CN101402878B - Method for removing nickel vanadium in crude oil with microwave chemical method - Google Patents
Method for removing nickel vanadium in crude oil with microwave chemical method Download PDFInfo
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- CN101402878B CN101402878B CN2008102027357A CN200810202735A CN101402878B CN 101402878 B CN101402878 B CN 101402878B CN 2008102027357 A CN2008102027357 A CN 2008102027357A CN 200810202735 A CN200810202735 A CN 200810202735A CN 101402878 B CN101402878 B CN 101402878B
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- 239000010779 crude oil Substances 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000000126 substance Substances 0.000 title claims abstract description 15
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 title claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 48
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 45
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 29
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
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- 239000003921 oil Substances 0.000 claims description 24
- 239000000839 emulsion Substances 0.000 claims description 12
- BSURVFMRBJIMSY-UHFFFAOYSA-M sodium N-ethyl-N-sulfidosulfanylethanamine Chemical group C(C)N(SS[Na])CC BSURVFMRBJIMSY-UHFFFAOYSA-M 0.000 claims description 9
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 6
- 239000005977 Ethylene Substances 0.000 claims description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 8
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 7
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 abstract 3
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- 239000009671 shengli Substances 0.000 description 6
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- 238000005516 engineering process Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
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- 239000002253 acid Substances 0.000 description 2
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- 239000000571 coke Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
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- 238000000605 extraction Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000004032 porphyrins Chemical class 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
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- 239000012362 glacial acetic acid Substances 0.000 description 1
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- 125000000168 pyrrolyl group Chemical group 0.000 description 1
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- 239000003352 sequestering agent Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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Abstract
The invention provides a method for removing nickel and vanadium in crude oil through a microwave chemical method and includes the following steps: (1) the crude oil is arranged in a microwave chemical reactor for microwave treatment; then a metal removing agent and water are added for reaction at the temperature of 80 to 90 DEG C; the metal removing agent is selected from more than one of sodiumdiethyldityiocarbamate, 1,2-ethylidene diamino double (sodium dimethyl-dithiocarbamate), double (1,2-ethylidene group) triamido three (sodium dimethyl-dithiocarbamate) or three(1,2-ethylidene group) tetramino four (sodium dimethyl-dithiocarbamate); and (2) an electric field processing method is adopted for processing, thus obtaining the crude oil the nickel and vanadium of which are removed. Whenthe method is adopted, the weight removing rate of the nickel in the crude oil can achieve more than 45 percent; the weight removing rate of the vanadium can achieve more than 70 percent; the device investment is less; no catalysts are used; the operation cost is low; and the method is convenient for industrial application.
Description
Technical field
The present invention relates to the removal methods of nickel vanadium in the crude oil.
Background technology
In recent years along with of the degree of depth exploitation of domestic and international each oil field to crude oil; Oil property trends towards heaviness, poor qualityization; The crude oil of high acid value, high sulfur content constantly increases; Crude oil that China's main oil producing area density is big, viscosity is high, metal content is high or heavy oil production cumulative year after year, like Liaohe River viscous crude, Kelamayi viscous crude, isolated island viscous crude etc., the metal content in these crude oil is the content height of heavy metal nickel, vanadium especially.Metal Distribution is different in the different crude oil, and Metal Distribution is different in the different crude oil, and calcium, iron level in some crude oil are higher, and nickel, content of vanadium in some crude oil are higher, and the metal content in the crude oil has the trend that increases day by day.Like nickel vanadium metal content in the heavy oil of the Liaohe River up to more than the 200 μ g/g; Heavy metal content also is higher than 150 μ g/g in the triumph heavy oil; In the viscous crude of Kelamayi only calcium contents just up to more than the 400 μ g/g, recently the exploitation the Xinjiang Tahe Crude Oil in only nickel vanadium metal content just up to more than the 400 μ g/g.External high-sulfur crude oil metal content is high, general vacuum residuum metal content all more than 100 μ g/g, have up to 800 μ g/g, and be mainly vanadium.Because the demand of crude oil deep processing at present, metallic impurity more and more receive people's attention to the harm of refining of petroleum in the crude oil.
Metal in the crude oil has a strong impact on the processing of crude oil, not only because of hydrolysis causes the distillation plant corrosion, and seriously influences the following process process.Not only make the catalyst deactivation of catalyzed cracking processing process, promote the generation of coke and gaseous product, reduce light oil yield; Can cause that also catalyst deactivation in the hydrogenation process, obstruction bed make system pressure increase, influence quality product, shorten on-stream time, increase running cost; Even also can influence residual oil visbreaking and delay coking process, and cause that visbreaking oil fuel stability reduces, cause the heating furnace tube coking, shorten on-stream time, reduce the coking distillate yield, make coke reduce quality because of ash is too high.
Nickel in the crude oil, vanadium enrichment mainly are that the form with organic porphyrin metal compound exists in residual oil, and the porphyrin vanadium compound is in the space in four pyrrole rings, combine with it and the complex compound that forms with covalent linkage and co-ordination bond form; The main existence form of non-vanadium porphyrin is to mix the entad four-coordinate complex of ligand, and the coordinate heteroatoms can be N, O, S.Similar with vanadium, nickel also is to be present in the crude oil with porphyrin compound and two kinds of forms of non-porphyrin compound.The porphyrin compound of nickel, vanadium is oil soluble, and is water insoluble, therefore can't they be removed from crude oil with conventional electric desalting method.
Nickel, vanadium existence form and physics thereof, chemical property in the based on crude can adopt methods such as sour extracting, hydrogenation, solvent extraction to remove.
The acid extraction process.This method mainly adopts hydrogen bromide-Glacial acetic acid min. 99.5 or hydrogen bromide-formic acid solution to make extraction solvent, and extracting goes out porphyrin and metal porphyrins.Be mainly used in the porphyrin compound of analyzing in the oil.
Hydrogenation method.Because nickel, vanadium mainly are present in the residual oil, when carrying out hydrogenating desulfurization or catalytic cracking, have a strong impact on product yield and catalyst activity, so some refinerys have adopted the HDM technology.The key of this technology is to adopt catalyst for demetalation, and nickel, vanadium porphyrin and complicated compound hydrogenation are decomposed, and nickel, vanadium is deposited on the catalyst for demetalation, thereby reduces nickel, content of vanadium in the residual oil.
Solvent extraction process.Because how nickel, vanadium exist with the porphyrin compound form in the oil, and porphyrin compound can dissolve each other with organic solvent, thereby can go out nickel, vanadium porphyrin compound with extracting from oil such as acetonitrile, DMF, but this method is used for analysis more, can't realize industriallization.Nickel, vanadium porphyrin compound are prone to and pitch generation association, form pitch gummed ion, thereby nickel, vanadium is present in the bituminous matter more, if pitch is removed, also can slough a part of nickel, vanadium.Because low molecular solvent such as propane, butane have the selection solvability to the different components in the residual oil; And can not the dissolution of metals porphyrin compound; Therefore utilize propane, butane equal solvent that pitch in the residual oil and non-asphaltene are separated, promptly remove pitch, also can reach the purpose of nickel removal, vanadium.Industrial application shows, from the bitumeniferous residual oil of height, can remove nickel, vanadium more than 50% with the solvent deasphalting method.
From industrialized nickel removal, vanadium method at present, also there are some problems.The HDM plant investment is big.And catalyzer be difficult to regeneration, cause spent catalyst to handle; Solvent deasphalting can only remove nickel, the vanadium in the high residual oil of asphalt content, and investment is big, and process cost is high, and therefore, industrial application is restricted.Comparatively speaking; If it is few to develop consumption; The nickel that sequestering power is strong, vanadium sequestrant adopt chelate separation process to remove nickel in the oil, vanadium and then can reduce facility investment and process cost, but owing to complicated component in the crude oil; The structure of nickel, vanadium compound is more stable, thereby can't effectively solve the problem of crude oil nickel removal vanadium with chemical method at present.
Summary of the invention
The purpose of this invention is to provide the method that a kind of microwave chemical method removes nickel vanadium in the crude oil, to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
(1) crude oil is placed microwave chemical reactor, microwave treatment 5～60 minutes adds metal remover and water then, at 80～90 ℃, and under preferred 85 ℃, reaction 10～30min;
The processing condition of microwave treatment are following: microwave frequency is 915MHz～2450MHz; Power is 100～800W;
Said microwave chemical reactor is conventional industrial little producer, is a kind of general-purpose equipment, is the product of MAS-III like the new appearance microwave chemical in the Shanghai Science and Technology Ltd. trade mark;
Said metal remover is selected from diethylamino dithio sodium formiate, 1; Amino two (the dithio sodium formiates), two (1 of 2-ethylene; 2-ethylidene) more than one in triamino three (dithio sodium formiate) or three (1,2-ethylidene) tetramino four (dithio sodium formiate);
The add-on of metal remover is 0.005～0.05% of a former weight of oil; The add-on of water is 3～9% of a former weight of oil;
(2) adopt the electric field treatment method to handle then, obtain to have removed the crude oil of nickel and vanadium, said electric field treatment method is a kind of prior art, and like petroleum refining engineering (Lin Shixiong work, petroleum industry press) document disclosed method, concrete process is following:
Adding emulsion splitter, shake 1～3 minute, place electric field then, is to leave standstill 10～30min under the condition of 500～1300V/cm in strength of electric field, and the upper strata crude oil in the collection product is the crude oil that has removed nickel and vanadium.
Said emulsion splitter is selected from one or more mixtures in alkyl phenolic resin polyoxy third rare Soxylat A 25-7, USP Kosher polyoxy third rare Soxylat A 25-7, stearyl alcohol polyoxy third rare Soxylat A 25-7 or the quadrol polyoxy third rare Soxylat A 25-7, and the add-on of emulsion splitter is 0.001～0.005% of a former weight of oil;
In the said crude oil, the content of nickel is 10～400 μ g/g, and the content of vanadium is 10～400 μ g/g;
Described diethylamino dithio sodium formiate, 1; Amino two (the dithio sodium formiates), two (1 of 2-ethylene; 2-ethylidene) triamino three (dithio sodium formiate) or three (1; 2-ethylidene) tetramino four (dithio sodium formiate) can adopt commercially available product, perhaps can adopt following method preparation:
Use diethylamine, quadrol, diethylenetriamine, triethylene tetramine and CS respectively
2Reaction can obtain diethylamino dithio sodium formiate, amino two (the dithio sodium formiates) of 1,2-ethylene, two (1,2-ethylidene) triamino three (dithio sodium formiate) and three (1,2-ethylidene) tetramino four (dithio sodium formiate);
With the diethylamine is example:
With diethylamine aqueous solution at 0～5 ℃, with dithiocarbonic anhydride and weight fraction be the aqueous solution of 0.02% sodium hydroxide, be warming up to 25～30 ℃, stirring reaction 1～3 hour is collected the crystallization of separating out, and is diethylamino dithio sodium formiate;
The weight concentration of diethylamine aqueous solution is 30～70%, and the adding weight of dithiocarbonic anhydride is 100～120% of diethylamine, and weight fraction is that the adding weight of 0.02% sodium hydroxide is 100～120% of diethylamine.
With same method, can synthesize amino two (the dithio sodium formiates) of 1,2-ethylene, two (1,2-ethylidene) triamino three (dithio sodium formiate) or three (1,2-ethylidene) tetramino four (dithio sodium formiate).
Adopt aforesaid method that crude oil is handled, the weight decreasing ratio of the nickel in the crude oil can reach more than 45%, and the weight decreasing ratio of vanadium can reach more than 70%, and the definition of decreasing ratio is following:
Adopt method of the present invention, the weight decreasing ratio of the nickel in the crude oil can reach more than 45%, and the weight decreasing ratio of vanadium can reach more than 70%, and facility investment is little, and without catalyzer, process cost is low, is convenient to industrial application.
Embodiment
The following handled crude oil of embodiment is Iran crude or Shengli crude, and in the Iran crude, the content of nickel is 56.84 μ g/g, and the content of vanadium is 74.51 μ g/g, and in the Shengli crude, the content of nickel is 44.56 μ g/g, and the content of vanadium is 30.11 μ g/g..
Microwave chemical reactor is the product of MAS-III for Xinyi Microwave Chemistry Tech Co., Ltd.'s trade mark.
Embodiment 1
Crude oil is Iran crude.
(1) crude oil is placed microwave chemical reactor, microwave treatment 45 minutes adds metal remover diethylamino dithio sodium formiate and water then, under 85 ℃, and reaction 20min;
The processing condition of microwave treatment are following: microwave frequency is 2450MHz; Power is 200W;
(2) add the mixture (1:1 of emulsion splitter USP Kosher polyoxy third rare Soxylat A 25-7 and quadrol polyoxy third rare Soxylat A 25-7 again; Weight ratio); Shaking 2 minutes, and placed electric field then, is to leave standstill 20min again under the condition of 500V/cm in strength of electric field; Collect the upper strata crude oil in the product, be the crude oil that has removed nickel and vanadium.Wherein, nickel content be 31.22 μ g/g, decreasing ratio is 45.08%, vanadium content be 19.23 μ g/g, decreasing ratio is 74.19%.
The adding weight of diethylamino dithio sodium formiate is 0.01% of crude oil;
The adding weight of water is 5% of crude oil;
The adding weight of emulsion splitter is 0.005% of crude oil;
As electric field method only, the content of nickel is 51.57 μ g/g, and decreasing ratio is 9.27%, and the content of vanadium is 55.25 μ g/g, and decreasing ratio is 25.58%.
Embodiment 2
Crude oil is Shengli crude.
(1) crude oil is placed microwave chemical reactor, microwave treatment 30 minutes adds metal remover diethylamino dithio sodium formiate and water then, under 85 ℃, and reaction 20min;
The processing condition of microwave treatment are following: microwave frequency is 2450MHz; Power is 200W;
(2) add the mixture (1:1 of emulsion splitter alkyl phenolic resin polyoxy third rare Soxylat A 25-7 and stearyl alcohol polyoxy third rare Soxylat A 25-7 again; Weight ratio); Shaking 3 minutes, and placed electric field then, is to leave standstill 20min again under the condition of 700V/cm in strength of electric field; Collect the upper strata crude oil in the product, be the crude oil that has removed nickel and vanadium.Wherein, nickel content be 24.29 μ g/g, decreasing ratio is 45.49%, vanadium content be 7.89 μ g/g, decreasing ratio is 73.78%.
The adding weight of diethylamino dithio sodium formiate is 0.01% of crude oil;
The adding weight of water is 5% of crude oil;
The adding weight of emulsion splitter is 0.005% of crude oil;
And adopt the electric field method, and the content of nickel is 37.97 μ g/g, and decreasing ratio is 14.79%, and the content of vanadium is 27.64 μ g/g, and decreasing ratio is 8.20%.
Embodiment 3
Adopt with embodiment 1 identical method and handle Iran crude, metal remover is amino two (the dithio sodium formiates) of 1,2-ethylene, and adding weight is 0.02% of crude oil; When microwave power is 100W, the microwave time is 60min, the crude oil after the processing, nickel content be 31.16 μ g/g, decreasing ratio is 45.18%, vanadium content be 18.49 μ g/g, decreasing ratio is 75.19%.
Embodiment 4
Adopt with embodiment 2 identical methods and handle Shengli crude, metal remover is amino two (the dithio sodium formiates) of 1,2-ethylene, and adding weight is 0.02% of crude oil; When microwave power is 100W, the microwave time is 60min, in the crude oil after the processing, nickel content be 24.25 μ g/g, decreasing ratio is 45.58%, the content of vanadium is 6.77 μ g/g, decreasing ratio is 77.51%.
Embodiment 5
Adopt with embodiment 1 identical method and handle Iran crude, metal remover is two (1,2-ethylidene) triamino three (dithio sodium formiate), and adding weight is 0.01% of crude oil; When microwave power is 300W, the microwave time is 5min, and result is following: nickel removal rate and vanadium removal rate can reach 48.64% and 87.50% respectively.
Embodiment 6
Adopt with embodiment 2 identical methods and handle Shengli crude, metal remover is two (1,2-ethylidene) triamino three (dithio sodium formiate), and adding weight is 0.01% of crude oil; When microwave power is 300W, the microwave time is 5min, and nickel removal rate and vanadium removal rate can reach 48.52% and 87.50% respectively.
Embodiment 7
Adopt with embodiment 1 identical method and handle Iran crude, metal remover is three (1,2-ethylidene) tetramino four (dithio sodium formiate), and adding weight is 0.03% of crude oil; Wherein: crude oil is handled 10min under the microwave of 800W power, adds emulsion splitter again and electric field dewaters, and the effect of nickel removal vanadium reaches 45.71% and 71.42% respectively.
Embodiment 8
Adopt with embodiment 2 identical methods and handle Shengli crude, metal remover is three (1,2-ethylidene) tetramino four (dithio sodium formiate), and adding weight is 0.03% of crude oil; Wherein: crude oil is handled 10min under the microwave of 800W power; Add emulsion splitter again and electric field dewaters, the effect of nickel removal vanadium reaches 49.22% and 75.67% respectively.
Claims (7)
1. microwave chemical method removes the method for nickel vanadium in the crude oil, it is characterized in that, comprises the steps:
(1) crude oil is placed microwave chemical reactor, microwave treatment adds metal remover and water then, 80～90 ℃ of reactions;
Said metal remover is selected from diethylamino dithio sodium formiate, 1; Amino two (the dithio sodium formiates), two (1 of 2-ethylene; The 2-ethylidene) more than one in triamino three (dithio sodium formiate) or three (ethylene) tetramino four (dithio sodium formiate);
(2) adopt the electric field treatment method to handle then, obtain to have removed the crude oil of nickel and vanadium.
2. method according to claim 1 is characterized in that, the processing condition of microwave treatment are following: microwave frequency is 915MHz～2450MHz; Power is 100～800W.
3. method according to claim 1 is characterized in that, microwave treatment 5～60 minutes adds metal remover and water then, reacts 10～30min down at 85 ℃.
4. method according to claim 1 is characterized in that, the add-on of metal remover is 0.005～0.05% of a former weight of oil; The add-on of water is 3～9% of a former weight of oil.
5. method according to claim 1; It is characterized in that the process of said electric field treatment method is following: add emulsion splitter, shook 1～3 minute; Place electric field then; Be to leave standstill 10～30min under the condition of 500～1300V/cm in strength of electric field, collect the upper strata crude oil in the product, be the crude oil that has removed nickel and vanadium.
6. method according to claim 5; It is characterized in that; Said emulsion splitter is selected from one or more mixtures of alkyl phenolic resin polyoxyethylene polyoxypropylene ether, USP Kosher polyoxyethylene polyoxypropylene ether, stearyl alcohol polyoxyethylene polyoxypropylene ether or quadrol polyoxyethylene polyoxypropylene ether, and the add-on of emulsion splitter is 0.001～0.005% of a former weight of oil.
7. according to each described method of claim 1～6, it is characterized in that in the said crude oil, the weight content of nickel is 10～400 μ g/g, the weight content of vanadium is 10～400 μ g/g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102027357A CN101402878B (en) | 2008-11-14 | 2008-11-14 | Method for removing nickel vanadium in crude oil with microwave chemical method |
Applications Claiming Priority (1)
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| CN102311773B (en) * | 2010-06-30 | 2013-12-25 | 中国石油化工股份有限公司 | Method for improving crude oil distillation yield by utilizing ultrasonic wave |
| CN102746881B (en) * | 2011-04-21 | 2014-10-29 | 中国石油化工股份有限公司 | Crude oil demetallization method |
| CN103374415B (en) * | 2012-04-17 | 2015-07-29 | 中国石油化工股份有限公司 | A kind of method removing nickel vanadium in hydrocarbon ils |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6068737A (en) * | 1997-05-16 | 2000-05-30 | Simon Bolivar University | Simultaneous demetallization and desulphuration of carbonaceous materials via microwaves |
| CN1356376A (en) * | 2001-11-22 | 2002-07-03 | 中国石油化工集团公司 | Process for removing Ni and V from fractional oil of crude oil |
| CN1408017A (en) * | 1999-11-16 | 2003-04-02 | Rmg服务控股有限公司 | Treatment of crude oils |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6068737A (en) * | 1997-05-16 | 2000-05-30 | Simon Bolivar University | Simultaneous demetallization and desulphuration of carbonaceous materials via microwaves |
| CN1408017A (en) * | 1999-11-16 | 2003-04-02 | Rmg服务控股有限公司 | Treatment of crude oils |
| CN1356376A (en) * | 2001-11-22 | 2002-07-03 | 中国石油化工集团公司 | Process for removing Ni and V from fractional oil of crude oil |
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