CN1233797C - Hydrogenating modifying process for direct liquefying diesel oil of coal - Google Patents
Hydrogenating modifying process for direct liquefying diesel oil of coal Download PDFInfo
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- CN1233797C CN1233797C CN 03134011 CN03134011A CN1233797C CN 1233797 C CN1233797 C CN 1233797C CN 03134011 CN03134011 CN 03134011 CN 03134011 A CN03134011 A CN 03134011A CN 1233797 C CN1233797 C CN 1233797C
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Abstract
The present invention discloses a hydrogenating modifying method for directly liquefying diesel oil by coal. A diesel oil fraction for coal liquification and hydrogen upstream contact on a catalyst under hydrofining conditions, the nitrogen content of a hydrofining liquid phase effluent is controlled to be 100 to 1000 mu g/g, the hydrofining liquid phase effluent and the hydrogen parallel flow to contact a hydrogenating conversting catalyst, and low cetane number arene is circularly opened into a high cetane number component. Meanwhile, esurfurizing reaction and denitrifying reaction further happen to obtain a modified diesel oil product with high quality. Compared with the prior art, the technology of the present invention has the advantages of high diesel oil yield, good quality of product diesel oil, low operating pressure, flexible operation, low hydrogen consumption, low equipment cost and operating cost, etc. The present invention is mainly used for the modified process of poor ignition quality fuel with high nitrogen contents.
Description
Technical field
The present invention relates to a kind of method for modifying of DCL/Direct coal liquefaction product, particularly produce the hydrogenation modification method of high quality clean fuel with the DCL/Direct coal liquefaction poor ignition quality fuel.
Background technology
DCL/Direct coal liquefaction is produced the industrial technology that liquid hydrocarbon technology is important alternative petroleum products.Coal through physical and chemical processes such as thermolysis, extraction heat and shortenings, can reduce the molecular weight of coal and derivative thereof significantly in the direct liquefaction process, change molecular structure, thereby significantly improve the H/C atomic ratio, remove heteroatomss such as S, N, O in a large number, obtain liquid product.But the quality of DCL/Direct coal liquefaction product is still very poor, needs further upgrading to use.The diesel oil distillate cetane value that obtains as DCL/Direct coal liquefaction is low especially, and other foreign matter content such as nitrogen content are high especially, and existent gum, acid number etc. are also very high, and general treatment process is difficult to satisfy existing diesel oil specification.The IGOR technology of Germany's exploitation is online refining with liquefied coal coil, and its diesel product that obtains can not satisfy the requirement of increasingly stringent environmental regulation because refining depth is low.
US4,447,312 with the hydrotreatment of the direct liquid oil content of coal distilled diesel oil distillate process, carries out alkylated reaction with alkene on the reactive resin an acidic catalyst then, obtains diesel product.Diesel oil distillate also can carry out alkylated reaction earlier, carries out hydrotreatment then.This method mainly exist technology complexity, diesel yield lower (about 85%), hydroprocessing condition comparatively harsh (air speed is low, the pressure height), therefore production cost is higher, and because alkylated reaction needs low-carbon alkene to participate in, has the source problem that comes of low-carbon alkene.
CN1382772A discloses a kind of method of producing diesel oil from liquefied coal coil, its process will be for carrying out high pressure (embodiment is 14MPa) hydro-upgrading through the diesel oil distillate and the tail oil cut of stable hydrogenation liquefied coal coil, and hydro-upgrading comprises the cascade reaction of hydrofining and hydrocracking.Its main deficiency is the reaction pressure height, and facility investment is big, the process cost height, and the hydrogen consumption is big, and cracking reaction is many, and diesel yield is low.In addition,, in hydrofining reaction, form a large amount of hydrogen sulfide and ammonia and enter hydrocracking reactor, influence the activity of hydrocracking catalyst because sulphur, nitrogen content in the raw material are very high.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of hydrogenation modifying process of gelatin liquefaction diesel oil, technology diesel yield height of the present invention, the product diesel quality is good, working pressure is low, flexible operation, hydrogen consumption is low, equipment and process cost are low.
The hydrogenation modifying process of gelatin liquefaction diesel oil of the present invention comprises: under the hydrofining condition, gelatin liquefaction diesel oil distillate and hydrogen counter current contact on catalyzer, the nitrogen content of control hydrofining liquid phase effluent is 100～1000 μ g/g, be preferably 200～600 μ g/g, the liquid phase effluent contacts with hydrogenation conversion catalyst with hydrogen and stream again, with low-cetane aromatic hydrocarbons open loop is the high hexadecane value component, and desulfurization and denitrification reaction further take place simultaneously, obtains high quality upgrading diesel product.
Compared with prior art, the characteristics that the inventive method is outstanding are to adopt the countercurrent hydrogenation process for refining, with the gelatin liquefaction diesel oil hydrofining, hydrogen sulfide and ammonia that reaction obtains do not enter the follow-up hydrogenation conversion reactor, and do not need to adopt two sections flow processs of the complexity that has middle separation system.In addition, nitrogen content by control hydrofining reaction effluent, reach the control hydroconversion reactions according to " the aromatic hydrocarbons open loop is high hexadecane value materials such as chain hydrocarbon or band side chain aromatic hydrocarbons; and further cracking reaction does not take place " reaction pattern carry out, promptly very high diesel yield can be obtained, the cetane value of product can be improved again greatly.Do not need to carry out reactions such as the desulfurization of the degree of depth, denitrogenation because countercurrent hydrogenation is refining, only need the sulphur in the raw material, nitrogen are partly removed, can reduce the severity of hydrofining reaction, improve treatment capacity, reduced facility investment and process cost.In addition, because hydrogenation conversion catalyst has hydrocon version functionality and hydrofining function simultaneously, though enter the material of hydroconversion reactions device impurity such as certain sulphur, nitrogen are arranged, but under the hydrogenating function effect of hydrogenation conversion catalyst, can further remove wherein sulphur, nitrogen, impurity in products content is lower, therefore, make full use of the various performances of hydrogenation conversion catalyst, also saved the consumption of front Hydrobon catalyst.The inventive method can be issued to the ideal effect at lower working pressure, and the hydrogen consumption is low, and facility investment and process cost are lower.
Embodiment
In the inventive method, the countercurrent hydrogenation treating process can be used conventional diesel oil hydrofining catalyst, usually be carrier with aluminum oxide and/or amorphous silicon aluminium, with VIB and VIII family metallic sulfide is active ingredient, the Hydrobon catalyst that preferably has strong denitrogenation ability becomes as the metal group of catalyzer: WO
3Be 17w%～21w%, MoO
3Be 8w%～10w%, NiO is 3.5w%～5.5w%; Physico-chemical property is: pore volume ≮ 0.25ml/g, specific surface area ≮ 120m
2/ g, bed voidage are 0.4～0.7.The FH-98 that produces as Wenzhou Hua Hua group company, FH-5 Hydrobon catalyst etc. can use.Countercurrent hydrogenation purification operations condition is: 270～380 ℃ of temperature, pressure 3.0～12.0MPa, air speed 0.5～3.0h
-1, hydrogen to oil volume ratio 100～800.
Hydrogenation conversion catalyst be a kind of be carrier with molecular sieve, aluminum oxide, unformed Si-Al, support hydrogenation metal.The used hydrogenation active metals of catalyzer is W, Ni, can add auxiliary agent in the catalyzer.Catalyzer consists of WO
310w%～30w%, NiO 2w%～15w%, molecular sieve 5w%～45w%, aluminum oxide 30w%～70w%, amorphous silicon aluminium 5w%～25w%.Its best group becomes WO
315w%～25w%, NiO4w%～10w%, molecular sieve 10w%～35w%, aluminum oxide 40w%～60w%, amorphous silicon aluminium 8w%～20w%, auxiliary agent fluorine 1w%～9w%.Wherein molecular sieve is a Y zeolite, and its infrared total acid is 0.5～1.1mmol/g, and lattice constant is 2.436～2.444nm.The concrete preparation method of catalyzer can be referring to CN1178238A.The hydrocracking operational condition is: temperature is that 340～390 ℃, pressure are 4.0～12.0MPa, air speed 0.5-3.0h
-1, hydrogen to oil volume ratio 500-1500.
Further specify the present invention program and effect below by specific embodiment.
Direct liquefaction with certain coal is an example, diesel oil in its liquiefied product (the cut scope is generally 150-380 ℃) accounts for about 60v%, table 1 is a kind of DCL/Direct coal liquefaction diesel component character, as can be seen, the main problem of DCL/Direct coal liquefaction combined diesel oil is the density height, and aromaticity content is up to more than the 50m%, and cetane value is below 20, sulphur nitrogen content, acidity, existent gum are all higher, reach the requirement of automotive fuel far away.
Certain DCL/Direct coal liquefaction of table 1 is produced diesel oil distillate character
| Project | Gelatin liquefaction diesel oil 1 | Gelatin liquefaction diesel oil 2 |
| Boiling range/℃ | ||
| IBP/10％ | 193/215 | 185/210 |
| 30％/50％ | 230/233 | 225/231 |
| 70％/90％ | 236/275 | 238/280 |
| 95％/FBP | 292/313 | 291/315 |
| Density (20 ℃), g/cm 3 | 0.9272 | 0.9156 |
| Kinematic viscosity (20 ℃), mm 2/s | 5.615 | 6.417 |
| Condensation point, ℃ | -26 | -24 |
| Existent gum, mg/100ml | 208 | 195 |
| Acidity, mgKOH/100ml | 25.38 | 27.54 |
| Sulphur, μ g/g | 2600 | 2913 |
| Nitrogen, μ g/g | 1869 | 2537 |
| The actual measurement cetane value | ＜20 | ＜20 |
| Total aromatic hydrocarbons, w% | 57.4 | 61.0 |
| Mononuclear aromatics, w% | 37.5 | 39.5 |
| Double ring arene, w% | 19.2 | 20.9 |
| Thrcylic aromatic hydrocarbon, w% | 0.7 | 0.6 |
Embodiment 1～3
The countercurrent hydrogenation catalyst for refining is commercial Hydrobon catalyst FH-98, and hydrogenation conversion catalyst is hydrogenation conversion catalyst C-1, C-2 and the C-5 that introduces among the CN1178238A embodiment, concrete processing condition and the results are shown in Table 2.
Character contrast before and after the table 2 DCL/Direct coal liquefaction combined diesel oil upgrading
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Raw material | Gelatin liquefaction diesel oil 1 | Gelatin liquefaction diesel oil 1 | Gelatin liquefaction diesel oil 2 |
| Catalyzer (refining/as to transform) | FH-98/C-1 | FH-98/C-2 | FH-98/C-5 |
| The reaction stagnation pressure, MPa (refining/as to transform) | 11.0/11.0 | 10.0/10.0 | 8.0/8.0 |
| Hydrogen to oil volume ratio (refining/as to transform) | 400/800 | 400/1000 | 500/1200 |
| Volume space velocity, h -1(refining/as to transform) | 1.5/1.2 | 1.5/1.0 | 1.0/1.0 |
| Average reaction temperature, ℃ (refining/as to transform) | 340/360 | 345/370 | 350/380 |
| The diesel oil distillate productive rate, v% | 98 | 96 | 96 |
| Boiling range/℃ | |||
| IBP/10％ | 152/208 | 146/201 | 144/202 |
| 30％/50％ | 232/251 | 228/248 | 225/243 |
| 70％/90％ | 270/304 | 265/300 | 268/302 |
| 95％/FBP | 313/328 | 305/325 | 304/330 |
| Density (20 ℃), g/cm 3 | 0.8701 | 0.8721 | 0.8730 |
| Kinematic viscosity (20 ℃), mm 2/s | 4.053 | 4.012 | 4.065 |
| Condensation point, ℃ | -33 | -32 | -32 |
| Existent gum, mg/100ml | ＜1 | ＜1 | ＜1 |
| Acidity, mgKOH/100ml | 1.85 | 1.75 | 1.82 |
| Sulphur, μ g/g | ＜10 | ＜10 | ＜20 |
| Nitrogen, μ g/g (refining/as to transform) | 242/1.0 | 438/2.0 | 672/5.0 |
| The actual measurement cetane value | 39.7 | 38.9 | 35.4 |
| Mass spectrum is formed, w% | |||
| Paraffinic hydrocarbons | 16.7 | 14.0 | 12.1 |
| Naphthenic hydrocarbon | 62.4 | 58.5 | 59.3 |
| Total aromatic hydrocarbons | 20.9 | 27.5 | 28.6 |
| Mononuclear aromatics | 19.2 | 24.2 | 24.6 |
| Double ring arene | 1.5 | 3.1 | 3.8 |
| Thrcylic aromatic hydrocarbon | 0.2 | 0.2 | 0.2 |
Can find out from last table, the principal feature of DCL/Direct coal liquefaction combined diesel oil cut is that density is higher, sulphur, nitrogen impurity content is higher, aromaticity content is high especially, reach more than the 55w%, cetane value low especially (＜20), acidity and gum level are all high especially in addition, differ greatly from the clean diesel specification, can not directly use as automotive fuel, and after taking the processing of this combination process, under the situation of diesel yield＞95v%, sulphur, nitrogen is removed substantially, aromaticity content reduces 40%-75%, it is about 0.05 that density reduces, and cetane value has improved 15-25 more than the unit, can be directly as automotive fuel or as the fine diesel oil blending component.
Claims (10)
1, a kind of hydrogenation modification method of DCL/Direct coal liquefaction diesel oil, it is characterized in that under the hydrofining condition, gelatin liquefaction diesel oil distillate and hydrogen counter current contact on catalyzer, the nitrogen content of control hydrofining liquid phase effluent is 100～1000 μ g/g, the liquid phase effluent contacts with hydrogenation conversion catalyst with hydrogen and stream again, with low-cetane aromatic hydrocarbons open loop is the high hexadecane value component, and desulfurization and denitrification reaction further take place simultaneously, obtains high quality upgrading diesel product.
2, in accordance with the method for claim 1, the nitrogen content that it is characterized in that described hydrofining liquid phase effluent is 200～600 μ g/g.
3, in accordance with the method for claim 1, it is characterized in that described countercurrent hydrogenation treating process use diesel oil hydrofining catalyst.
4, in accordance with the method for claim 3, it is characterized in that described diesel oil hydrofining catalyst is a carrier with aluminum oxide and/or amorphous silicon aluminium, is active ingredient with VIB and VIII family metallic sulfide.
5, in accordance with the method for claim 1, it is characterized in that described countercurrent hydrogenation purification operations condition is: 270～380 ℃ of temperature, pressure 3.0～12.0MPa, air speed 0.5～3.0h
-1, hydrogen to oil volume ratio 100～800.
6, in accordance with the method for claim 1, it is characterized in that described hydrogenation conversion catalyst is a carrier with molecular sieve, aluminum oxide, unformed Si-Al, supports hydrogenation metal.
7, in accordance with the method for claim 6, it is characterized in that described hydrogenation conversion catalyst consists of WO
310w%～30w%, NiO 2w%～15w%, molecular sieve 5w%～45w%, aluminum oxide 30w%～70w%, amorphous silicon aluminium 5w%～25w%.
8, in accordance with the method for claim 6, the WO that consists of that it is characterized in that described catalyzer
315w%～25w%, NiO 4w%～10w%, molecular sieve 10w%～35w%, aluminum oxide 40w%～60w%, amorphous silicon aluminium 8w%～20w%, auxiliary agent fluorine 1w%～9w%.
9, according to claim 6,7 or 8 described methods, it is characterized in that the contained molecular sieve of described hydrogenation conversion catalyst is a Y zeolite, its infrared total acid is 0.5～1.1mmol/g, lattice constant is 2.436～2.444nm.
10, in accordance with the method for claim 1, it is characterized in that described hydrocracking operational condition is: temperature is that 340～390 ℃, pressure are 4.0～12.0MPa, air speed 0.5-3.0h
-1, hydrogen to oil volume ratio 500-1500.
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|---|---|---|---|
| CN 03134011 CN1233797C (en) | 2003-09-15 | 2003-09-15 | Hydrogenating modifying process for direct liquefying diesel oil of coal |
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|---|---|---|---|
| CN 03134011 CN1233797C (en) | 2003-09-15 | 2003-09-15 | Hydrogenating modifying process for direct liquefying diesel oil of coal |
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| CN1233797C true CN1233797C (en) | 2005-12-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092573B (en) * | 2006-06-22 | 2011-08-10 | 中国石油化工股份有限公司 | A hydrogenation method for producing diesel oil in low sulphur |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101085936B (en) * | 2006-06-07 | 2010-05-26 | 神华煤制油研究中心有限公司 | Method for preparing thermal conductive oil by using coal liquefied oil |
| CN101591564B (en) * | 2008-05-29 | 2014-04-09 | 北京三聚环保新材料股份有限公司 | Hydrofining method of diesel oil distillates in direct coal liquefied oil |
| FR2957607B1 (en) * | 2010-03-18 | 2013-05-03 | Inst Francais Du Petrole | PROCESS AND CONVERSION PRODUCTS OF CHARCOAL COMPRISING TWO STEPS OF DIRECT LIQUEFACTION IN BOILING BED AND A FIXED BED HYDROCRACKING STEP |
| CN103773481B (en) * | 2012-10-24 | 2015-12-09 | 中国石油化工股份有限公司 | A kind of Unicracking-JHC method of processing inferior raw material |
| CN107629817B (en) * | 2017-10-20 | 2020-01-31 | 神华集团有限责任公司 | Preparation method of white oil |
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2003
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101092573B (en) * | 2006-06-22 | 2011-08-10 | 中国石油化工股份有限公司 | A hydrogenation method for producing diesel oil in low sulphur |
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