CN1865404A - Biological decalcification method for hydrocarbon - Google Patents
Biological decalcification method for hydrocarbon Download PDFInfo
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- CN1865404A CN1865404A CN 200510070798 CN200510070798A CN1865404A CN 1865404 A CN1865404 A CN 1865404A CN 200510070798 CN200510070798 CN 200510070798 CN 200510070798 A CN200510070798 A CN 200510070798A CN 1865404 A CN1865404 A CN 1865404A
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Abstract
The invention discloses a hydrocarbon oil chemical sedimenting decalcification method of metal calcium, which comprises the following steps: adopting molasses through microbe in the environment to proceed anaerobic ferment for 3-5 days at 30-60 deg.c; blending the ferment liquid, hydrocarbon oil and demulsifying agent with 3-0.5: 1 blending proportion for ferment liquid and hydrocarbon oil; proceeding emulsion for 2-15 min at 40-160 deg.c; separating water from oil for 10-60 min at 50-140 deg.c. The invention can strip metal calcium with over 100 ug per g calcium content in the hydrocarbon oil, which doesn't generate erosion for equipment.
Description
Technical field
The present invention relates to the Application Areas of biological fermentation product in petrochemical complex, more specifically say so and utilize the biological fermentation product to remove a kind of biological decalcification method for hydrocarbon of the calcium metal in the hydrocarbon ils.
Background technology
The output of China's mink cell focus constantly increases and a large amount of external heavy crude of import at present, metal content in these crude oil, particularly the content of some alkaline-earth metal such as calcium, magnesium is higher, as Xinjiang Junggar Basin viscous crude calcium contents up to 250 μ g/g, the super viscous crude calcium contents in the Liaohe River greater than 300 μ g/g and CNPC at the Fula-north of the Sudan's cooperative exploitation viscous crude calcium contents usually at 800-1600 μ g/g.Studies show that the calcium metal content in the crude oil increases, will make in refinery's crude oil processing catalyst deactivation to occur that quality product descends, and process unit and quality product have been brought disadvantageous effect, makes refinery's crude oil processing suffer financial loss.And concerning general terrestrial facies heavy crude, the content of calcium metal is much larger than other metal content, be less than 25 μ g/g as Xinjiang Junggar Basin viscous crude MAGNESIUM METAL, vanadium, nickel three sum, the calcium metal that therefore removes in the heavy crude is even more important to the complete processing of heavy crude.
Calcium metal part in the crude oil is with water-soluble salt, slightly soluble salt such as calcium chloride, Calcium hydrogen carbonate, and forms such as calcium sulfate, calcium phosphate exist, and another part exists with the form of petroleum acid calcium.In general refinery, can remove the salt and the hydrophilic inorganic calcium salt particle of most solubilities in the electric desalting process; Then almost there is not removal effect for the lipophilicity inorganic calcium salt particle and the petroleum acid calcium that are present in the oil phase, this part metals calcium has a negative impact to the crude oil processing of postorder, and the decalcification of mentioning indication in all crude oil decalcifying technology (method) in the present invention is the calcium metal of this type.
Present known crude oil decalcifying technology can be summed up as chemical chelating method, chemical acidic treatment and chemical precipitation method.The patented technology of chemistry chelating method has CN8610728A, CN1036981A, CN87105863, these patents adopt and can carry out crude oil decalcifying with aminocarboxylic acid, di-carboxylic acid, the hydroxycarboxylic acid that Ca generates water soluble chelate compound, this class methods medicament price is comparatively expensive, is difficult to industrialization; The patented technology of chemistry acidic treatment has CN1112424C, CN1454967A, this class patented technology utilizes in the organic or inorganic petroleum acid calcium in the strong acid and crude oil to carry out that the hydrionic principle of strong acid is petroleum acid with the petroleum acid calcium reduction in the weak acid displacement, remove the calcium in the crude oil, these class methods to decreasing ratio of the calcium in the crude oil up to more than 90%, shortcoming is that the industrial acids that adopts is unfriendly and industrial equipments had corrosive nature to environment, need select corrosion resistant apparatus for use, also exist calcium to remove shortcomings such as back acid value for crude oil rising; The patented technology of chemical precipitation method has CN1055552A, CN1054261A, CN1078234C, petroleum acid calcium effect generation slightly soluble in this class methods employing water soluble sulfate, phosphoric acid salt and crude oil or water-fast calcium sulfate, calcium phosphate, under the effect of solid wetting agent, be deposited on water and reach decalcification, this class decalcification method is comparatively friendly to environment and equipment, and weak point is that a decreasing ratio to metals in hydrocarbon oil calcium is only at 60-70%.In above chemical chelating method and chemical precipitation method, they are more undesirable to calcium contents its decalcification effect of high calcium content crude oil more than 200 μ g/g.
Summary of the invention
The object of the present invention is to provide a kind of biological decalcification method for hydrocarbon that utilizes the biological fermentation product to remove metals in hydrocarbon oil calcium, this method can remove calcium effectively and contain calcium metal in the above high calcium content crude oil of 100 μ g/g, remove mild condition, environmental sound does not produce corrosion to equipment.
The present invention is achieved in that
The present invention relates to a kind of method of hydrocarbon ils biological decalcification, definite say so that to utilize the microorganism in the environment earlier be that nutrition carried out anaerobically fermenting more than 1 day under 30～60 ℃ with molasses, its fermented liquid mixes with hydrocarbon ils, emulsion splitter again, make oily water separation after the emulsification, the oil-water emulsion time is 2～15 minutes, and emulsifying temperature is 40 ℃～160 ℃.
In the present invention, our said all proportions all is a part by weight.Microorganism in the environment of the present invention refers to the microorganism that exists in the air, and said molasses are a kind of byproducts of sugarcane or beet-sugar factory, claim tangerine water again.The molasses dry substance concentration is very big, itself contains 40～70% fermentable sugars, at present industrial be the good raw material of producing alcohol.The consumption of molasses accounts for 1～8%, preferred 3～6% of fermentation liquid measure in the present invention.
Said emulsion splitter answers the based on crude kind to select, can be single emulsion splitter or composite demulsifying agent, consumption is 20～100ppm of hydrocarbon ils weight, the effect of emulsion splitter is to promote that profit separates rapidly, as FC9301 (Luoyang, Henan petrochemical corporation (complex) product), OP-10 (the new Australia of Kelamayi City chemical industry company limited product) etc.
Molasses fermented in the present invention temperature is 30～60 ℃, preferred 40 ℃; Fermentation time is more than 1 day, preferred 3～5 days; The ratio of mixture of fermented liquid and hydrocarbon ils is 3～0.5: 1, preferred 2～1: 1; The oil-water emulsion time is 2～15 minutes, and emulsifying temperature is 40 ℃～160 ℃, and the preferred oil emulsifying water time is 3～7 minutes, and emulsifying temperature is 80 ℃～100 ℃; The oily water separation time is 10～60 minutes, and separation temperature is 50 ℃～140 ℃, and the preferred oil water sepn time is 30 ~ 40 minutes, and separation temperature is 70 ℃～120 ℃.
Biological decalcification method provided by the invention utilizes environmental microorganism molasses meta-bolites to carry out the crude oil decalcifying effect, simple to operate, with low cost, removal efficiency is high, be specially adapted to the above hydrocarbon ils of calcic 100 μ g/g, as Xinjiang heavy crude oil, Liaohe Oil Field viscous crude, the Sudan's crude oil and residual oil etc., the crude oil calcium metal decreasing ratio after its one-level is handled can reach 70%～97%.
The method of biological hydrocarbon oil decalcifying provided by the invention is as follows:
(1) tap water is inserted in the open container, in physical environment room temperature (20～40 ℃), place more than 5 days, make to have environmental microorganism in the water.
(2) add 1%～8% molasses in above-mentioned tap water, standing for fermentation obtained the anaerobic fermented liquid of molasses more than 1 day under 30～60 ℃ of anaerobic conditions.
(3) with molasses anaerobic fermented liquid and hydrocarbon ils in 3～0.5: 1 ratio is put in the mixing vessel, adds emulsion splitter, with high speed shear mulser thorough mixing, makes oil, the complete emulsification of water, and the oil-water emulsion time is 2 ~ 15 minutes, and emulsifying temperature is 40 ℃～160 ℃.
(4) the hydrocarbon ils dehydration is to carry out on the electric desalting tester, and the oily water separation time decides according to the device condition, is generally 10～60 minutes, and separation temperature is 50～140 ℃.
The effect of invention
Utilize this method to carry out the above hydrocarbon oil decalcifying of calcium content 100 μ g/g, its decreasing ratio can reach 70%～97%.
Embodiment
Embodiment 1: meet tap water 3000ml with a 5000ml beaker, open wide and be placed on the room 6 days, in tap water, add molasses 90 grams (3% concentration) then, respectively tap water is poured into after stirring in the narrow-mouthed bottle of three 1000ml band soft rubber balls, it is full of bottle mouth position to replenish bottle with distilled water, filled in soft rubber ball, on soft rubber ball, plugged syringe and make gas release that molasses fermented process produces in syringe.These three narrow-mouthed bottles are placed on leave standstill respectively in 40 ℃ the biochemical incubator and cultivate 3 days, 5 days, 6 days (numbering is respectively No. 1, No. 2, No. 3).With No. 1, No. 2, No. 3 each 1000ml of sample is Xinjiang Jiu Qu heavy crude 500 grams of 242 μ g/g and 100ppm OP-10 (the new Australia of Kelamayi City chemical industry company limited product) thorough mixing 5 minutes under the high speed shear mulser stirs with calcium metal content respectively, this moment mixed solution temperature 60 ℃～100 ℃ scope.Mixed solution left standstill 2 hours, after telling the water of lower floor crude oil emulsion is put into SH-2 type electric desalting tester, under 120 ℃, weak electric field 500V/cm 21 minutes, highfield 1000V/cm 7 minutes, 7 minutes settling times condition, dewater, analysis calcium contents wherein draws oil sample, calcium contents is respectively 33.5 μ g/g, 23.1 μ g/g, 23.3 μ g/g after the dehydrating of crude oil of No. 1, No. 2, No. 3 sample effect, and the decalcification rate is respectively: 86.2%, 90.5%, 90.4%.
Embodiment 2: meet tap water 3000ml with a 5000ml beaker, open wide and be placed on the room 6 days, in tap water, add molasses 180 grams (6% concentration) then, respectively tap water is poured into after stirring in the narrow-mouthed bottle of three 1000ml band soft rubber balls, it is full of bottle mouth position to replenish bottle with distilled water, filled in soft rubber ball, on soft rubber ball, plugged syringe and make gas release that molasses fermented process produces in syringe.These three narrow-mouthed bottles are placed on leave standstill respectively in 40 ℃ the biochemical incubator and cultivate 3 days, 5 days, 6 days (numbering is respectively No. 4, No. 5, No. 6).With No. 4, No. 5, No. 6 each 1000ml of sample is Xinjiang Jiu Qu heavy crude 500 grams of 242 μ g/g and 100ppm OP-10 (the new Australia of Kelamayi City chemical industry company limited product) thorough mixing 5 minutes under the high speed shear mulser stirs with calcium metal content respectively, this moment mixed solution temperature 60 ℃～100 ℃ scope.Mixed solution left standstill 2 hours, after telling the water of lower floor crude oil emulsion is put into SH-2 type electric desalting tester, under 120 ℃, weak electric field 500V/cm 21 minutes, highfield 1000V/cm 7 minutes, 7 minutes settling times condition, dewater, analysis calcium contents wherein draws oil sample, calcium contents is respectively 22.8 μ g/g, 13.6 μ g/g, 11.3 μ g/g after the dehydrating of crude oil of No. 4, No. 5, No. 6 sample effects, and the decalcification rate is respectively: 90.6%, 94.4%, 95.3%.
Embodiment 3: meet tap water 3000ml with a 5000ml beaker, open wide and be placed on the room 6 days, in tap water, add molasses 180 grams (6% concentration) then, respectively tap water is poured into after stirring in the narrow-mouthed bottle of three 1000ml band soft rubber balls, it is full of bottle mouth position to replenish bottle with distilled water, filled in soft rubber ball, on soft rubber ball, plugged syringe and make gas release that molasses fermented process produces in syringe.These three narrow-mouthed bottles are placed on leave standstill respectively in 60 ℃ the biochemical incubator and cultivate 3 days, 5 days, 6 days (numbering is respectively No. 7, No. 8, No. 9).With No. 7, No. 8, No. 9 each 1000ml of sample is Xinjiang Jiu Qu heavy crude 500 grams of 242 μ g/g and 100ppm OP-10 (the new Australia of Kelamayi City chemical industry company limited product) thorough mixing 5 minutes under the high speed shear mulser stirs with calcium metal content respectively, this moment mixed solution temperature 60 ℃～100 ℃ scope.Mixed solution left standstill 2 hours, after telling the water of lower floor crude oil emulsion is put into SH-2 type electric desalting tester, under 120 ℃, weak electric field 500V/cm 21 minutes, highfield 1000V/cm 7 minutes, 7 minutes settling times condition, dewater, analysis calcium contents wherein draws oil sample, calcium contents is respectively 60.7 μ g/g, 43.8 μ g/g, 44.3 μ g/g after the dehydrating of crude oil of No. 7, No. 8, No. 9 sample effects, and the decalcification rate is respectively: 74.9%, 81.9%, 81.7%.
Embodiment 4: meet tap water 3000ml with a 5000ml beaker, open wide and be placed on the room 6 days, in tap water, add molasses 180 grams (6% concentration) then, respectively tap water is poured into after stirring in the narrow-mouthed bottle of three 1000ml band soft rubber balls, it is full of bottle mouth position to replenish bottle with distilled water, filled in soft rubber ball, on soft rubber ball, plugged syringe and make gas release that molasses fermented process produces in syringe.These three narrow-mouthed bottles are placed on leave standstill respectively in 40 ℃ the biochemical incubator and cultivate 3 days, 5 days, 6 days (numbering is respectively No. 10, No. 11, No. 12).With No. 10, No. 11, No. 12 each 500ml of sample is Xinjiang Jiu Qu heavy crude 500 grams of 242 μ g/g and 100ppm OP-10 (the new Australia of Kelamayi City chemical industry company limited product) thorough mixing 5 minutes under the high speed shear mulser stirs with calcium metal content respectively, this moment mixed solution temperature 60 ℃～100 ℃ scope.Mixed solution left standstill 2 hours, after telling the water of lower floor crude oil emulsion is put into SH-2 type electric desalting tester, under 120 ℃, weak electric field 500V/cm 21 minutes, highfield 1000V/cm 7 minutes, 7 minutes settling times condition, dewater, analysis calcium contents wherein draws oil sample, calcium contents is respectively 42.2 μ g/g, 35.9 μ g/g, 36.7 μ g/g after the dehydrating of crude oil of No. 10, No. 11, No. 12 sample effects, and the decalcification rate is respectively: 82.6%, 85.2%, 84.8%.
Embodiment 5: meet tap water 3000ml with a 5000ml beaker, open wide and be placed on the room 6 days, in tap water, add molasses 180 grams (6% concentration) then, respectively tap water is poured into after stirring in the narrow-mouthed bottle of three 1000ml band soft rubber balls, it is full of bottle mouth position to replenish bottle with distilled water, filled in soft rubber ball, on soft rubber ball, plugged syringe and make gas release that molasses fermented process produces in syringe.These three narrow-mouthed bottles are placed on leave standstill respectively in 40 ℃ the biochemical incubator and cultivate 3 days, 5 days, 6 days (numbering is respectively No. 13, No. 14, No. 15).With No. 13, No. 14, No. 15 each 250ml of sample is Xinjiang Jiu Qu heavy crude 500 grams of 242 μ g/g and 100ppm OP-10 (the new Australia of Kelamayi City chemical industry company limited product) thorough mixing 5 minutes under the high speed shear mulser stirs with calcium metal content respectively, this moment mixed solution temperature 60 ℃～100 ℃ scope.Mixed solution left standstill 2 hours, after telling the water of lower floor crude oil emulsion is put into SH-2 type electric desalting tester, under 120 ℃, weak electric field 500V/cm 21 minutes, highfield 1000V/cm 7 minutes, 7 minutes settling times condition, dewater, analysis calcium contents wherein draws oil sample, calcium contents is respectively 70.9 μ g/g, 62.2 μ g/g, 60.7 μ g/g after the dehydrating of crude oil of No. 13, No. 14, No. 15 sample effects, and the decalcification rate is respectively: 70.7%, 74.3%, 74.9%.
Embodiment 6: meet tap water 3000ml with a 5000ml beaker, open wide and be placed on the room 6 days, in tap water, add molasses 180 grams (6% concentration) then, respectively tap water is poured into after stirring in the narrow-mouthed bottle of three 1000ml band soft rubber balls, it is full of bottle mouth position to replenish bottle with distilled water, filled in soft rubber ball, on soft rubber ball, plugged syringe and make gas release that molasses fermented process produces in syringe.These three narrow-mouthed bottles are placed on leave standstill respectively in 40 ℃ the biochemical incubator and cultivate 3 days, 5 days, 6 days (numbering is respectively No. 16, No. 17, No. 18).With No. 16, No. 17, No. 18 each 1000ml of sample is the Sudan's crude oil 500 grams of 702 μ g/g and 100ppm XJ-420 (Xi'an petrochemical industry branch office of Sinopec stock company product) thorough mixing 5 minutes under the high speed shear mulser stirs with calcium metal content respectively, this moment mixed solution temperature 60 ℃～100 ℃ scope.Mixed solution left standstill 2 hours, after telling the water of lower floor crude oil emulsion is put into SH-2 type electric desalting tester, under 140 ℃, weak electric field 500V/cm 21 minutes, highfield 1000V/cm 7 minutes, 7 minutes settling times condition, dewater, analysis calcium contents wherein draws oil sample, calcium contents is respectively 28.2 μ g/g, 15.2 μ g/g, 17.9 μ g/g after the dehydrating of crude oil of No. 16, No. 17, No. 18 sample effects, and the decalcification rate is respectively: 96.0%, 97.8%, 97.5%.
Claims (3)
1, a kind of biological decalcification method for hydrocarbon, it is characterized in that utilize the microorganism in the environment that molasses were carried out anaerobically fermenting 3～5 days earlier, the temperature of molasses anaerobically fermenting is 30～60 ℃, its fermented liquid mixes with hydrocarbon ils, emulsion splitter again, the ratio of mixture of fermented liquid and hydrocarbon ils is 3～0.5: 1, carries out emulsification, and the oil-water emulsion time is 2～15 minutes, emulsifying temperature is 40 ℃～160 ℃, make oily water separation then, the oily water separation time is 10～60 minutes, and separation temperature is 50 ℃～140 ℃.
2, method according to claim 1 is characterized in that, the consumption of fermentation molasses accounts for 1～8% of fermentation liquid measure.
3, method according to claim 1 is characterized in that, the ratio of mixture of fermented liquid and hydrocarbon ils is 2～1: 1.
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| CNB2005100707988A CN100413942C (en) | 2005-05-20 | 2005-05-20 | Biological decalcification method for hydrocarbon |
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| CN100413942C CN100413942C (en) | 2008-08-27 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210193B (en) * | 2007-12-25 | 2010-11-24 | 天津市工业微生物研究所 | Pipeline transportation method for easy-condensing high-viscous crude oil after degraded by microorganism |
| CN101200651B (en) * | 2006-12-12 | 2011-04-20 | 中国石油天然气股份有限公司 | Microbiological crude oil decalcifying agent as well as preparation method and decalcifying method thereof |
| CN101457156B (en) * | 2007-12-12 | 2012-05-30 | 中国石油天然气股份有限公司 | Crude oil decalcification method by using microorganism |
| CN101457155B (en) * | 2007-12-12 | 2012-05-30 | 中国石油天然气股份有限公司 | Crude oil decalcification and cogeneration hydrogen method by using microorganism |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208434C (en) * | 2003-06-03 | 2005-06-29 | 克拉玛依市金山石油化工有限公司 | Hydrocarbon oil demetalizing agent, and preparing method and use method thereof |
| CN1252218C (en) * | 2003-10-27 | 2006-04-19 | 中国石油化工股份有限公司 | Method for decalcifying hydrocarbon oil |
-
2005
- 2005-05-20 CN CNB2005100707988A patent/CN100413942C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200651B (en) * | 2006-12-12 | 2011-04-20 | 中国石油天然气股份有限公司 | Microbiological crude oil decalcifying agent as well as preparation method and decalcifying method thereof |
| CN101457156B (en) * | 2007-12-12 | 2012-05-30 | 中国石油天然气股份有限公司 | Crude oil decalcification method by using microorganism |
| CN101457155B (en) * | 2007-12-12 | 2012-05-30 | 中国石油天然气股份有限公司 | Crude oil decalcification and cogeneration hydrogen method by using microorganism |
| CN101210193B (en) * | 2007-12-25 | 2010-11-24 | 天津市工业微生物研究所 | Pipeline transportation method for easy-condensing high-viscous crude oil after degraded by microorganism |
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