CN1211468C - Hydrocracking method for increasing quality of refined diesel oil - Google Patents
Hydrocracking method for increasing quality of refined diesel oil Download PDFInfo
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- CN1211468C CN1211468C CN 02133120 CN02133120A CN1211468C CN 1211468 C CN1211468 C CN 1211468C CN 02133120 CN02133120 CN 02133120 CN 02133120 A CN02133120 A CN 02133120A CN 1211468 C CN1211468 C CN 1211468C
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- hydrocracking
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Abstract
The present invention discloses a hydrocracking technology by which the quality of refined diesel oil can be improved. The present invention is mainly characterized in that hydrodesulfurization is carried out to inferior diesel oil, the refined diesel oil after desulphurization is mixed with refined hydrocracking raw oil and enters a hydrocracking reactor, and the sulfur content and the nitrogen content of the mixed oil of the refined diesel oil and the refined hydrocracking raw oil can meet the feeding requirement for the hydrocracking reactor. Compared with the prior art, the method does not affect the original hydrocracking operation basically, and simultaneously, the quality of the inferior diesel oil is improved by a hydrocracking device, and therefore, high quality clean fuel is obtained. Simultaneously, the method is favorable to the operating stability of the hydrocracking device, and the problem that the temperature of a refining section is not matched with that of a cracking section in the hydrocracking technology is solved.
Description
1. technical field
The invention discloses a kind of improved hydrocracking method, particularly improve the method for hydrogen cracking of secondary processing diesel oil and straight-run diesel oil quality inferior.
2. background technology
Along with the sustainable development of national economy and the increasingly stringent of environmental regulation, require to produce a large amount of light clean fuels, this has quite high requirement to existing oil Refining Technologies.And the raw material of each refinery is worse and worse at present, straight(-run) diesel distillate can not satisfy specification of quality and come the direct production qualified product, and resembling the such light materialization of heavy oil heavy oil conversion device of catalytic cracking and coking still extensively exists, must produce the secondary processing diesel oil cut, the non-constant of these cut character is difficult to the qualified product that direct production conforms to quality requirements with existing technology.
Original purification techniques has the medium-pressure hydrocracking of secondary processing diesel oil cut refining, as FR2764902, RU2058371, US5068025, US5543036, US5817594, US5035793 etc., they can be easy to make the sulphur content in the cut to reach present specification of quality, but aromaticity content is difficult to meet the requirements; Use two sections purification techniquess of noble metal catalyst can guarantee that aromaticity content reaches requirement, as US5556824 and US5651878 etc., but its one-time investment is very huge, divides two sections operations again, and is cumbersome; If use high-pressure hydrogenation purified method,, also have the big problem of facility investment though can reach the requirement of sulphur content and aromaticity content simultaneously.
Nearly all refinery all has hydroeracking unit at present, only in this way just can produce high-quality light Fuel product and increase economic efficiency, and its processing complete processing has US6224747 and US6296758 etc.For hydroeracking unit, especially one-stage serial hydrocracking device, the tempo of development of Hydrobon catalyst is more many slowly than the tempo of development of hydrocracking catalyst, the activity of Hydrobon catalyst catalyst activity raising than before just is limited, and the catalyst activity before the specific activity of hydrocracking catalyst is much higher.Along with the increase of the treatment capacity of hydroeracking unit, raw material is poorer than in the past again, causes the temperature out of refining reaction device very high.In contrast to this, the cracking case temperature in is relatively low, this just needs to use a large amount of cold hydrogen, to reach the temperature of cracking case inlet, not only increased the power consumption of circulating hydrogen compressor, the also corresponding reserve level of device accident that increased with hydrogen, very unfavorable to the safety operation of hydroeracking unit.
3. summary of the invention
At the deficiencies in the prior art, the object of the present invention is to provide a kind of improved hydrocracking process, it can produce the lightweight clean diesel product that meets the high quality requirement under the situation of not obvious increase equipment and goods and materials investment.
Method of the present invention comprises: the mixing oil of secondary processing diesel oil such as (1) catalytic diesel oil, coker gas oil and straight run poor ignition quality fuel enters the medium-pressure hydrocracking desulfurizer, obtains refined diesel oil; (2) the hydroeracking unit raw material at first enters the hydrofining reactor of hydroeracking unit, obtains the refining wax oil of organic sulfide removal thing and organic nitrogen compound; (3) mixing oil of refined diesel oil and refining hydrocracking raw material (refining wax oil) enters the hydrocracking reactor of hydroeracking unit, obtain hydrocracking and generate oil, wherein the weight ratio of refined diesel oil and refining wax oil is 1: 5～5: 1, and organonitrogen content is less than 100 μ g/g in the mixing oil; (4) hydrocracking generates oil and enters separation column, and fractionation obtains various lightweight and clean fuel oils.
Compared with prior art, characteristics of the present invention are: it can produce the lightweight clean diesel product that meets the high quality requirement under the situation of not obvious increase equipment and goods and materials investment.It only needs to increase a high-pressure pump (being used for refined diesel oil is pressurized to the working pressure of hydroeracking unit) and high pressure line.For the medium-pressure hydrocracking refining plant, basic not variation.And refined diesel oil and refining wax oil mix, and can effectively reduce the temperature of refining wax oil, and reach the temperature in requirement of hydrocracking reactor, and this has saved a large amount of cold hydrogen, corresponding hydrogen reserve level and the required energy of compression of having reduced.The hydrogen to oil volume ratio of certainly corresponding increase hydrofining reactor improves refining effect, reduces temperature of reaction.Hydrofining diesel oil is by the high-pressure hydrocracking reactor, and aromatic hydrocarbons obtains saturated, has reduced the aromaticity content of diesel oil, finally reaches the purpose of producing clean fuel.
4. description of drawings
Fig. 1 is a principle process flow diagram of the present invention.
5. embodiment
As shown in Figure 1, the mixture 1 and the hydrogen 2 of secondary processing diesel oil and straight-run diesel oil inferior is mixed into the medium-pressure hydrocracking desulphurization reactor of filling Hydrobon catalyst, and the treated oil that obtains obtains refined diesel oil 6 in the high-pressure separator separation; Hydroeracking unit raw material 7 is mixed into the hydrofining reactor 9 that loads Hydrobon catalyst with high pressure hydrogen, obtains the refining wax oil of organic sulfide removal and organonitrogen; Refined diesel oil 6 is pumped to the working pressure of hydroeracking unit, and with refining wax oil and hydrocracking turning oil be mixed into the filling hydrocracking catalyst hydrocracking reactor 11, the hydrocracking logistics that obtains separates in high-pressure separator 13 and obtains hydrocracking and generate oil 15, its fractionation in the separation column 16 again, obtain gaseous fraction 17, petroleum naphtha 18, rocket engine fuel 19, diesel oil 20 and hydrocracking tail oil 21, tail oil 21 can be used as turning oil, also can be used as preparing ethylene by steam cracking, catalytically cracked material, the basic wet goods of high-viscosity index lubricating oil.
Operational condition to each device is described below below.
The medium-pressure hydrocracking desulphurization reactor main purpose of technology of the present invention is to remove the most sulphur, part nitrogen and the part aromatic hydrocarbons that mix in the poor ignition quality fuel oil to carry out saturatedly, and wherein sulphur and nitrogen transformation are hydrogen sulfide and ammonia.Secondary processing diesel oil is the diesel oil distillate that comprises that secondary processing devices such as catalytic cracking, coking, viscosity breaking and thermally splitting obtain, and its cut scope is 132～380 ℃; Straight-run diesel oil inferior is meant that sulphur content and aromaticity content do not reach the normal decompression straight run of specification of quality, and its cut scope is 132～380 ℃; The ratio of each cut is looked the practical situation decision without limits in the Medium diesel oil.The catalyzer that it uses is made up of carrier and the hydrogenation metal that is loaded in above it, is benchmark with the weight percent, and hydrogenation component comprises group vib active metal component (as tungsten and/or molybdenum), counts 10%～30% with metal oxide, and 15～25% is better; Group VIII active metal component (as nickel and/or cobalt) counts 1%～7% with metal oxide, and 1.5%～6% is better, and carrier is aluminum oxide or siliceous aluminum oxide etc., the FH-5 that commercial catalysts such as Wenzhou catalyst plant are produced, FH-5A and FH-98 etc.Operational condition: reacting total pressure pressure is 3.0MPa～12.0MPa, preferably 5.0MPa～11.0MPa; Average reaction temperature is 280 ℃～400 ℃, best 320 ℃～370 ℃; Volume space velocity 0.1h during liquid
-1～4.0h
-1, best 0.4h
-1～2.5h
-1Hydrogen to oil volume ratio is 100: 1～3000: 1, best 350: 1～1500: 1.The outlet of medium-pressure hydrocracking desulphurization reactor generates oily organic sulfur content less than 1500 μ g/g, and better less than 800 μ g/g, organonitrogen content is less than 500 μ g/g, and is better less than 100 μ g/g.
Hydrocracking technology is the indispensable important means of modern refineries production high-quality clean fuel, raw material can be residual oil, gas oil, heavy gas oil, topped oil, resinous shale, coal transform oil and burnt transform wet goods can be nitrogenous also can nonnitrogenous component hydro carbons.Can be divided into three kinds by work flow: two-stage method flow process, one-stage serial flow process and method by single-stage flow process.Wherein in the two-stage method work flow in second section reactor the catalyzer of adorning mostly be noble metal catalyst, generally adopt extinction recycle operation.The characteristics of method by single-stage flow process are less investments, but raw material is limited to some extent, and quality product is edge often also.The inventive method preferably includes the one-stage serial flow process of hydrofining and hydrocracking.
The one-stage serial flow process comprises hydrofining reactor, hydrocracking reactor and hydrogenation fractionating tower three parts.Wherein Hydrobon catalyst in the reactor and hydrocracking catalyst, they all are made up of carrier and the hydrogenation metal that is loaded in above it, with the weight percent is benchmark, hydrogenation metal is a base metal, comprise group vib active metal component in the periodic table of elements, as tungsten and/or molybdenum, count 10%～35% with metal oxide, 15～30% is better; And the group VIII reactive metal, as nickel and/or cobalt, count 1%～7% with metal oxide, 1.5%～6% is better.The carrier that Hydrobon catalyst uses is an inorganic refractory oxide, as aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., commercial Hydrobon catalyst mainly contains: 3936,3996 etc. of the HC-K of Uop Inc., HC-T, HC-P and Fushun Petrochemical Company catalyst plant.The carrier of hydrocracking catalyst is aluminum oxide and molecular sieve, and molecular sieve content is generally 20%～60%, and commercial hydrocracking catalyst mainly contains: 3971,3974 etc. of the HC-12 of Uop Inc., HC-14 and Fushun Petrochemical Company catalyst plant.Catalyzer layering filling has cold hydrogen hand-hole between each bed, inject cold hydrogen during operation, takes away the reaction heat that hydrogenation reaction and cracking reaction produce, and makes temperature of reaction within the specific limits, makes operation safe, steady.Described hydrofining reactor operational condition is: pressure is 5.0MPa～19.0MPa, preferably 10.0MPa～16.0MPa; Average reaction temperature is 300 ℃～440 ℃, best 330 ℃～420 ℃; Volume space velocity 0.1h during liquid
-1～4.0h
-1, best 0.4h
-1～2.0h
-1Hydrogen to oil volume ratio is 100: 1～3000: 1, best 500: 1～2000: 1.The hydrofining reactor outlet is refining to generate oily organonitrogen content less than 100 μ g/g, preferably less than 80 μ g/g.The logistics of coming out from hydrofining reactor mixes with refined diesel oil, enters hydrocracking reactor then.Described hydrocracking reactor operational condition is: pressure is 5.0MPa～19.0MPa, preferably 10.0MPa～16.0MPa; Average reaction temperature is 300 ℃～440 ℃, best 350 ℃～420 ℃; Volume space velocity 0.1h during liquid
-1～3.0h
-1, best 0.4h
-1～1.8h
-1Hydrogen to oil volume ratio is 100: 1～3000: 1, best 500: 1～2000: 1.But product and hydrocracking tail oils such as described hydrogenation fractionating tower direct production liquefied gas, light naphthar, heavy naphtha, aviation kerosene, diesel oil.
Below by embodiment the present invention program and effect are described
Medium diesel oil at first inferior enters the medium-pressure hydrocracking desulphurization reactor, obtains refined diesel oil through hydrogenation reaction.See the following form 1.
Table 1
| | | |
| Stock oil character | ||
| Density, g/cm 3 | 0.8273 | 0.9035 |
| Cetane value | 59.7 | 35.2 |
| Sulphur content, μ g/g | 988 | 6200 |
| Nitrogen content, μ g/g | 1200 | 1500 |
| The hydrodesulfurization condition | ||
| Catalyzer | FH-98 | FH-5 |
| Pressure, Mpa | 7.0 | 6.8 |
| Temperature, ℃ | 300 | 320 |
| Air speed, h -1 | 1.5 | 1.5 |
| Hydrogen to oil volume ratio | 1000∶1 | 1000∶1 |
| Refined diesel oil character | ||
| Sulphur content, μ g/g | 300 | 200 |
| Nitrogen content, μ g/g | 100 | 300 |
| Cetane value | 62 | 40 |
| Aromaticity content, m% | 35.0 | 50.2 |
Hydrocracking raw material at first enters hydrofining reactor, obtains the hydrofining wax oil.See the following form 2.
Table 2
| | | |
| Stock oil character | ||
| Density, g/cm 3 | 0.8952 | 0.9180 |
| Sulphur content, wt% | 14800 | 24600 |
| Nitrogen content, μ g/g | 1280 | 733 |
| The hydrofining technology condition |
| Catalyzer | 3936 | 3936 |
| Pressure, Mpa | 15.7 | 15.7 |
| Medial temperature, ℃ | 376 | 386 |
| Temperature out, ℃ | 400 | 410 |
| Volume space velocity, h -1 | 1.08 | 1.0 |
| Hydrogen to oil volume ratio | 950∶1 | 700∶1 |
| Refining wax oil character | ||
| Nitrogen content, μ g/g | ＜10 | 30 |
Refined diesel oil and refining wax oil enter hydrocracking reactor after mixing.See the following form 3.
Table 3
| | Reference example 1 | | Reference example 2 | |
| The weight blending ratio | 70∶30 | 100∶0 | 85∶15 | 100∶0 |
| Stock oil character | ||||
| Density, g/cm 3 | 0.8748 | - | 0.9158 | - |
| Nitrogen content, μ g/g | 30 | ＜10 | 84 | 30 |
| The hydrocracking process condition | ||||
| Catalyzer | 3974 | 3974 | 3971 | 3971 |
| Pressure, Mpa | 15.7 | 15.7 | 15.7 | 15.7 |
| Temperature in, ℃ | 350 | 350 | 360 | 360 |
| Medial temperature, ℃ | 375 | 375 | 389 | 389 |
| Volume space velocity, h -1 | 1.42 | 1.0 | 1.41 | 1.2 |
| Hydrogen to oil volume ratio | 1200∶1 | 1200∶1 | 900∶1 | 900∶1 |
| ＜350 ℃ of cut yields, v% | 70 | 60 | 65 | 60 |
| Each cut character of hydrocracking | ||||
| The rocket engine fuel smoke point, mm | 25 | 25 | 25 | 25 |
| Aromatic hydrocarbon content of diesel oil cut fraction, wt% | 12.0 | 9.5 | 14.8 | 13.0 |
| The diesel oil distillate cetane value | 58.0 | 60.6 | 57 | 62.3 |
| Sulphur content of diesel fraction, μ g/g | ＜15 | ＜15 | ＜15 | ＜15 |
By embodiment as can be seen,, use conventional device and equipment, can produce the light clean fuel that meets the quality product requirement by improvement technology of the present invention.
Claims (10)
1, a kind of method for hydrogen cracking that improves quality of refined diesel oil, under hydrocracking condition, with hydrocracking raw material by hydrofining and hydrocracking catalyst bed, it is characterized in that poor ignition quality fuel through the medium-pressure hydrocracking desulfurization, be mixed into the hydrocracking catalyst bed with hydrogenating desulfurization diesel oil and through the hydrocracking raw material oil after the hydrofining then, wherein oil of the cracking stock after the hydrofining and hydrofining diesel oil weight ratio are 1: 5～5: 1, and the organonitrogen content in the mixing oil is less than 100 μ g/g.
2, in accordance with the method for claim 1, it is characterized in that described poor ignition quality fuel is selected from a kind of or mixing oil in catalytic diesel oil, coker gas oil, viscosity breaking diesel oil, thermally splitting diesel oil and the straight run poor ignition quality fuel.
3, according to claim 1 or 2 described methods, it is characterized in that the employed catalyzer of described poor ignition quality fuel hydrogenating desulfurization is an active ingredient with group vib and group VIII metal, with aluminum oxide or siliceous aluminum oxide is carrier, the operational condition of hydrogenating desulfurization is: reaction stagnation pressure 3.0MPa～12.0MPa, average reaction temperature is 280 ℃～400 ℃, volume space velocity 0.1h during liquid
-1～4.0h
-1, hydrogen to oil volume ratio is 100: 1～3000: 1, generates oily organic sulfur content less than 1500 μ g/g, organonitrogen content is less than 500 μ g/g.
4, in accordance with the method for claim 3, it is characterized in that the group vib active metal component is tungsten and/or molybdenum in the described catalyzer, count 10%～30% with metal oxide weight, the group VIII active metal component is nickel and/or cobalt, count 1%～7% with metal oxide weight, operational condition is: the reaction stagnation pressure is 5.0MPa～11.0MPa, and average reaction temperature is 320 ℃～370 ℃, volume space velocity 0.4h during liquid
-1～2.5h
-1, hydrogen to oil volume ratio is 350: 1～1500: 1, generates oily organic sulfur content less than 800 μ g/g, organonitrogen content is less than 100 μ g/g.
5, in accordance with the method for claim 1, it is characterized in that described hydrocracking is an one-stage serial technology, comprise hydrofining reactor, hydrocracking reactor and hydrogenation fractionating tower three parts.
6, in accordance with the method for claim 5, it is characterized in that the catalyzer that described hydrofining reactor uses is active ingredient with group vib and group VIII metal, is carrier with the inorganic refractory oxide; Operational condition is: pressure is 5.0MPa～19.0MPa, and average reaction temperature is 300 ℃～440 ℃, volume space velocity 0.1h during liquid
-1～4.0h
-1, hydrogen to oil volume ratio is 100: 1～3000: 1, the hydrofining reactor outlet is refining to generate oily organonitrogen content less than 100 μ g/g.
7, in accordance with the method for claim 6, it is characterized in that described group vib metal is tungsten and/or molybdenum, count 10%～35% with metal oxide weight, the group VIII metal is nickel and/or cobalt, counts 1%～7% with metal oxide weight; Operational condition is: pressure is 10.0MPa～16.0MPa, and average reaction temperature is 330 ℃～420 ℃, volume space velocity 0.4h during liquid
-1～2.0h
-1, hydrogen to oil volume ratio is 500: 1～2000: 1; The hydrofining reactor outlet is refining to generate oily organonitrogen content less than 80 μ g/g.
8, in accordance with the method for claim 5, it is characterized in that described hydrocracking reactor uses the carrier of hydrocracking catalyst to be aluminum oxide and molecular sieve, the molecular sieve weight content is 20%～60%.
9, in accordance with the method for claim 5, it is characterized in that described hydrocracking operational condition is: pressure is 5.0MPa～19.0MPa, and average reaction temperature is 300 ℃～440 ℃, volume space velocity 0.1h during liquid
-1～3.0h
-1, hydrogen to oil volume ratio is 100: 1～3000: 1.
10, in accordance with the method for claim 5, it is characterized in that described hydrocracking operational condition is: pressure is 10.0MPa～16.0MPa, and average reaction temperature is 350 ℃～420 ℃, and volume space velocity is 0.4h during liquid
-1～1.8h
-1, hydrogen to oil volume ratio is 500: 1～2000: 1.
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| CN 02133120 CN1211468C (en) | 2002-10-10 | 2002-10-10 | Hydrocracking method for increasing quality of refined diesel oil |
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|---|---|---|---|
| CN 02133120 CN1211468C (en) | 2002-10-10 | 2002-10-10 | Hydrocracking method for increasing quality of refined diesel oil |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453535A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrocracking method for reforming material yield increase |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1955257B (en) * | 2005-10-24 | 2010-05-12 | 中国石油化工股份有限公司 | Hydrocracking method for producing chemical raw material |
| CN102453536B (en) * | 2010-10-25 | 2014-08-20 | 中国石油化工股份有限公司 | Integrated hydrogenation method for producing clean diesel |
| CN103059969B (en) * | 2011-10-21 | 2014-12-31 | 中国石油化工股份有限公司 | Startup passivation method of hydrocracking catalyst |
| CN103059986B (en) * | 2011-10-24 | 2015-02-25 | 中国石油化工股份有限公司 | Hydrocracking method for producing chemical materials |
| CN103059972B (en) * | 2011-10-24 | 2015-02-25 | 中国石油化工股份有限公司 | Combined hydrogenation method of producing chemical materials |
| FR2983866B1 (en) * | 2011-12-07 | 2015-01-16 | Ifp Energies Now | PROCESS FOR HYDROCONVERSION OF PETROLEUM LOADS IN BEDS FOR THE PRODUCTION OF LOW SULFUR CONTENT FIELDS |
| CN114437777B (en) * | 2020-10-19 | 2023-07-28 | 中国石油化工股份有限公司 | Method for producing lubricating oil base oil |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102453535A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrocracking method for reforming material yield increase |
| CN102453535B (en) * | 2010-10-22 | 2014-08-20 | 中国石油化工股份有限公司 | Hydrocracking method for reforming material yield increase |
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