CN1140610C - Process for removing Ni and V from fractional oil of crude oil - Google Patents
Process for removing Ni and V from fractional oil of crude oil Download PDFInfo
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- CN1140610C CN1140610C CNB011382120A CN01138212A CN1140610C CN 1140610 C CN1140610 C CN 1140610C CN B011382120 A CNB011382120 A CN B011382120A CN 01138212 A CN01138212 A CN 01138212A CN 1140610 C CN1140610 C CN 1140610C
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- vanadium
- nickel
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Abstract
The present invention discloses a technical process for removing nickel and vanadium from fractional oil of crude oil. The present invention is characterized in that 100 to 1000 ppm of demetallization agents are added to the fractional oil of the crude oil to react for 20 to 30 minutes at the temperature of 200 to 400 DEG C, and then is cooled to the temperature of 100 to 150 DEG C; water which accounts for 1 to 10% of the weight of the fractional oil of the crude oil, and 10 to 100 ppm of demulsifying agents are added; the fractional oil of the crude oil is separated under the condition of 200 to 1500 V/cm of electric field intensity to removing nickel and vanadium.
Description
Technical field
The invention belongs to the oil-refining chemical field, relate to the processing method that from fraction oil, removes metal, particularly from fractional oil of crude oil, remove the processing method of nickel vanadium.
Background technology
The existence of nickel vanadium has very big harm to petroleum refining industry in the fraction oil, according to nickel vanadium in the petroleum cuts oil have form and physics thereof, a chemical property, can adopt methods such as sour extracting, hydrogenation, chelating separation, solvent extraction to remove.From present domestic and international application situation, has only hydrogenation method industrial application.
Because the nickel vanadium mainly is 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 has adopted the hydrodemetallation (HDM) technology.The key of this technology is to adopt catalyst for demetalation, and nickel, vanadium porphyrin and complicated compound hydrogenation are decomposed, and the nickel vanadium is deposited on the catalyst for demetalation, thereby reduces the nickel content of vanadium in the residual oil.Domestic certain refinery has been introduced this technology, makes nickeliferous 43ppm, and the isolated island vacuum residuum of vanadium 2ppm takes off back nickeliferous 5.4ppm, vanadium 0.5ppm.This technology nickel vanadium decreasing ratio is higher, but the hydrodemetallation (HDM) plant investment is huge, and the difficult life of catalyzer, causes spent catalyst to handle.
More external patents have been introduced some compound and can have been reacted with nickel vanadium porphyrin and complex compound thereof, form non-oil-soluble material, thereby with physical method it are separated, and reach the purpose that removes the nickel vanadium.For example usefulness phosphoric acid such as United States Patent (USP) 4464251,4465589,4522702,4529503 and salt thereof remove nickel, the vanadium in the residual oil.In these patents, raw materials used oil is boiling point at 205～538 ℃ residual oil and artificial petroleum, wherein contains very high nickel and vanadium, contains 10～1000ppm vanadium and 5～500ppm nickel usually, also contains impurity such as sulphur, nitrogen, carbon residue simultaneously.United States Patent (USP) 4646589 is with inorganic phosphate and organophosphorus aqueous acid, to nickeliferous, the stock oil of vanadium carries out counter-current extraction, to wherein nickel, vanadium is extracted into water, its processing method is: the raw material that contains the nickel vanadium contacts in counter-current extraction tower with the water that contains metal remover, metal remover in nickel vanadium and the water forms water-soluble or hydrophilic compounds enters water trap, the complex compound of nickeliferous vanadium flows out from the water trap bottom, and most of unreacted metal remover continues to recycle, the metal remover raw material is discharged from extraction tower top, nickel, the vanadium decreasing ratio can reach 35% and 37%.United States Patent (USP) 3622505 is to be sequestrant with polyphosphoric acid, under 200～400 ℃ of temperature, removes the nickel vanadium in the vacuum residuum, and decreasing ratio can reach 80%, and shortcoming is that corrodibility is strong, can't industrial application.
Also there are some problems from present industrialized nickel removal vanadium method.The hydrodemetallation (HDM) plant investment is huge, and spent catalyst is difficult to regeneration, causes spent catalyst to be difficult to handle, and solvent deasphalting can only remove nickel, the vanadium in the high residual oil of asphalt content, and investment is big, the process cost height, so industrial application is restricted.Comparatively speaking, if it is few to develop consumption, the nickel vanadium sequestrant that sequestering power is strong adopts a retort and a cover electric desalting equipment, selects proper technical conditions, and the nickel, the vanadium that remove in the oil with the isolating method of chelating are feasible.
Summary of the invention
Because the nickel vanadium compound in the oil mostly is oil-soluble, therefore be difficult to remove with general electric desalting method, if but be translated into water-soluble or hydrophilic compound earlier, then can wash separation with water and remove.
The purpose of this invention is to provide a kind of processing method that removes the nickel vanadium from fractional oil of crude oil, this method required equipment is simple, easy to operate.
The present invention removes the processing method of nickel vanadium from fractional oil of crude oil, it is characterized in that: the metal remover that adds 100～1000ppm in the fractional oil of crude oil, be to react 20min～300min under 200～400 ℃ the condition in temperature, be cooled to 100～150 ℃ then, be preferably 100～140 ℃, adding and to account for the water of crude oil fraction weight of oil 1～10% and the emulsion splitter of 10～100ppm, is to separate under the condition of 200～1500V/cm in strength of electric field, removes the nickel vanadium.
Among the present invention, the adding of metal remover is a successive.In fraction oil, add metal remover, can make nickel vanadium porphyrin and non-porphyrin oil-soluble compounds in the fraction oil be converted into hydrophilic compound, add water, added electric field separation again, the nickel vanadium is removed.
Metal remover of the present invention is optional from phosphorous organism, and as HMPA etc., this HMPA is a colourless transparent liquid, density 1.021g/cm3 (60 ℃), 230～232 ℃ of boiling points, 2～7 ℃ at zero pour, specific refractory power 1.4572.Water soluble, polarity and non-polar solvent, inflammable, low toxicity.
The present invention is applicable to normal post-decompression residual oil, to different fraction oil, only needs according to the fraction oil properties, and suitably the adjusting process condition gets final product.Utilize the present invention that fraction oil is carried out the nickel vanadium and remove, compare with existing technology, its a whole set of technology required equipment is simple, easy to operate, and the total decreasing ratio of nickel vanadium can reach 70%.
Accompanying drawing and description of drawings
Fig. 1 is a crude oil fractions oil nickel removal vanadium process schematic representation, and this figure does not limit the present invention.
As shown in Figure 1, the metal remover HMPA 2 that adds 100～1000ppm in the stock oil 1, enter reactor 4, under 200～400 ℃ temperature, react, reaction times is 20min～300min, be cooled to 100～150 ℃ then, add and account for the water of crude oil fraction weight of oil 1～10% and the emulsion splitter 3 of 10～100ppm, in strength of electric field is under the condition of 200～1500V/cm, carrying out secondary in separator 5 and 6 separates, the stock oil 7 that removes behind nickel vanadium and the water goes out device, and sewage 8 to waste disposal plant is handled.
Embodiment
Arabic light oil residual oil (laboratory experiment)
Experimental technique: take by weighing 50g stock oil, put into the 100ml band and stir there-necked flask, splash into metal remover, metal remover is 1: 3000 with the ratio of stock oil, logical nitrogen-sealed, heated and stirred reaction, 300 ℃ of temperature of reaction, reaction times 60min, the reaction postcooling takes out about 20g, add stainless steel tube, 120 ℃ of constant temperature add water, emulsion splitter thorough mixing, and added electric field separates, and get oil phase and analyze metal content.Gained result such as following table 1.
The Arabic light oil residual oil of table 1 experimental result
Embodiment 2 domestic residual oil (industry test) residual oil flow: 1m
3/ h 3m
3/ h (maximum) the desalination water yield: 0.1m
3/ h 0.2m
3/ h (maximum) residue oil temperature: 300 ℃ of metal remover consumptions: the 500ppm technical process is a retort series connection secondary electrical desalter.Gained result such as table 2
| Embodiment | Before taking off (ppm) | Take off back (ppm) | The total decreasing ratio of Ni+V (%) | ||
| ?Ni | ?V | ?Ni | ?V | ||
| ?1a | ?11.5 | ?13.3 | ?5.4 | ?2.0 | 70.2 |
The domestic residual oil pilot-scale experiment of table 2
| Embodiment | Before taking off (ppm) | Take off back (ppm) | The total decreasing ratio of Ni+V (%) | ||
| Ni | ?V | ?Ni | ?V | ||
| ?2a | 7.5 | ?13.9 | ?3.6 | ?2.6 | 71.1 |
Claims (2)
1. processing method that from fractional oil of crude oil, removes the nickel vanadium, it is characterized in that: the metal remover that adds 100～1000ppm in the fractional oil of crude oil continuously, be to react 20min～300min under 200～400 ℃ the condition in temperature, be cooled to 100～150 ℃ then, add and account for the water of crude oil fraction weight of oil 1～10% and the emulsion splitter of 10～100ppm, be to separate under the condition of 200～1500V/cm in strength of electric field, remove the nickel vanadium, described metal remover is a HMPA.
2. by the described processing method that removes the nickel vanadium of claim 1, it is characterized in that: described cooling temperature is 100～140 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011382120A CN1140610C (en) | 2001-11-22 | 2001-11-22 | Process for removing Ni and V from fractional oil of crude oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011382120A CN1140610C (en) | 2001-11-22 | 2001-11-22 | Process for removing Ni and V from fractional oil of crude oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1356376A CN1356376A (en) | 2002-07-03 |
| CN1140610C true CN1140610C (en) | 2004-03-03 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011382120A Expired - Fee Related CN1140610C (en) | 2001-11-22 | 2001-11-22 | Process for removing Ni and V from fractional oil of crude oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1140610C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101402878B (en) * | 2008-11-14 | 2012-11-14 | 华东理工大学 | Method for removing nickel vanadium in crude oil with microwave chemical method |
| CN103146421B (en) * | 2011-12-07 | 2016-03-16 | 中国石油化工股份有限公司 | A kind of crude oil process for demetalizating |
| CN115612520B (en) * | 2021-07-13 | 2024-03-12 | 中国石油化工股份有限公司 | Method for removing metal in heavy oil |
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2001
- 2001-11-22 CN CNB011382120A patent/CN1140610C/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN1356376A (en) | 2002-07-03 |
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Granted publication date: 20040303 Termination date: 20111122 |