CN102703118A - Preparation method of diesel - Google Patents
Preparation method of diesel Download PDFInfo
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- CN102703118A CN102703118A CN2012101823844A CN201210182384A CN102703118A CN 102703118 A CN102703118 A CN 102703118A CN 2012101823844 A CN2012101823844 A CN 2012101823844A CN 201210182384 A CN201210182384 A CN 201210182384A CN 102703118 A CN102703118 A CN 102703118A
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Abstract
The invention provides a preparation method of diesel. The preparation method comprises the following steps: hydrogenating diesel materials under the catalysis of a catalyst in a hydrogen atmosphere; carrying out oil-gas separation on products of the hydrogenation reaction by a high-temperature high-pressure separator to obtain high-temperature high-pressure separated gas and high-temperature high-pressure separated liquid; adding deionized water to the high-temperature high-pressure separated gas and then carrying out water-oil-gas separation in a low-temperature high-pressure separator to obtain low-temperature high-pressure separated light oil, low-temperature high-pressure separated water phase and low-temperature high-pressure separated gas phase; separating heavy distillate oil out of the high-temperature high-pressure separated liquid in a high-temperature low-pressure separator; carrying out debutanization on the low-temperature high-pressure separated light oil and the heavy distillate oil to obtain primary diesel; and carrying out the above operation steps twice or more than twice on the primary diesel serving as a diesel material. According to the technical scheme, the hydrofining process is carried out several times, hydrogenated products such as hydrothion and ammonia are all separated out in each hydrofining operation, and therefore the hydrofining effect is improved.
Description
Technical field
The present invention relates to the diesel oil preparation field, in particular to a kind of preparation method of diesel oil.
Background technology
Washing oil is that the coal tar boiling range is 230-300 ℃ a cut, and its productive rate is the 4.5%-5.5% of anhydrous tar, and main ingredient has methylnaphthalene, dimethylnaphthalene, acenaphthene, biphenyl, fluorenes, dibenzofuran, methyl fluorenes, quinoline, indoles and high boiling point phenol etc.Washing oil is mainly used in and absorbs contained benzene and the homologue of coke-oven gas, and also further rectifying cuts narrow fraction, to extract products such as methylnaphthalene, indoles, biphenyl, acenaphthene, dibenzofuran and fluorenes.Deep processing and utilization to washing oil concentrates in the processing extraction to its staple mostly at present, and is remaining then with low value-added product form inflow fuel oil market.
Carbolineum is that the coal tar boiling range is 280 ~ 360 ℃ a cut, and chemical constitution is the aromatic hydrocarbons and a little colloid group more than 90%, and main constituent has anthracene, phenanthrene, fluorenes, acenaphthene, carbazole.The at present domestic thick product such as carbon black raw oil oil fuel and mixing asphalt oil or separation and Extraction naphthalene, anthracene, acenaphthene, phenanthrene, carbazole that mainly is used as; Product purity is low, energy consumption is high, value-added content of product is little but these methods exist; Shortcomings such as deficiency in economic performance; When resource is caused significant wastage, environment is caused severe contamination.
At present domestic diesel oil market is but increasing the demand of diesel oil day by day, but more and more shortage and nervous of petroleum resources, price rises steadily, and concentrates on the hydrotreatment aspect of coal tar both at home and abroad mostly for the refining of coal-tar type diesel.LURGI adopts hydrogenation modifying process that coal tar is carried out deep processing and handles, and has improved the quality of oil product greatly, makes it reach the vehicle fuel oil standard.The coal tar hydrogenation modification technology of Chang Ling petrochemical industry scientific and technological development ltd exploitation, Xie Huachang realized industriallization in Yunnan in 1997, produced qualified vapour, diesel oil.There is the complete processing more complicated in above-mentioned coal tar hydrogenating technology, long flow path, defectives such as tooling cost height.
Chinese patent CN101486926A discloses the method for a kind of washing oil hydrogenation preparing gasoline and diesel oil on July 22nd, 2009.The boiling range scope of washing oil is 230-300 ℃, and after unifining and hydro-upgrading, the doing all less than 300 ℃ of diesel product makes to lack the component greater than 300 ℃ in the diesel product, influences the use properties of diesel oil.In addition; This patent hydrogenation reaction is carried out in the hydrogenator of 1-6 arranged in series setting; Hydrogenation products such as hydrogen sulfide that the front reaction device produces and ammonia can influence the hydrogenation reaction in the reactor drum of rear end; Be that hydrogen sulfide has restraining effect to hydrodesulfurization reaction, ammonia is because there is negative impact in competitive adsorption to follow-up hydrogenation desulfurization removing nitric, alkene and aromatic hydrogenation saturated reaction, and ammonia has serious restraining effect to the acid sites of hydrocracking reaction catalyzer.In addition; This patent hydrogenation reaction is carried out in the hydrogenator of 1-6 arranged in series setting; Hydrogenation products such as hydrogen sulfide that the front reaction device produces and ammonia can influence the hydrogenation reaction in the reactor drum of rear end; Be that hydrogen sulfide has restraining effect to hydrodesulfurization reaction, ammonia is because there is negative impact in competitive adsorption to follow-up hydrogenation desulfurization removing nitric, alkene and aromatic hydrogenation saturated reaction.
Summary of the invention
The present invention aims to provide a kind of preparation method of diesel oil, to solve the technical problem that the unifining effect is influenced by hydrogen sulfide and ammonia in the prior art.
To achieve these goals, according to an aspect of the present invention, a kind of preparation method of diesel oil is provided.This method may further comprise the steps: under hydrogen atmosphere, diesel raw material is carried out hydrogenation reaction under the catalysis of catalyzer; Hydrogenation reaction product is carried out gas-oil separation through high-temperature high-pressure separator, obtain HTHP divided gas flow and HTHP separating liquid; Carry out the water, oil, gas separation with sending into the cryogenic high pressure separator behind the HTHP divided gas flow injection deionized water, obtain cryogenic high pressure separation of lighter oil, cryogenic high pressure water phase separated and cryogenic high pressure and separate gas phase; The HTHP separating liquid is sent into the high-temperature low-pressure separator separates go out heavy distillate; Cryogenic high pressure separation of lighter oil and heavy distillate are carried out the debutylize processing obtain elementary diesel oil; Elementary diesel oil is repeated aforesaid operations step 2 time as diesel raw material or more than 2 times.
Further, elementary diesel oil is repeated aforesaid operations step 2-3 time as diesel raw material.
Further, diesel raw material is mixed according to mass ratio 20:80-80:20 by washing oil, carbolineum and is obtained.
Further, the boiling range of diesel raw material is 180-500 ℃, and density is 1.01-1.15g/cm
3
Further, the boiling range of diesel raw material is 200-420 ℃, and density is 1.01-1.10g/cm
3
Further, the condition of hydrogenation reaction is: temperature of reaction 300-420 ℃, and reaction pressure 8-15MPa, hydrogen to oil volume ratio 300-2000, volume space velocity 0.5-2.5h
-1
Further, the condition of hydrogenation reaction is: temperature of reaction 320-400 ℃, and reaction pressure 12-15MPa, hydrogen to oil volume ratio 500-1000, volume space velocity 0.5-2.0h
-1
Further, hydrogenation reaction comprises repeatedly hydrofining reaction, and hydrofining reaction comprises the step that makes diesel raw material under hydrogen atmosphere, pass through protective material and unifining agent successively.
Further, protective material comprises that the quality percentage composition is the MoO of 6.0%-8.0%
3, the NiO of 1.0%-2.0%, and the carrier of surplus, the unifining agent comprises that the quality percentage composition is the MoO of 16%-20%
3, the WO of 25%-28%
3, the NiO of 3.0%-6.0%, the P of 3.0%-6.0%
2O
5, and the carrier of surplus.
Further, in hydrofining reaction, make diesel raw material under hydrogen atmosphere, pass through successively between the step of protective material and unifining agent, further comprise step through metal remover.
Use technical scheme of the present invention, adopt the multipass hydrogen refining process, and each is divided equally all over unifining and leaves away except that hydrogenation products such as hydrogen sulfide, ammonia.Because hydrogen sulfide has restraining effect to hydrodesulfurization reaction; Ammonia is because there is negative impact in competitive adsorption to follow-up hydrogenation desulfurization removing nitric, alkene and aromatic hydrogenation saturated reaction; Leave away except that hydrogenation products such as hydrogen sulfide, ammonia so each is divided equally all over unifining, improved the unifining effect.In addition, compare, adopt the multipass hydrogen refining process can improve diesel yield with hydrogenation modifying process.
Description of drawings
Figure of description is used to provide further understanding of the present invention, constitutes a part of the present invention, and illustrative examples of the present invention and explanation thereof are used to explain the present invention, does not constitute improper qualification of the present invention.In the accompanying drawings:
Fig. 1 shows the process flow sheet of the diesel preparation method of one exemplary embodiments according to the present invention.
Embodiment
Need to prove that under the situation of not conflicting, embodiment and the characteristic among the embodiment among the present invention can make up each other.Below with reference to accompanying drawing and combine embodiment to specify the present invention.
A kind of typical embodiment according to the present invention provides a kind of preparation method of diesel oil.This method may further comprise the steps: under hydrogen atmosphere, diesel raw material is carried out hydrogenation reaction under the catalysis of catalyzer; Hydrogenation reaction product is carried out gas-oil separation through high-temperature high-pressure separator, obtain HTHP divided gas flow and HTHP separating liquid; Carry out the water, oil, gas separation with sending into the cryogenic high pressure separator behind the HTHP divided gas flow injection deionized water, obtain cryogenic high pressure separation of lighter oil, cryogenic high pressure water phase separated and cryogenic high pressure and separate gas phase; The HTHP separating liquid is sent into the high-temperature low-pressure separator separates go out heavy distillate; Cryogenic high pressure separation of lighter oil and heavy distillate are carried out the debutylize processing obtain elementary diesel oil; Elementary diesel oil is repeated aforesaid operations step 2 time as diesel raw material or more than 2 times.Use technical scheme of the present invention, adopt the multipass hydrogen refining process, and each is divided equally all over unifining and leaves away except that hydrogenation products such as hydrogen sulfide, ammonia.Because hydrogen sulfide has restraining effect to hydrodesulfurization reaction; Ammonia is because there is negative impact in competitive adsorption to follow-up hydrogenation desulfurization removing nitric, alkene and aromatic hydrogenation saturated reaction; Leave away except that hydrogenation products such as hydrogen sulfide, ammonia so each is divided equally all over unifining, improved the unifining effect.
Comprehensive production cost and quality product consider that preferably, elementary diesel oil repeats aforesaid operations step 2-3 time as diesel raw material.
A kind of typical embodiment according to the present invention, diesel raw material are mixed according to mass ratio 20:80-80:20 by washing oil, carbolineum and are obtained.The present invention adopts washing oil, the carbolineum raw material as diesel oil, compares with using petroleum fractions in the prior art, and cost of material of the present invention is cheap, and has solved the problem that washing oil, both independent converted products boiling ranges of carbolineum are difficult for meeting the demands.In addition, method clean utilization of the present invention washing oil, carbolineum, improved washing oil, anthracene oil product added value.
The boiling range scope of washing oil is 230-300 ℃, after unifining, and the doing of diesel product all less than 300 ℃; Make and lack component in the diesel product greater than 300 ℃; Influence the use properties of diesel oil, therefore, in washing oil, add carbolineum and just can address this problem as diesel raw material.But in order to improve the use properties of prepared diesel oil, mix according to mass ratio 20:80-80:20 on the diesel raw material basis that obtains at washing oil, carbolineum, preferably, the boiling range of diesel raw material is 180-500 ℃, and density is 1.01-1.15g/cm
3, further preferably, the boiling range of diesel raw material is 200-420 ℃, density is 1.01-1.10g/cm
3Because the boiling range of this boiling range scope and diesel oil is more approaching, be more conducive to the production of fine-quality diesel oil.
Preferably, the method for preparing diesel oil of the present invention further comprises: cryogenic high pressure separator separates water is sent into waste water tank; And cryogenic high pressure is separated gas phase measure back emptying.Above-mentioned cryogenic high pressure separator separates water can get into follow-up wastewater treatment program.
A kind of typical embodiment according to the present invention, the condition of hydrogenation reaction is: temperature of reaction 300-420 ℃, reaction pressure 8-15MPa, hydrogen to oil volume ratio 300-2000, volume space velocity 0.5-2.5h
-1Under this reaction conditions, being convenient to catalytic hydrogenation reaction carries out more fully.Preferably, the condition of hydrogenation reaction is: temperature of reaction 320-400 ℃, and reaction pressure 12-15MPa, hydrogen to oil volume ratio 500-1000, volume space velocity 0.5-2.0h
-1
A kind of typical embodiment according to the present invention; Hydrogenation reaction comprises repeatedly hydrofining reaction successively; Hydrofining reaction comprises the step that makes diesel raw material under hydrogen atmosphere, pass through protective material and unifining agent successively; Each all separates removal with hydrogenation products such as hydrogen sulfide and ammonia all over unifining process, the influence of having avoided hydrogen sulfide and ammonia that follow-up hydrogenation is reacted.
Preferably, protective material comprises that the quality percentage composition is the MoO of 6.0%-8.0%
3, the NiO of 1.0%-2.0%, and the carrier of surplus, the unifining agent comprises that the quality percentage composition is the MoO of 16%-20%
3, the WO of 25%-28%
3, the NiO of 3.0%-6.0%, the P of 3.0%-6.0%
2O
5, and the carrier of surplus.
Metal content is higher in diesel raw material, or protective material is not when having the demetalization function, and diesel raw material is passed through protective material, metal remover and unifining agent successively under hydrogen atmosphere.
In the hydrofining reaction; Load partial protection agent and metal remover earlier at the first reactor inlet place; Slow down reactor head and cause local very exothermic because of the quick hydrogenation saturated reaction of alkene; And coking precursor such as colloid meets hot green coke and causes the catalyzer coking and reduce the deposition of metal at the Primary Catalysts bed, helps the carrying out of subsequent reactions.
To combine specific embodiment to further specify beneficial effect of the present invention below.
Embodiment 1-4
The concrete parameter of embodiment 1-4 is referring to table 1-3; Wherein, Table 1 is the component and the relevant nature (adopting Ma'an Mountain's coal tar wash oil, carbolineum is raw material) of diesel raw material; Table 2 is formed for alumina base catalyst, and table 3 is produced the processing condition of diesel oil and the diesel product character that obtains for adopting hydrogen refining process.
Technical process is as shown in Figure 1; Washing oil, the carbolineum mixed in the ratio shown in the table 1 add in the material tank as diesel raw material; Diesel raw material is mixed into first reactor drum (unifining) through raw oil pump metering back with hydrogen (warp measures); First reactor effluent gets into second reactor drum (unifining); Second reactor effluent gets into high-temperature high-pressure separator (being called for short hot high score) and carries out oil, gas separation, and the HTHP divided gas flow after the separation injects deionized water (preventing the ammonium salt blocking pipeline) back and gets into cryogenic high pressure separator (being called for short cold high score), carries out water, oil, gas and separates.The clean cargo that the cryogenic high pressure separator separates goes out directly get into debutanizing tower.The isolated cryogenic high pressure water phase separated in cryogenic high pressure separator bottom gets into waste water tank, and the cryogenic high pressure that comes out in cryogenic high pressure separator top separates gas phase emptying after metering.The isolated HTHP separating liquid in high-temperature high-pressure separator bottom gets into the high-temperature low-pressure separator separates and goes out heavy distillate; This heavy distillate gets into debutanizing tower; Cat head separates gas phase metering back emptying; Oil gets into the product jar and obtains elementary diesel oil at the bottom of the tower, and this elementary diesel oil repeats aforesaid operations one time again as diesel raw material, obtains diesel oil.
Table 1
Table 2
Table 3
Visible by table 3, raw material through twice unifining after, product oil yield reaches more than 99%, boiling range is between 110-370 ℃; Sulphur content is less than 10ppm, and nitrogen content is less than 2ppm, and condensation point is lower than-50 ℃; Cold filter clogging temperature is lower than-40 ℃, and cetane value belongs to high-grade low-freezing clean diesel component more than 30.
The above is merely the preferred embodiments of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.All within spirit of the present invention and principle, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the preparation method of a diesel oil is characterized in that, may further comprise the steps:
Under hydrogen atmosphere, diesel raw material is carried out hydrogenation reaction under the catalysis of catalyzer;
Hydrogenation reaction product is carried out gas-oil separation through high-temperature high-pressure separator, obtain HTHP divided gas flow and HTHP separating liquid;
Carry out the water, oil, gas separation with sending into the cryogenic high pressure separator behind the said HTHP divided gas flow injection deionized water, obtain cryogenic high pressure separation of lighter oil, cryogenic high pressure water phase separated and cryogenic high pressure and separate gas phase;
Said HTHP separating liquid is sent into the high-temperature low-pressure separator separates go out heavy distillate;
Said cryogenic high pressure separation of lighter oil and heavy distillate are carried out the debutylize processing obtain elementary diesel oil;
Said elementary diesel oil is repeated aforesaid operations step 2 time as diesel raw material or more than 2 times.
2. method according to claim 1 is characterized in that, said elementary diesel oil is repeated aforesaid operations step 2-3 time as diesel raw material.
3. method according to claim 1 is characterized in that, said diesel raw material is mixed according to mass ratio 20:80-80:20 by washing oil, carbolineum and obtained.
4. method according to claim 3 is characterized in that, the boiling range of said diesel raw material is 180-500 ℃, and density is 1.01-1.15g/cm
3
5. method according to claim 4 is characterized in that, the boiling range of said diesel raw material is 200-420 ℃, and density is 1.01-1.10g/cm
3
6. method according to claim 1 is characterized in that, the condition of said hydrogenation reaction is: temperature of reaction 300-420 ℃, and reaction pressure 8-15MPa, hydrogen to oil volume ratio 300-2000, volume space velocity 0.5-2.5h
-1
7. method according to claim 6 is characterized in that, the condition of said hydrogenation reaction is: temperature of reaction 320-400 ℃, and reaction pressure 12-15MPa, hydrogen to oil volume ratio 500-1000, volume space velocity 0.5-2.0h
-1
8. method according to claim 6 is characterized in that said hydrogenation reaction comprises repeatedly hydrofining reaction, and said hydrofining reaction comprises the step that makes said diesel raw material under hydrogen atmosphere, pass through protective material and unifining agent successively.
9. method according to claim 8 is characterized in that, said protective material comprises that the quality percentage composition is the MoO of 6.0%-8.0%
3, the NiO of 1.0%-2.0%, and the carrier of surplus, said unifining agent comprises that the quality percentage composition is the MoO of 16%-20%
3, the WO of 25%-28%
3, the NiO of 3.0%-6.0%, the P of 3.0%-6.0%
2O
5, and the carrier of surplus.
10. method according to claim 8 is characterized in that, in said hydrofining reaction, makes said diesel raw material under hydrogen atmosphere, pass through successively between the step of said protective material and unifining agent, further comprises the step through metal remover.
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105295998A (en) * | 2014-07-25 | 2016-02-03 | 中国石油化工股份有限公司 | Method for producing small-molecule aromatics from diesel oil raw material |
CN105586087A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Hydrocracking method |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102041073A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Hydrocracking method for anthracene oil |
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2012
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Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102041073A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Hydrocracking method for anthracene oil |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105295998A (en) * | 2014-07-25 | 2016-02-03 | 中国石油化工股份有限公司 | Method for producing small-molecule aromatics from diesel oil raw material |
CN105295998B (en) * | 2014-07-25 | 2017-08-25 | 中国石油化工股份有限公司 | A kind of method that small molecule aromatic hydrocarbons is produced by diesel raw material |
CN105586087A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Hydrocracking method |
CN105586087B (en) * | 2014-10-24 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of method being hydrocracked |
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