CN100532508C - Modifying technique for sulfur-containing fuel oil - Google Patents
Modifying technique for sulfur-containing fuel oil Download PDFInfo
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- CN100532508C CN100532508C CNB2007101072897A CN200710107289A CN100532508C CN 100532508 C CN100532508 C CN 100532508C CN B2007101072897 A CNB2007101072897 A CN B2007101072897A CN 200710107289 A CN200710107289 A CN 200710107289A CN 100532508 C CN100532508 C CN 100532508C
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Abstract
The invention discloses a reforming process for cycloparaffin and intermediate base containing sulfur fuel oil. The process applies the hydro thermal cracker, coke suppressing additive agent and hydrogen donor, wherein the hydrogen donor is provided by material oil own fractions at 360-450 DEG C. The hydro thermal cracker is back mixing, has an even reacting temperature and a simple structure. The process can produce the light fuel oil containing low sulfur, and obtains light fraction oil of 50-70 wt% under the medium harsh condition. The process combines with the coking process to produce light oil fraction with a high yield and largely reduce green coke amount and gas generation. The produced light fraction oil can be processed into naphth and diesel oil products and can be as the material for producing chemical products.
Description
Technical field:
The present invention relates to a kind of refining of petroleum technology, especially to the method for modifying of sulfurous fuels oil.
Background technology:
Sulfurous fuels oil uses mainly as boiler oil or other industrial fuel, because its sulphur content can cause environmental pollution during than high combustion.In addition, oil fuel also can be used as the oil lighting end of the charging of coking process with the acquisition some amount, but because the coke and the dry gas yied of this technology are higher, and liquid yield and benzoline yield are subjected to certain limitation.So far still unmatchful sulfurous fuels oil carries out the technology of upgrading.
Summary of the invention:
The objective of the invention is to provide a kind of processing method of sulfurous fuels oil upgrading, can under mitigation thermally splitting condition, can produce the low-sulfur light-weight fuel oil, under medium severe condition, can generate a considerable amount of light ends oil, with the condition of coking process combination under, compare and to increase substantially light oil yield with carrying out coking process separately, reduce coke yield and gas recovery ratio.
The object of the present invention is achieved like this, is raw material with cycloalkanes, intermediate base sulfurous fuels oil, adopts at the hydrogen supply agent that presses down in the presence of the burnt additive and face the hydrogen thermocracking process.Pressing down burnt additive is the mixture or the water-soluble microemulsion of various oil soluble organometallic compounds, and hydrogen supply agent is self contained component with hydrogen supply capacity in 360～450 ℃ of cuts that produce in the thermal cracking process.The temperature of reaction is 380～450 ℃, and the hydrogen dividing potential drop of reaction is 4～10Mpa, raw material air speed 0.5～1.5h
-1
The present invention adopts hydrogen supply agent to face the hydrogen thermocracking process, and adopts and efficiently to press down burnt additive and because under the acting in conjunction of hydrogen pressure, hydrogen supply agent, thereby has suppressed burnt growing amount significantly.In cycloalkanes, intermediate base sulfurous fuels oil and 360～450 ℃ of products of pyrolysated thereof, contain a considerable amount of components with hydrogen supply capacity, the homologue of naphthane, dihydroanthracene, dihydro phenanthrene, octahydro phenanthrene, octahydro anthracene etc. for example, thereby these components can provide the effect that the hydrogen atom of some amount plays hydrogenation under the thermolysis condition, under the acting in conjunction of hydrogen pressure, coke inhibitor, its hydrogenation better effects if has improved light oil yield and because the saturation of the hydrogen atom that hydrogen supply agent provided has suppressed the generation of coke greatly.
Description of drawings:
Fig. 1 is the full scale plant principle flow chart according to quality modifying technique for sulfur-containing fuel oil provided by the present invention.
Embodiment:
Describe the present invention in detail below in conjunction with drawings and Examples, but embodiment should not limit the scope of the invention.
Experiment shows, at cycloalkanes, in 360～450 ℃ of products of intermediate base sulfurous fuels oil and pyrolysated thereof, contain a considerable amount of components with hydrogen supply capacity, naphthane for example, dihydroanthracene, the dihydro phenanthrene, the octahydro phenanthrene, the homologue of octahydro anthracene etc., thereby these components can provide the effect that the hydrogen atom of some amount plays hydrogenation under the thermolysis condition, at hydrogen pressure, coke inhibitor exists down, with 360～450 ℃ of cuts that generate in thermal response cracking that circulates, not only improve light oil yield but also because the saturation of the hydrogen atom that hydrogen supply agent provided has suppressed the generation of coke greatly.Experimental data confirms (seeing Table 1), and under same reaction conditions, the present invention compares with other thermocracking process under same coking yield (1.5wt%), and its lighting end yield will improve 10～30wt%.The tail oil that technology of the present invention generated still can be used as the charging of coking process.After technology of the present invention and the coking process combination, compare with carrying out coking process separately, total green coke amount reduces by 5～7wt%, and gas yield reduces by 3～5wt%, and liquid yield increases by 8～11wt%, and the light oil distillate yield increases considerably (seeing Table 2):
Table 1 triumph oil fuel is lighting end yield under the 1.5wt% at coking yield under same reaction conditions
| Technology type | The heavy % of lighting end yield |
| Conventional viscosity breaking hydrovisbreaking cracking hydrogen supply agent viscosity breaking technology of the present invention | 26.8 30.6 44.3 56.8 |
Table 2 triumph heavy fuel oil (HFO) adopts the result of two kinds of hot-work schemes to compare
As shown in Figure 1, the hydrogen supply agent of flow process of the present invention with full back-mixing formula faces system's characteristics such as hydrogen thermal cracking reactor and product separation.Cycloalkanes, intermediate base sulfurous fuels oil adds and presses down burnt additive and mix to mix with hydrogen partial or whole hydrogen with 360～450 ℃ of distillates that contain hydrogen donor component again and be pumped to No. 1 process furnace of oil fuel, after being heated to 380～450 ℃, enter the middle and upper part of facing hydrogen thermal cracking reactor K-1.Another road hydrogen is delivered to No. 2 process furnace (if all hydrogen advance No. 1 process furnace process furnace of then can stopping using No. 2) and also is heated to and enters the bottom of facing hydrogen thermal cracking reactor K-1 after 380～450 ℃, the gaseous stream that reactor K-1 comes out at the top separates through overheated high score K-2, its gas phase part enters cold high score K-3 through cooling, liquid phase stream and cracking case bottoms are mixed into flash tank K-4, flash tank K-4 overhead stream with enter atmospheric distillation tower K-5 after cold low minute K-8 bottoms mixed, flash tank K-4 bottoms enters vacuum fractionation tower K-6, the logistics of vacuum fractionation top of tower enters separator K-7, vacuum distillation tower K-6 bottom capable of circulation time cracking case of tail oil or deliver to coker.360～450 ℃ of cuts that vacuum fractionation tower side line contains the hydrogen supply agent component and the cracking that circulates again after oil fuel mixes.The gasoline of atmospheric fractional tower K-5 side line and diesel oil distillate are delivered to hydro-refining unit to obtain high quality vapour, diesel product.
Technology proposed by the invention is compared difference with other technology and is:
(1) this technology is added specific oil soluble or water-soluble microemulsion presses down burnt additive (additive is made up of the mixture or the water-soluble microemulsion of various oil soluble organometallic compounds) in reaction.These press down burnt additive has basic difference with the boiler tube coke inhibitor that furnace tubing is at present adopted, this technology to press down burnt additive mainly be the generation that is suppressed at coke in the reactor.
(2) another characteristics of this technology are, the raw material that this technology adopted is sulfur-bearing cycloalkanes, the intermediate base oil fuel that is rich in the hydrogen supply agent component.The oil fuel that this technology is not suitable for the low-sulfur paraffinic base is raw material.
(3) this technology is at hydrogen pressure and press down in the presence of the burnt additive, to reacting 360～450 ℃ of cuts that are rich in hydrogen supply agent that then the generated cracking that circulates.Because cracking under hydrogen pressure, coke inhibitor, this three's of hydrogen supply agent component acting in conjunction, thereby the generation of coke in the inhibited reaction significantly, thereby improved the yield of light oil.
(4) this technology (380～410 ℃ of temperature of reaction) under the mitigation condition transforms, and can produce the low-sulfur light-weight fuel oil; Transform down at medium severity (410～450 ℃ of temperature of reaction), can obtain 50～70wt% light ends oil; If this technology and coking process combination will reduce coke and gas yield significantly, improve liquid yield and light oil yield.
(5) the light ends oil produced of this technology both can further be processed into the raw material that petroleum naphtha and diesel product also can be used as the production chemical product.
(6) key distinction such as the table 3 of this technology and other heavy oil heat processing technique:
The difference of table 3 technology of the present invention and other heat processing technique of heavy oil
Embodiment: Middle East sulphur heavy oil fuel is on the pilot plant of laboratory, and the reaction conditions that is adopted is: 380～450 ℃ of temperature of reaction, hydrogen dividing potential drop 4～10Mpa, total raw material air speed 1.0～1.5h
-1, fresh feed air speed 0.4～0.8h
-1Its reaction result such as table 4:
Table 4 Middle East sulfur-bearing cycloalkyl heavy fuel oil (HFO) faces the hydrogen heat cracking reaction under coke inhibitor, hydrogen supply agent
Beneficial effect of the present invention is:
1. because the present invention adopts and efficient presses down burnt additive and because under the acting in conjunction of hydrogen pressure, hydrogen supply agent, thereby significantly suppressed burnt growing amount. The present invention compares with other thermal conversion process, and under identical coking yield (1.5 wt%), its light distillate yield increases by 10～30wt%.
2. because the used raw material of the present invention is cycloalkanes, intermediate base sulfurous fuels oil, its 360～450 ℃ of cuts are rich in hydrogen supply agent, this distillate circulation cracking both can obtain in a large number＜360 ℃ light fraction, can provide hydrogen donor component again, thereby it has saved the hydrogen supply agent cost greatly than the cracking technique that adds hydrogen supply agent.
3. the present invention can produce the low-sulfur light-weight fuel oil under mitigation condition; The yield that can obtain light component (＜360 ℃) under medium reaction severity is 50～70wt%; If the present invention and coking process combination then can reduce coke production rate 5～7wt%, reduce cooking gas productive rate 3～5wt%, thereby increase substantially the liquid yield of coking.
4. the benzoline that the present invention generated both can be processed into the raw material that petroleum naphtha and diesel product also can be used as the production chemical product.
5. compare with present heavy oil hydrogenation process, reaction pressure of the present invention is low, and (the plant construction cost of investment is low for hydrogen dividing potential drop 4～10Mpa), technical process simple (only needing a reactor).
Claims (3)
1. the modifying process of a sulfurous fuels oil, the hydrogen thermal cracking reactor is faced in employing, pressing down in the presence of burnt additive and the hydrogen supply agent, 380～450 ℃ of control reaction temperature, wherein pressing down burnt additive is the mixture or the water-soluble microemulsion of various oil soluble organometallic compounds, it is characterized in that this technological process is to be raw material, to face hydrogen heat cracking reaction technological process under hydrogen supply agent with cycloalkanes, intermediate base sulfurous fuels oil, the hydrogen dividing potential drop that hydrogen supply agent faces hydrogen heat cracking reaction system is 4～10MPa, gross space speed 1.0～1.5h
-1, fresh feed air speed 0.4～0.8h
-1
2. the modifying process of sulfurous fuels oil according to claim 1 is characterized in that hydrogen supply agent is provided by 360～450 ℃ of cuts of raw material self and thermal decomposition product thereof.
3. the modifying process of sulfurous fuels oil according to claim 1 is characterized in that but the consumption of burnt additive is 50～1000ppm.
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| CNB2007101072897A CN100532508C (en) | 2007-05-28 | 2007-05-28 | Modifying technique for sulfur-containing fuel oil |
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| CNB2007101072897A CN100532508C (en) | 2007-05-28 | 2007-05-28 | Modifying technique for sulfur-containing fuel oil |
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| CN100532508C true CN100532508C (en) | 2009-08-26 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101899324B (en) * | 2009-05-27 | 2013-06-05 | 中国石油化工股份有限公司 | Catalytic conversion method for producing light diesel oil with high hexadecane value and low olefin gasoline |
| CN102504862B (en) * | 2011-11-18 | 2014-04-02 | 中国石油天然气股份有限公司 | Hydrogen-donating thermal cracking method |
| CN104164255A (en) * | 2013-05-20 | 2014-11-26 | 中国石油大学(华东) | Inferior heavy oil hydro-thermal cracking and tail oil decarbonization composite process and device |
| CN105647554B (en) * | 2014-12-04 | 2018-08-14 | 中国石油化工股份有限公司 | A kind of dry distillation of coal and coal tar distillation combined technical method |
| CN111004644A (en) * | 2019-12-16 | 2020-04-14 | 冯炳焕 | Efficient and environment-friendly oil refining method |
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Non-Patent Citations (2)
| Title |
|---|
| 催化剂和供氢剂及其前身物对二苯甲烷裂化反应的影响. 石斌，丁军委，王继乾，阙国和.石油大学学报，第28卷第2期. 2004 |
| 催化剂和供氢剂及其前身物对二苯甲烷裂化反应的影响. 石斌，丁军委，王继乾，阙国和.石油大学学报，第28卷第2期. 2004 * |
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Assignee: Shandong Jiangshan Polymer Material Co., Ltd. Assignor: China Petroleum University (East China) Contract record no.: 2010370000590 Denomination of invention: Quality modifying technique for sulfur-containing fuel oil Granted publication date: 20090826 License type: Exclusive License Open date: 20071017 Record date: 20101217 |
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