, 0.5%, 0.5% and 0.05% respectively; Be mixed with microbial fermentation solution, again microbial fermentation solution and crude oil added in the encloses container by weight 0.3: 1, under 30 ℃ of temperature of reaction and obstructed air conditions, carry out the thorough mixing reaction; Keep the amphimicrobian state in the entire reaction course; Collect the gas that reaction process produces simultaneously, through cultivating reaction 3 days, the calcium contents of crude oil is reduced to 23 μ g/g by 296 μ g/g; The decalcification rate is 92.2%, and the output of hydrogen is 0.6mol.mol -1Substratum, the purity of hydrogen are 90.4%.

Claims (5)

1. the method for a crude oil mikrobe decalcification co-producing hydrogen; It is characterized in that: with each bacterial classification of required mikrobe; Adopt the conventional mikrobe mode of spreading cultivation to spread cultivation, above-mentioned bacterium and tunning thereof after will spreading cultivation respectively mix by arbitrary proportion again, and making its bacterium index reach concentration is 10 8~10 10Individual/the ml mixed bacterium, the pH value is 5~7, and surviving rate is 85~99%; Add mentioned microorganism mixed bacterium and tunning thereof in tap water or the oilfield injection water to cultivation fiduciary point tap water or oilfield injection water weight 1~6% amount by accounting for tap water or oilfield injection water weight 1~10% then; Be mixed with microbial fermentation solution, microbial fermentation solution and crude oil join in the encloses container by weight the ratio that is 0.1: 1~0.5: 1, are 25~55 ℃ in temperature; Cultivating the reaction times is 1~5 day; Carry out the thorough mixing reaction under the obstructed air conditions, keep the amphimicrobian state in the entire reaction course, collect the gas that reaction process produces;
Described microbe-derived in oil field mining liquid or oil field soil sample; Be one or more the mikrobe associate strain in subtilis (Bacillus subtilis), bacillus cereus (Bacillus cereus), Bacillus licheniformis (Bacillus licheniformis) or the pseudomonas aeruginosa (Pseudomonas aeruginosa), said bacterial classification provides by China Committee for Culture Collection of Microorganisms common micro-organisms center.
2. the method for crude oil mikrobe decalcification co-producing hydrogen according to claim 1 is characterized in that: microbial inoculum and crude oil operative temperature are 30~45 ℃, and cultivating the reaction times is 2~3 days.
3. the method for crude oil mikrobe decalcification co-producing hydrogen according to claim 1 is characterized in that: substratum is one or more a material of waste molasses, beef extract or inorganic salt micronutrient element.
4. the method for crude oil mikrobe decalcification co-producing hydrogen according to claim 3; It is characterized in that: the waste molasses add-on accounts for 1~6% of microbial fermentation solution weight in the substratum; The beef extract add-on accounts for 0~0.5% of microbial fermentation solution weight; In the inorganic salt micronutrient element, the ammonium salt add-on account for microbial fermentation solution weight 0~0.5%, the sodium salt add-on account for microbial fermentation solution weight 0~0.5%, the sylvite add-on account for microbial fermentation solution weight 0~0.5%, the magnesium salts add-on accounts for 0~0.05% of microbial fermentation solution weight.
5. the method for crude oil mikrobe decalcification co-producing hydrogen according to claim 4; It is characterized in that: waste molasses is the beet waste molasses; Beef extract is that one or both combination of components in Carnis Bovis seu Bubali cream or the peptone form, and ammonium salt is an ammonium nitrate or ammonium sulfate, and sodium salt is Sodium phosphate, dibasic or SODIUM PHOSPHATE, MONOBASIC; Sylvite is potassium primary phosphate or potassium hydrogenphosphate, and magnesium salts is a sal epsom.
CN2007101792718A 2007-12-12 2007-12-12 Method for microbial decalcification and co-production of hydrogen in crude oil Expired - Fee Related CN101457155B (en)

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CN1865404A (en) * 2005-05-20 2006-11-22 中国石油天然气股份有限公司 Hydrocarbon oil biological decalcification method

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Publication number Priority date Publication date Assignee Title
CN1865404A (en) * 2005-05-20 2006-11-22 中国石油天然气股份有限公司 Hydrocarbon oil biological decalcification method

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于娟等.微生物脱除高钙原油中钙的研究.《新疆石油天然气》.2007,第3卷(第2期), *

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