CN105778994A - Combined process method for producing ultra-low-sulfur diesel - Google Patents
Combined process method for producing ultra-low-sulfur diesel Download PDFInfo
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- CN105778994A CN105778994A CN201610178560.5A CN201610178560A CN105778994A CN 105778994 A CN105778994 A CN 105778994A CN 201610178560 A CN201610178560 A CN 201610178560A CN 105778994 A CN105778994 A CN 105778994A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
The invention discloses a combined process method for producing an ultra-low-sulfur diesel. The combined process method for producing the ultra-low-sulfur diesel is characterized by comprising the following steps of mixing inferior high nitrogen diesel raw materials, partially circulated hydrofining diesel oil products and hydrogen; heating through a heating furnace; entering into a liquid phase hydrogenation reactor; carrying out olefin hydrogenation saturation, desulfuration, denitrification and aromatic saturation; discharging a reaction by-product gas out of a reaction system; partially circulating the hydrofining diesel oil products; entering into a catalyzed adsorption desulfurization reactor after mixing the other parts with the hydrogen; removing residual sulfide, and obtaining the ultra-low-sulfur clean diesel.The combined process method provided by the invention combines liquid-phase circulation hydrogenation and catalyzed adsorption desulfurization, removes a sulfur compound in the diesel step by step, not only solves the difficult problems that the diesel liquid-phase circulation hydrogenation reaction condition is strict and the product sulphur content is difficult to meet the national V/VI standard, but also avoids the defects of short catalyzed adsorption desulfurization operation period and frequent use of loading and unloading agent, and has the advantages of low operation pressure, small hydrogen consumption, small investment and the like.
Description
Technical field
The present invention relates to a kind of combined technical method producing ultra-low-sulphur diesel, specifically, relate to high nitrogen diesel oil liquid phase circulation hydrogenation-catalytic adsorption desulfurization inferior and produce the combined technical method of ultra-low-sulphur diesel.
Background technology
In recent years, along with in world wide, crude oil in poor quality tendency is day by day obvious, in oil product, sulfur nitrogen and arene content increase day by day；Meanwhile, various countries are also more and more higher to the requirement of environmental protection, and Oil Refining Industry faces the pressure of oil quality upgrading.Reduce the sulfur content in diesel oil and arene content can reduce the Powelery Solids Emission of exhaust gas from diesel vehicle, reduce atmospheric pollution.Euro V emissions requires that light diesel fuel sulfur content is less than 10 μ g/g, and China has performed the state V derv fuel standard suitable with Europe V in some areas, and tightened up state's VI standard is just under consideration.The upgrading of current Petrochemical Enterprises diesel quality all suffers from greatly that diesel oil hydrogenation scarce capacity, hydrogen resources be inadequate and the problems such as hydrogenation depth is unreasonable.For tackling the production of New emission standard diesel oil, the newly-built hydrogenation plant in part refinery carries out deep hydrodesulfurizationof of diesel oil, improves Cetane number, improves oil quality；On the other hand, enterprise is more likely to adopt existing apparatus transformation to produce ultra-low-sulphur diesel.Modification scheme usually considers from following several respects: substitutes with the catalyst that activity is higher and now uses catalyst；Carry High Operating Temperature；Improve hydrogen purity or improve hydrogen dividing potential drop；Improve reactor；Improve the charging distribution of beds；Hydrogen sulfide etc. is removed from circulating air.These measures can cause cost of investment to be significantly increased without exception.
Currently, the hydrogen addition technology of domestic most main flow adopts recycle hydrogen hydrogenation technique.In this process, in order to control the reaction temperature of beds and avoid catalyst carbon deposit to inactivate, generally adopt bigger hydrogen-oil ratio.At a large amount of hydrogen of beds internal recycle during operation, needed for it consumes hydrogen than chemistry, hydrogen amount to exceed 10 times.Chinese patent CN200710148432.7 discloses a kind of method producing ultra-low-sulphur diesel.With diesel oil distillate for raw oil, adopting single hop or one-stage serial technological process, having at least a kind of catalyst in the catalyst of hydroconversion reaction zone is bulk phase catalyst.The method uses tradition trickle bed, and by using high performance hydrogenation catalyst to produce ultra-low-sulphur diesel, catalyst is expensive.Chinese patent CN201110180906.2 discloses the production method of a kind of ultra-low-sulphur diesel, straight run atmosphere 3rd side cut fraction and/or diesel oil heavy distillat enter the first hydroconversion reaction zone after mixing with hydrogen, react under the effect of catalyst for hydro-upgrading and Hydrobon catalyst, straight run normal two wires fraction and/or diesel oil light fraction enter the second hydroconversion reaction zone after mixing with the reaction effluent of the first hydroconversion reaction zone, react under the effect of Hydrobon catalyst, obtain naphtha cut and diesel product.The method adopts two reactors in series and sectional feeding technique, and flow process is complicated, and equipment investment is bigger.During hydrogenation plant is built, the ratio making an investment in whole process cost of hydrogen circulation link is very big.If able to the hydrogen flowing quantity in hydroprocessing processes is reduced and is saved hydrogen gas circulating system and circulating hydrogen compressor, it is possible to be greatly saved investment for enterprise.
Liquid phase circulation hydrogenation technique eliminates gas phase blood circulation, the needs of the hydrogen supply hydrogenation reaction by being dissolved in circulation liquid phase.US Patent No. 6213835, US6428686 etc. disclose the hydrogenation technique of a kind of molten hydrogen in advance, and by hydrogenated oil circulation increased molten hydrogen amount, but it is not solved by the H that will produce in hydrogenation process2S、NH3Deng the problem of objectionable impurities elimination, H2S、NH3Accumulate in reactor Deng constantly, it is suppressed that hydrogenation reaction, greatly reduce catalyst hydrogenation activity.Chinese patent CN102029128A discloses the hydrotreating method of a kind of product circulation, and reactor top arranges air stripping tower tray, hydrogen and liquid phase material and contacts the H that air stripping goes out in liquid phase material on air stripping tower tray2S and NH3, hydrogen is dissolved in liquid phase material further simultaneously.A large amount of air stripping tower tray is set in this patent reactor, causes reactor effectively to utilize volume to reduce, add the workload of shut-down (breakdown) mainteance simultaneously.Chinese patent CN101724443A discloses a kind of distillate two-phase hydrogenation processing method, it is saturated that raw material, hydrogen and circulation hydrogenation products carry out hydrogen in presaturation pressure pan, form two liquid phase mixtures of a kind of raw material/hydrogenation products/hydrogen, isolate the hydrogen in liquid phase mixture, the mixture of saturated dissolved hydrogen passes through single-stage or multiple-stage internal cross-flow reactor, although solve molten hydrogen and H2S、NH3Etc. harmful gas release And Spread of Solute, but its cross-flow structure of reactor is complicated, and reactor bottom sets cross-flow stripping zone, and reactor volume is big, and operating process is complicated.
Chinese patent CN101942327B discloses a kind of hydrotreatment combined technical method producing ultra-low-sulphur diesel, and reactive moieties includes gas phase circulation hydrogenation unit and liquid phase circulation hydrogenation unit.Wherein, liquid phase circulation hydrogenation unit is according to process conditions, it is determined that be mixed into the amounts of hydrogen in charging, and amounts of hydrogen is higher than reaction hydrogen-consuming volume, and control to be constant basis, control the amount of liquid in reactor and pressure by controlling reactor capacity (and lifting rate)；Gas phase circulation hydrogenation unit is conventional trickle bed reaction, and hydrogen circulates at beds, and consumption is more than 10 times of chemical hydrogen consumption, and the hydrogen of consumption supplements from gas phase.Although the method solves ultra-low-sulphur diesel and produces problem, but adopts two set hydrogenation plants, investment and complicated operation degree is caused to be greatly improved.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of combined technical method producing ultra-low-sulphur diesel, it particularly relates to high nitrogen diesel oil liquid phase circulation hydrogenation-catalytic adsorption desulfurization inferior produces the combined technical method of ultra-low-sulphur diesel.Liquid phase circulation hydrogenation is combined by the present invention with catalytic adsorption desulfurization, plays two kinds of respective advantages of technology, the sulfur compound in substep elimination diesel oil, reaches the purpose of ultra-deep desulfurization.When the method had both solved diesel oil liquid phase circulation process high-nitrogen raw oil, hydrogenation conditions is harsh, product sulfur content is difficult to meet a difficult problem for state V/VI derv fuel standard, turn avoid the drawback of catalytic adsorption desulfurization handling agent short, frequent service cycle, pressure is low, reaction temperature relaxes, hydrogen consumption is little, invest the advantages such as little to have operation.
A kind of combined technical method producing ultra-low-sulphur diesel provided by the invention, the method comprises the following steps:
The hydrogenated diesel oil product that high nitrogen diesel raw material inferior, part circulate mixes with hydrogen, after the heating of heated stove, the liquid material of saturated dissolved hydrogen enters liquid phase circulation hydrogenation reactor, carries out olefins hydrogenation, desulfurization, denitrogenation and aromatic hydrocarbons saturated reaction, byproduct of reaction H2S、NH3Deng discharge response system；Hydrogenation products circulates to liquid phase circulation hydrogenation reactor partly as hydrogenation recycle oil, after hydrogenation products remainder mixes with hydrogen, enters catalytic adsorption desulfurization reactor, the sulfide of elimination residual, obtains ultra-low sulfur clean diesel；
The liquid material of described saturated dissolved hydrogen by the reaction condition of liquid phase circulation hydrogenation reactor beds is: reaction pressure is 4.0～12.0MPa, and fresh diesel raw material volume space velocity is 0.5～2.0h-1, temperature is 300～420 DEG C.
Described hydrogenation products remainder by the reaction condition of catalytic adsorption desulfurization reactor beds is: reaction pressure is 0.5～3.0MPa, hydrogen-oil ratio 100:1～400:1, and volume space velocity is 1.0～4.0h-1, temperature is 260～450 DEG C.
Liquid phase circulation hydrogenation reactor in combined technical method of the present invention includes the single-stage hydrogenation reactor that at least two is one another in series, and is arranged in series in a reactor；The top of single-stage hydrogenation reactor is provided with gas liberation port, discharges hydrogenation reaction by-product H2S、NH3Deng.
Catalytic adsorption desulfurization reactor in combined technical method of the present invention preferably fixes the one in bed, moving bed, ebullated bed, slurry bed system, fluid bed.
In combined technical method of the present invention, it is preferable that hydrogenated diesel oil product initially enters high pressure air stripping separator before entering catalytic adsorption desulfurization reactor, hydrogen the H dissolved is proposed2S and NH3Deng.
In combined technical method of the present invention, described hydrogenation recycle oil and the volume ratio of the high nitrogen diesel raw material of poor quality are preferably 1:1～4:1.
The liquid phase material of the saturated dissolved hydrogen entering liquid phase circulation hydrogenation reactor in combined technical method of the present invention, the amounts of hydrogen of dissolving is preferably 1.5～10 times of course of reaction chemical hydrogen consumption amount.
Poor quality high nitrogen diesel oil in combined technical method of the present invention is preferably selected from the mixture of one or more in high nitrogen straight-run diesel oil, catalytic diesel oil, coker gas oil.
Compared with prior art, this have the advantage that:
(1) compared with tradition trickle bed hydrogenation technique, eliminating hydrogen gas circulating system and circulating hydrogen compressor, investment for trnasforming urban land cost is low, and operating flexibility is big；
(2) the by-product H that reaction can be produced by combined method of the present invention2S、NH3Deng discharge in time, when solving high nitrogen diesel raw material hydrotreatment, H2S and NH3Strong inhibition effect to hydrogenation reaction, improves reaction effect, it is ensured that hydrogenation activity that catalyst is higher and stability.Simultaneously, owing to the sulfide of the overwhelming majority removes and discharges at liquid phase circulation hydrogenation reaction unit outside system, catalytic adsorption desulfurization unit only processes the trace sulfide of residual, greatly reduces the process load of absorption desulfurization unit, it is ensured that the life-span of adsorbent and long-term operation；
(3) liquid phase circulation hydrogenation-catalytic adsorption desulfurization combined technical method is used, classification elimination sulfur-containing compound, both played liquid phase circulation hydrogenation runs cycle length, advantage that reaction stability is high, make use of again the advantage that catalytic adsorption desulphurization reaction condition relaxes, desulfurization precision is high, significantly reduce high nitrogen poor ignition quality fuel hydrogenation and produce the operating severity of super-low sulfur product；
(4) existing hydrogen addition technology is carried out efficient organic integration by the inventive method, and technical difficulty, risk and improvement cost are all relatively low, and scheme is flexible, and simple to operate, operating cost is low.
Accompanying drawing explanation
Fig. 1 is the process flow diagram (liquid phase circulation reactor is two-stage series connection reactor, and catalytic adsorption desulfurization reactor is single slage fixed bed reactor) that the present invention produces a kind of preferred implementation of the combined technical method of ultra-low-sulphur diesel.
Wherein: 1 is new hydrogen, 2 is high nitrogen diesel raw material inferior, 3 as the hydrogenation products being hydrogenated with recycle oil, 4 is the hydrogenation products being discharged into high pressure stripping separator from reactor bottom, and 5 is liquid phase circulation hydrogenation reactor, and 5A is first order reactor, 5B is second level reactor, 6 is high pressure stripping separator, and 7 is catalytic adsorption desulfurization reactor, and 8,9,10 is comprise H2S、NH3Etc. the release gas of hydrogenation byproduct, 11 is ultra-low-sulphur diesel product, and 12 is heating furnace.
Detailed description of the invention
The combined technical method that the present invention produces ultra-low-sulphur diesel below in conjunction with Figure of description and specific embodiment is described further.
For ease of further illustrating the hydroprocessing processes that the present invention produces the combined technical method of ultra-low-sulphur diesel, the detailed process of the present invention is described as follows.As shown in Figure 1, high nitrogen diesel raw material 2 inferior mixes with hydrogenation recycle oil 3, new hydrogen 1, entrance liquid phase circulation reactor 5 after heat exchange, carrying out the reaction such as olefins hydrogenation, desulfurization, denitrogenation and Tuo Fang, the new hydrogen of part supplements at reactor 5B top, the second level, simultaneously excessive hydrogen and H2S、NH3Etc. hydrogenation byproduct (8,9) from liberation port discharge system.The hydrogenation products that second level reactor 5B discharges is divided into two-way logistics, and a road is circulated as hydrogenation recycle oil 3, and a road enters follow-up high pressure stripping separator 6 as hydrogenation products 4, through the H of the new hydrogen stripping elimination overwhelming majority2S、NH3After hydrogenation byproduct 10, enter catalytic adsorption desulfurization reactor 7 after mixing with new hydrogen and carry out further desulphurization reaction, it is thus achieved that ultra-low-sulphur diesel product.
Apply combined technical method of the present invention, for sulfur content 50～350 μ g/g diesel hydrotreater originally can only be produced, after technological transformation, it is possible to be directly produced the sulfur content ultra-low-sulphur diesel less than 10 μ g/g.
Liquid phase circulation hydrogenation reactor in combined technical method of the present invention, suitable hydrogenation catalyst is used according to reaction needed, such as Hydrobon catalyst, catalyst for hydro-upgrading, hydrotreating catalyst etc., various catalyst can select commercial catalyst, it is also possible to prepares according to prior art.
Catalytic adsorption desulfurization reactor in combined technical method of the present invention, uses suitable catalytic adsorption desulfurizing agent according to reaction needed, it is possible to select commercial catalyst, it is also possible to prepare according to prior art.
The liquid phase feeding amount entering each reactor of the present invention can be evenly distributed, it is possible to has difference, requires to be adjusted with specific reference to feedstock property, reaction condition and product quality.Equally, liquid phase circulation hydrogenation reactor and in catalytic adsorption desulfurization reactor in each single-stage reactor, the filling ratio of various catalyst is determined also dependent on raw material and product requirement.Such as these many variations, are all protection scope of the present invention.
The inventive method does not set hydrogen gas circulating system and circulating hydrogen compressor, can control catalyst bed reaction temperature well by product liquid phase circulation；Reaction mass fine dispersion on catalyst surface can be realized without the need for the extra reactor inner member that increases, improve hydrogenation reaction efficiency；The by-product H simultaneously reaction produced2S、NH3Deng discharging in time, reduce its inhibitory action to hydrogenation reaction, it is ensured that the activity of catalyst and stability；Additionally, the sulfide of the hydrogenation products residual low content after liquid phase circulation hydrogenation reactor processes, it is possible to being easy to be caught elimination by catalytic adsorption desulfurizing agent, reaction pressure is low, and the elimination degree of depth is high, and device is long for service cycle.
Technical scheme is expanded on further below in conjunction with specific embodiment.
Embodiment
Adopting the scheme that two-stage series connection liquid phase circulation reactor uses with the combination of catalytic adsorption desulfurization reactor, raw materials used oil is in Table 1-1.Hydrogenation main reactor loads industrial conventional FH-98 Hydrobon catalyst, and catalytic adsorption desulfurization reactor loads Ni-based adsorption desulfurizing agent.Process conditions are in Table 1-2, and refined diesel oil character is in Table 1-3.
Table 1-1 raw oil character
| Oil property | New raw material oil |
| Density (20 DEG C), g/cm3 | 0.8621 |
| Initial boiling point～end point of distillation, DEG C | 171～372 |
| Sulfur, μ g/g | 2608 |
| Nitrogen, μ g/g | 1845 |
| Polycyclic aromatic hydrocarbon content, % | 38.6 |
| Cetane index | 50.6 |
| IBP | 186 |
| 10% | 228 |
| 50% | 269 |
| 90% | 352 |
| FBP | 368 |
Table 1-2 process conditions
Table 1-3 hydrofining diesel oil character
Comparative example 1
Compared with embodiment, not adopting catalytic adsorption desulfurization reactor, circulation products mixes with raw material, hydrogen, be directly entered thtee-stage shiplock liquid phase circulation hydrogenation reactor after heat exchange.The same embodiment of raw materials used oil, catalyst type and loadings.Process conditions are in Table 2-1, and hydrofining diesel oil character is in Table 2-2.
Table 2-1 process conditions
| Process conditions | Liquid phase circulation reactor |
| Reaction temperature, DEG C | 370 |
| Reaction pressure, MPa | 6.5 |
| Circulation volume ratio (recycle oil: fresh feed) | 5:1 |
| Fresh feed volume space velocity, h-1 | 1.0 |
| Mixed hydrogen amount/inlet amount (wt%) | 0.8 |
| Dissolved hydrogen sulfide (entrance sampling detection), μ g/g in raw oil | 500 |
Table 2-2 hydrofining diesel oil character
Comparative example 2
Compared with embodiment, do not adopt liquid phase circulation-catalytic adsorption group technology, but adopt tradition trickle bed reactor, once by not circulation technology.The same embodiment of raw materials used oil, catalyst type and loadings.Process conditions are in Table 3-1, and hydrofining diesel oil character is in Table 3-2.
Table 3-1 process conditions
Table 3-2 hydrofining diesel oil character
It can be seen that liquid phase circulation-catalytic adsorption group technology has significantly energy-saving and cost-reducing advantage, and product quality is more excellent.When individually adopting tradition trickle bed hydrogenation technique to process high-nitrogen raw oil, H2S and NH3Hydrogenation reaction has stronger inhibitory action, and this causes reaction operating mode harshness, and (reaction temperature is higher, and 375 DEG C, air speed is little, 0.8h-1, hydrogen-oil ratio reaches 600:1), hydrogenation products sulfur and nitrogen content is higher and raises very fast, catalyst stability is poor, and later product cannot meet state's V diesel oil standard of 10ppm.Individually adopt liquid phase circulation technique, H2S and NH3Can discharging response system in time, reduce its inhibitory action to hydrogenation reaction, operating condition and product quality are better than tradition trickle bed hydrogenation technique, but temperature drift, air speed is less than normal, and energy consumption is bigger than normal.Adopting liquid phase circulation hydrogenation-catalytic adsorption desulfurization group technology, it is possible to solve the problems referred to above, under the reaction condition substantially relaxed, (two temperature of reactor are 356 and 365 DEG C respectively, air speed 1.2h-1And 2.0h-1, recycle ratio 4:1), hydrogenated products sulfur content meets state's V diesel oil standard, and device run stability is good, and energy conservation and consumption reduction effects is notable.
Claims (7)
1. the combined technical method producing ultra-low-sulphur diesel, it is characterised in that:
The hydrogenated diesel oil product that high nitrogen diesel raw material inferior, part circulate mixes with hydrogen, after the heating of heated stove, the liquid material of saturated dissolved hydrogen enters liquid phase circulation hydrogenation reactor, carries out olefins hydrogenation, desulfurization, denitrogenation and aromatic hydrocarbons saturated reaction, byproduct of reaction H2S、NH3Discharge response system；Hydrogenation products circulates to liquid phase circulation hydrogenation reactor partly as hydrogenation recycle oil, after hydrogenation products remainder mixes with hydrogen, enters catalytic adsorption desulfurization reactor, the sulfide of elimination residual, obtains ultra-low sulfur clean diesel；
The liquid material of described saturated dissolved hydrogen by the reaction condition of liquid phase circulation hydrogenation reactor beds is: reaction pressure is 4.0～12.0MPa, and fresh diesel raw material volume space velocity is 0.5～2.0h-1, temperature is 300～420 DEG C.
Described hydrogenation products remainder by the reaction condition of catalytic adsorption desulfurization reactor beds is: reaction pressure is 0.5～3.0MPa, hydrogen-oil ratio 100:1～400:1, and volume space velocity is 1.0～4.0h-1, temperature is 260～450 DEG C.
2. a kind of combined technical method producing ultra-low-sulphur diesel described in claim 1, it is characterised in that liquid phase circulation hydrogenation reactor includes the single-stage hydrogenation reactor that at least two is one another in series, and is arranged in series in a reactor；The top of single-stage hydrogenation reactor is provided with gas liberation port, discharges hydrogenation reaction by-product H2S、NH3。
3. a kind of combined technical method producing ultra-low-sulphur diesel described in claim 1, it is characterised in that catalytic adsorption desulfurization reactor is the one in fixing bed, moving bed, ebullated bed, slurry bed system, fluid bed.
4. a kind of combined technical method producing ultra-low-sulphur diesel described in claim 1, it is characterised in that described hydrogenation products initially enters high pressure air stripping separator before entering catalytic adsorption desulfurization reactor, is proposed the H dissolved by new hydrogen2S and NH3。
5. a kind of combined technical method producing ultra-low-sulphur diesel described in claim 1, it is characterised in that the volume ratio adding described hydrogenation recycle oil and the high nitrogen diesel raw material of poor quality is 1:1～4:1.
6. a kind of combined technical method producing ultra-low-sulphur diesel described in claim 1, it is characterised in that the liquid phase material of the described saturated dissolved hydrogen entering liquid phase circulation hydrogenation reactor, the amounts of hydrogen of dissolving is 1.5～10 times of course of reaction chemical hydrogen consumption amount.
7. a kind of combined technical method producing ultra-low-sulphur diesel described in claim 1, it is characterised in that the high nitrogen diesel oil inferior mixture of one or more in high nitrogen straight-run diesel oil, catalytic diesel oil, coker gas oil.
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