CN1415706A - Method for producing the clean diean diesel oil with low sulfur and low arene - Google Patents
Method for producing the clean diean diesel oil with low sulfur and low arene Download PDFInfo
- Publication number
- CN1415706A CN1415706A CN 01133378 CN01133378A CN1415706A CN 1415706 A CN1415706 A CN 1415706A CN 01133378 CN01133378 CN 01133378 CN 01133378 A CN01133378 A CN 01133378A CN 1415706 A CN1415706 A CN 1415706A
- Authority
- CN
- China
- Prior art keywords
- reaction
- hydrogen
- reactor
- gas
- oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
A process for preparing low-sulfur low-arylhydrocarbon clean diesel oil includes such steps as hydrorefining/hydrocracking raw hydrocarbon to obtain intermediate fraction oil, catalytic stripping to separate light fraction from heavy fraction, hydrorefining the light fraction to remove residual S and impurities, and catalytic stripping of heavy fraction for removing sulfure and arylhydrocarbon to obtain final product. Its advantage is cyclic use of two reactino segments for low cost.
Description
1, technical field
The present invention relates to a kind of processing hydrocarbon raw material and produce the method for low-sulfur, low aromatic hydrocarbons clean fuel (especially clean diesel), more particularly, is the hydrogenation technique combination technique that hydrocarbon raw material is changed into low-sulfur, low aromatic fuel.
2, background technology
As everyone knows, along with transportation in the world wide and rapid development of automobile industry, the demand of derv fuel oil increases sharply.Control about motor vehicle exhaust in the meanwhile new environmental regulation requires more and more higher to diesel quality, " world's fuel oil standard " particularly delivered in 1997 all proposed strict more requirement to sulphur content, cetane value, aromaticity content (comprising polycyclic aromatic hydrocarbon content) and the density etc. of diesel oil.Therefore, improving automobile-used fuel mass such as vapour, diesel oil is the ultimate challenge that world today's oil refining enterprise faces.
Hydrofining is one of effective means that solves at present diesel oil sulphur and aromaticity content, but because under the hydrofining operational condition of routine, catalyzer aromatic hydrocarbons saturability is limited, can not reduce aromatic content of diesel oil significantly.Therefore, in order to produce low-sulfur, low aromatics diesel product,, then must reduce air speed and improve reaction pressure if adopt conventional Hydrobon catalyst and technology.High working pressure causes high plant investment and running cost.Therefore countries in the world all can reduce the working method that aromatic content of diesel oil reduces plant investment and running cost again as far as possible significantly trying to explore to develop.
Production low-sulfur, low aromatics diesel have four kinds of routes at present:
1. high pressure, medium air speed (LHSV) single hop are saturated.This method takes 〉=pressure of 10.34MPa, and air speed is～1.0h
-1, using the catalyzer of aluminum oxide as carrier, the aromatic hydrocarbons saturation exponent can reach more than 50%.
2. high pressure, medium air speed hydrocracking.This method can be processed a certain proportion of turning oil and wax tailings, and technical process can be that single hop also can be two sections, adopts aluminum oxide, silicon-aluminum oxide or molecular sieve catalyst, and working pressure is 10.34MPa～13.79MPa.
3. two sections of middle pressures are saturated.First section is taked aluminum oxide is the catalyzer of carrier, takes noble metal catalyst for second section, and working pressure is generally 6.27MPa～10.34MPa.
4. low pressure, low-speed single hop are saturated.Working pressure is generally≤4.83MPa, and air speed is decided according to product needed, is generally 0.5h
-1Even lower, the aromatic hydrocarbons saturation exponent can reach 40%-50%.
External many companies aspect single hop flow process and two sections flow processs application patent, many documents are also introduced to some extent.
USP5114562 has described a kind of intermediate oil hydrogenating desulfurization and the saturated two-stage method work flow of aromatic hydrocarbons.This method is to adopt two independently reactors, first reactor adopts Hydrobon catalyst, and (with the aluminum oxide is carrier, with nickel, molybdenum, cobalt/molybdenum is active ingredient) the intermediate oil raw material is carried out hydrotreatment earlier, stripping tower in the middle of its resultant enters removes H through hydrogen adverse current stripping
2S and NH
3After carry out reheat, and then enter second reactor; Second reactor adopts noble metal catalyst (as platinum or palladium/aluminum oxide), operational condition and first reactor are in a ratio of high pressure low temperature, mainly carry out the aromatic hydrogenation saturated reaction, obtain meeting the generation oil of aromaticity content requirement, generate oil again through stripping, remove sulphur, gas and petroleum naphtha and obtain the finished product diesel oil.This type of two-stage method flow process is a kind of sophisticated hydrogenation technique process, and industrial application gets also many, can reach than deep desulfuration, the purpose of taking off aromatic hydrocarbons.But because this type of two-stage hydrogenation technical process complexity, increased a lot of equipment, though it in depress operation, compare with single hop high-pressure hydrogenation treatment process, investment and process cost all exceed about 20%.
Deliver the article that is entitled as " SYN TECHNOLOGY AN ATTRACTIVESOLUTION FOR MEETING FUTURE DIESEL SPECIFICATIONS " at document ARTC-99, introduced the SYNSAT flow process.The SYNSAT flow process that is used to produce low-sulfur, hang down the aromatic hydrocarbons clean diesel mainly contains two kinds, and a kind of flow process with the USP5114562 description is basic identical; Another kind of flow process is that two reactors with hydrogenating desulfurization and hydrogenation aromatics-removing are combined into a reactor, the conventional Hydrobon catalyst of reactor top filling, gas and liquid flowing flows downward, reactor lower part both can load conventional non-noble metal hydrogenation catalyst for refining, also can load noble metal catalyst, adopt the gas-liquid counter current mode to operate, downward liquid flow, gas enters reactor from reactor bottom and upwards flows, the reactor middle part is provided with gas-liquid separation zone, the H that reactant gases that comes from the reactor upper and lower and reaction generate
2S, NH
3Go out device with a small amount of lighter hydrocarbons after separate this disengaging zone and loop back the inlet on reactor top, liquid enters the bottom of reactor and takes off the aromatic hydrocarbons reaction.Though this technical process is the occupation of land and the investment of economy system greatly, but still there are 2 deficiencies: the one, the regulation range of reactor lower part dearomatization catalyst bed temperature of reaction is very narrow, owing to there is not process furnace, therefore, the temperature of reaction of taking off the aromatic hydrocarbons reaction bed must be lower than the temperature of reaction of desulfurization bed, but the temperature of reaction of taking off the arylation reaction bed again can not be lower too much than the temperature of reaction of desulfurization bed, otherwise, need to use a large amount of cold hydrogen, thereby increase the energy consumption of device, simultaneously, this flow process requires the deactivation rate basic synchronization of desulfurization catalyst and dearomatization catalyst; The 2nd, reactant gases is extracted out from the middle part of reactor, guarantees again simultaneously not carry liquid as far as possible, and this design will be very complicated.
The flow process that a kind of two-stage method is produced low-sulfur, low aromatic hydrocarbons introduced in article " Flexible new process converts aromatics in variety of dieselfeedstocks ".This method also adopts integrated reactor, reactor comprises two reaction zones up and down, fresh feed mixes with hydrogen and circulation gas through entering the upper catalyst bed layer from the integrated reactor top after the heating, this bed adopts NiMo, CoMo, the NiW catalyzer, after process and the reaction of stream full contact, reactant enters an external gas-liquid separation/recycle system, through concentrating, cooling, after the flash distillation, gas phase turns back to the top reaction zone as circulation gas, liquid phase enters the reactor lower part beds through after the heat exchange, this bed is taked the high pressure low temperature operation, adopt arene saturating activity than higher catalyzer, logistics is carried out and flows contacting at catalyst surface with hydrogen, fully obtains low-sulfur after the reaction, low aromatic hydrocarbon product.This technical process instead would not be very abundant because material carries out and flow contacting at catalyst surface with hydrogen, and mixed effect can not be fine, in addition, a gas-liquid separation/recycle system must be set, and increased facility investment.
3, summary of the invention
Purpose of the present invention is exactly the deficiency at above-mentioned Technology, develop and a kind of hydrocarbon raw material is carried out deep desulfuration, takes off aromatic hydrocarbons, the low-sulfur of specification requirement, low aromatic hydrocarbons clean diesel are satisfied in production, the hydrofining novel process of many characteristics such as can integrate investment simultaneously, expense is lower and reaction effect is good.
The invention provides a kind of hydrocarbon raw material and carry out deep desulfuration, take off aromatic hydrocarbons, produce the method for clean fuel (particularly diesel oil).Include two reaction zones in this method: first reaction zone and second reaction zone.First reaction zone comprises at least one reactor: hydrofining/cracking case and at least one reaction bed; Second reaction zone comprises a catalysis gas extracting reactor, the integrated reaction device that this catalysis gas extracting reactor is made of middle stripping stage, upper reaction section and lower reaction section three parts.
Specific embodiments of the present invention comprises the steps:
(1) first reaction zone, under the condition of hydrogen and catalyzer existence, hydrocarbon raw material carries out hydrotreatment under the hydrofining/cracking reaction condition of routine, obtain the intermediate oil logistics;
(2) at second section reaction zone, to directly deliver to the middle stripping stage of the catalysis gas extracting reactor of second section reaction zone from the reactant flow of step (1), carrying out the weight cut separates, obtain light ends and last running, described light ends is mainly hydrogen, hydrogen sulfide, ammonia and a small amount of gasifiable light hydrocarbon component;
(3) light ends that obtains in step (2) upper reaction section that enters catalysis gas extracting reactor with gas phase, further remove sulphur, aromatic hydrocarbons and other impurity remaining in the lighter hydrocarbons, the light ends reactant is discharged from the outlet of catalysis gas extracting reactor upper reaction section, and isolates hydrogen-rich gas and high pressure hydrocarbon liquid through high-pressure separator;
(4) heavy ends that step (2) the is obtained lower reaction section that enters catalysis gas extracting reactor downwards with the new hydrogen that enters from reactor bottom or through the recycle hydrogen counter current contact of depriving hydrogen sulphide, is not having H substantially
2S, NH
3Under the poisonous substance condition, carry out deep desulfuration, take off aromatic hydrocarbons, obtain reacting overhead product;
(5) will remove H from the hydrogen-rich gas of step (3) through washing or alkali cleaning
2S and NH
3After, send into circulating hydrogen compressor, enter first section reaction zone as recycle hydrogen with hydrocarbon raw material, this recycle hydrogen also can enter second section reaction zone bottom;
(6) the reaction overhead product that will obtain in step (4) is through cooling, after high pressure hydrocarbon liquid from step (3) mixes, separates through low pressure and to send into the steam gas stripping column again and separate, and obtains gas, petroleum naphtha and final diesel product.
The described hydrocarbon raw material of step (1) can be selected from oil, oil shale, gelatin liquefaction gained hydro carbons; Can be the straight run hydro carbons of refinery's atmospheric and vacuum distillation unit production, also can be in secondary processing device (as catalytic cracking, delayed coking, solvent deasphalting etc.) the gained hydro carbons one or more, comprise intermediate oil, wax oil and residue oil fraction.
The described reaction zone of step (1) adopts conventional hydrofining/cracking technology and catalyzer that those skilled in the art of the present technique were familiar with, and reactor is fixed-bed reactor; Employed catalyzer generally be with aluminum oxide, amorphous silicon aluminium and (or) molecular sieve is carrier, is active ingredient, optionally adds the refining or hydrocracking catalyst of non-noble metal hydrogenation of other various auxiliary agents such as P, Si, elements such as F, B with the oxide compound of VIB and VIII family metal such as W, Mo, Co, Ni etc.The common operational condition of described hydrotreatment reaction zone is: pressure is 2MPa-15MPa, 5MPa-10MPa preferably, temperature is 250 ℃-500 ℃, preferably 300 ℃-425 ℃, volume space velocity and hydrogen dividing potential drop are to select according to the characteristic for the treatment of material and the transformation efficiency and the refining depth of requirement during liquid.Volume space velocity is generally at 0.1h during liquid
-1-3.0h
-1, 0.5h preferably
-1-2.0h
-1Scope in.Hydrogen to oil volume ratio is 100-3000, is preferably 300-1000.
The cut scope of said intermediate oil logistics is 150 ℃～420 ℃ in the step (1), and the organosulfur weight content is～500 μ g/g.
The middle stripping stage of catalysis gas extracting reactor described in the step (2) adopts hydrogen stripped, carries out the weight cut and separates, and takes away H simultaneously
2S and NH
3, in order to avoid cause the hydrogenation catalyst (particularly noble metal catalyst) of hypomere reaction zone to poison or inhibition hydrogenation performance, thus the reaction efficiency of Hydrobon catalyst, the purpose that realizes deep desulfuration, takes off virtue improved.Catalysis gas carry device middle stripping stage adopt hydrogen stripped, reaction conditions is: pressure is 0.1MPa-15MPa, 4MPa-12MPa preferably, temperature is 100 ℃-500 ℃, preferably 250 ℃-380 ℃.
The upper reaction section of the described catalysis gas of step (3) extracting reactor comprises at least one reaction bed, and the Hydrobon catalyst that filling is conventional carries out hydrofining reaction, and reactant flow contacts with the hydrogen concurrent.Reaction conditions is: pressure is 0.1MPa-15MPa, 4MPa-12MPa preferably, and temperature is 100 ℃-500 ℃, preferably 250 ℃-380 ℃, volume space velocity and hydrogen dividing potential drop are to decide according to the characteristic and the product requirement for the treatment of material during liquid, generally at 0.2h
-1-6.0h
-1, 1.0h preferably
-1-3.5h
-1Scope in, hydrogen to oil volume ratio is 100-3000, is preferably 300-1000.
The lower reaction section of the described catalysis gas of step (4) extracting reactor comprises at least one reaction bed, load the higher non-noble metal hydrogenation catalyst for refining of traditional arene saturating activity or be the catalyzer of active ingredient, require as the requirement of sulphur, aromaticity content is selected according to the feed properties of this conversion zone and quality product with precious metals such as platinum, palladiums.Reactant flow contacts with the hydrogen reverse flow reacts, and can reach the effect that agent oil fully contacts, reaction effect is good, thus the purpose that realizes deep desulfuration, takes off aromatic hydrocarbons.The operational condition and the upper reaction section of this conversion zone are in a ratio of high pressure low temperature: pressure is 0.1MPa-15MPa, 4MPa-12MPa preferably, and temperature is 100 ℃-500 ℃, preferably 250 ℃-380 ℃, volume space velocity is generally at 0.1h during liquid
-1-3.0h
-1, 0.8h preferably
-1-2.0h
-1Scope in.Hydrogen to oil volume ratio is 100-3000, is preferably 500-800.
Described upper and lower two conversion zones of step (3) and step (4) for control reaction temperature, improve the distribution of catalyst bed interlayer temperature, inject cold hydrogen or quenching oil at the catalyst bed interlayer, and quenching oil can be the described reaction overhead product of step (4).
Diesel product sulphur content, the aromaticity content of step (6) gained can reach II, III series products quality standard in " world's fuel oil standard ", and promptly aromaticity content is not more than 15v%～20v%, sulphur content is not less than 53～55 less than 30 μ g/g～50 μ g/g, cetane value.
Compare with existing Technology, the present invention is owing to adopt conventional hydrofining/hydrocracking reaction section and catalysis gas to propose organic associating of conversion zone, particularly second section reaction zone catalysis gas is proposed the application of reaction tower, has not only saved floor space and equipment, thereby has saved investment; And widened raw material sources, strengthened the adaptability to raw material of technology.Simultaneously, the middle stripping stage of carrying reaction tower owing to second section catalysis gas adopts hydrogen stripped, takes away H
2S and NH
3, HDS, the HDA of lower reaction zone are reflected at does not have H substantially
2S and NH
3Carry out under the condition Deng the poisonous substance existence, thereby the reaction efficiency of raising Hydrobon catalyst is realized deep desulfuration, the purpose of taking off aromatic hydrocarbons.Under identical pressure, air speed condition, to compare with traditional hydrofining, the desulfuration efficiency raising 30% of hydrofining novel process disclosed in this invention, aromatic hydrocarbons saturation exponent improve 40%.In addition, lower reaction zone can be taken off aromatic hydrocarbons active high precious metal or non-noble metal hydrogenation catalyst or adopt both grading loadings according to feed properties and quality product requirement filling, has therefore increased the flexibility of operation of this two-stage hydrogenation technology.
Using the machinable raw material range of working method set forth in the present invention sees the following form:
| Severe API | ????16.8-29.9 |
| The H/C atomic ratio | ????1.4-1.9 |
| ?S，wt％ | ????0.2-1.2 |
| ?N，wt％ | ????0.01-0.1 |
| ?FIA，v％ | |
| Aromatic hydrocarbons | ????35-60 |
| Alkene | ????1-4 |
| Stable hydrocarbon | ????36-64 |
| Boiling range, ℃ | |
| ?IBP | ????154-221 |
| ?10％ | ????199-257 |
| ?50％ | ????266-302 |
| ?90％ | ????329-366 |
| ?FBP | ????371-416 |
Process the hydrocarbon raw material of above-mentioned scope with the method that this invention is set forth, but the production sulphur content is 5ppm-50ppm, aromaticity content is 5v%-20v%, and cetane value is not less than 53～55, and density is 0.81g/cm
3-0.85g/cm
3Diesel product, satisfy the requirement that following clean diesel is produced fully.
4, description of drawings
Fig. 1 is a kind of simple and easy schematic flow sheet of the present invention.
As shown in Figure 1, the charging that stock oil 1 and circulation gas 2 are formed enters fixed bed hydrogenation, and refining/cracking case 3 carries out hydrotreatment, obtain intermediate reaction overhead product 4, reaction overhead product 4 enters the middle stripping stage 5 of catalysis gas extracting reactor, obtain light ends and heavy ends through the hydrogen stripped separation, light ends enters the upper reaction section 6 of catalysis gas extracting reactor, under the hydrogen existence condition, light ends carries out with catalyst surface with hydrogen and flows contacting and reacting, reaction product 8 is after supercooler or interchanger 9 coolings, logistics 11 with enter high-pressure separator 12 after washing water 10 mix, separate and obtain gas and liquid product 15 and sour water 14, gas is sent into circulating hydrogen compressor 13 and is done the recycle hydrogen use, heavy ends from 5 enters the lower reaction section 7 of catalysis stripping reactor, contact with hydrogen 18 anti-phases, carry out deep hydrofinishing, obtain reaction product 19, reaction product 19 is through interchanger or water cooler 20 heat exchange, partial reflux is made quenching oil to catalysis stripping tower lower reaction section 7 and is used (if desired), together enter light pressure separator 22 after liquid product 21 and liquid product 15 mixing from high score 12, separate and obtain resultant 25 and sewage 24 and gas 23, resultant 25 enters product stripping tower 26 and carries out vapor-liquid separation, obtain gas 27 and product 28, gas 14 can carry out the gas comprehensive utilization, and product 28 is exactly the fine low-sulfur, low aromatic hydrocarbons clean diesel.
5, embodiment:
The raw material that present embodiment is processed is: straight-run diesel oil: coker gas oil=0.56: 0.44 (as shown in table 1), can find out in the table 1 that the sulphur content of this raw material is 1.059%, and nitrogen content is 915ppm, aromaticity content is up to 49.3v%.
This hydrofining of table 1 novel process feed properties
| Form | 56% coker gas oil: 44% catalytic diesel oil |
| Ultimate analysis | |
| S，wt％ | 1.059 |
| N，μg/g | 915 |
| Density (20 ℃), g/cm 3 | 0.8689 |
| Cetane value | 43.1 |
| Total aromatic hydrocarbons, m% | 49.3 |
| Two ring and above aromatic hydrocarbons, m% | 28.4 |
| Boiling range (D-86), ℃ | |
| IBP | 68 |
| 10％ | 181 |
| 30％ | 236 |
| 50％ | 266 |
| 70％ | 302 |
| 90％ | 340 |
| 95％ | 353 |
| FBP | 366 |
First reaction zone of present embodiment adopts conventional hydrofining technology, the FH-98 Hydrobon catalyst of filling Fushun petrochemical industry research institute exploitation, and processing condition are:
Hydrogen dividing potential drop: 6.0MPa temperature of reaction: 360 ℃
Volume space velocity: 0.6h
-1Hydrogen to oil volume ratio: 400
Hydrofining generates oil and sees Table 2, and as can be seen from Table 2, after stock oil was handled through hydrofining, the sulphur nitrogen impurity reduced, and can satisfy the charging requirement of catalysis gas extracting reactor, but aromaticity content decline is few.
Treated oil character behind table 2 FH-98 catalyst treatment table 1 stock oil
| Density (20 ℃), g/cm 3 | ????0.8688 |
| Sulphur content, ppm | ????435 |
| Nitrogen content, ppm | ????105 |
| The bromine valency | ????2.5 |
| The boiling range scope, ℃ | ????153～354 |
| Aromatic hydrocarbons, v% | ????46.1 |
When table 3 has been listed with the stock oil shown in this hydrofining novel process processing table 1, the processing condition of catalysis gas extracting reactor.Catalysis stripping tower top filling FH-98 Hydrobon catalyst, ASAT (t-2629) catalyzer of German southwestern chemical company exploitation is loaded in the bottom, and other processing condition see Table 3.
This hydrofining of table 3 novel process catalysis stripping reactor process condition
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Upper reaction section | ||||
| Pressure, MPa | ??4.0 | ??4.5 | ??6.0 | ??7.0 |
| Temperature, ℃ | ??420 | ??400 | ??405 | ??405 |
| Air speed h -1 | ??0.5 | ??0.5 | ??0.8 | ??0.8 |
| Hydrogen-oil ratio (v/v) | ??400 | ??400 | ??400 | ??400 |
| Middle stripping stage | ||||
| Pressure, MPa | ??2.0 | ??2.0 | ??2.0 | ??2.0 |
| Temperature, ℃ | ??260 | ??260 | ??260 | ??260 |
| Lower reaction section | ||||
| Pressure, MPa | ??6.5 | ??6.5 | ??8.0 | ??8.5 |
| Temperature, | ??340 | ??330 | ??320 | ??320 |
| Air speed, h -1 | ??0.8 | ??0.8 | ??1.5 | ??1.5 |
| Hydrogen-oil ratio (v/v) | ??800 | ??800 | ??800 | ??800 |
Table 4 has provided the diesel product character of 4 embodiment
The final diesel product character of this hydrofining of table 4 novel process
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Density (20 ℃), g/cm 3 | ????0.8158 | ????0.8210 | ????0.8175 | ????0.8113 |
| Aromaticity content, v% | ????17.5 | ????17.0 | ????10 | ????9.0 |
| Sulphur content, ppm | ????45 | ????40 | ????20 | ????10 |
| Cetane value | ????58 | ????58 | ????62 | ????63 |
| Boiling range, ℃ | ||||
| IBP | ????189 | ????185 | ????191 | ????190 |
| 10％ | ????224 | ????221 | ????228 | ????227 |
| 50％ | ????285 | ????280 | ????290 | ????291 |
| 90％ | ????335 | ????329 | ????330 | ????336 |
| FBP | ????352 | ????348 | ????349 | ????350 |
Use the raw material shown in the hydrofining novel process processing table 1 set forth in the present invention from four embodiment as can be seen, when the bottom reactor operating pressure of catalysis gas extracting reactor is 6.5MPa, air speed is 0.8h
-1The time, the arene engaging scraping rate can reach about 65% (content is less than 20v%), and sulphur content is less than 50ppm, and cetane value can be produced " world fuel standards II class diesel oil greater than 55; If catalysis gas extracting reactor bottom pressure is brought up to 8.0MPa-8.5MPa, air speed is brought up to 1.5h
-1The time, the arene engaging scraping rate can reach about 80% (content is less than 10v%), and sulphur content is less than 30ppm, and cetane value can be produced " world fuel standards III class diesel oil greater than 55.
From above four embodiment as can be seen, the hydrofining novel process of using this invention to set forth is processed boiling spread at 154 ℃～416 ℃, sulphur content＜1.2wt%, when aromaticity content is a hydrocarbon raw material between 35v%～60v%, but the production sulphur content is 5ppm-50ppm, aromaticity content is the low-sulfur of 5v%-20v%, low aromatics diesel, and other index also can reach requirement, meets needs and more and more stricter environmental requirement that following clean fuel oil is produced fully.
Claims (11)
1. a hydrocarbon raw material carries out deep desulfuration, takes off aromatic hydrocarbons, produce the method for clean fuel, it is characterized in that including in this method two reaction zones: first reaction zone and second reaction zone, first reaction zone comprise a reactor: hydrofining/cracking case and at least one reaction bed; Second reaction zone comprises a catalysis gas extracting reactor, and this reactor is by middle stripping stage, the integrated reaction device that upper reaction section and lower reaction section three parts constitute.
2. according to the method for the described production clean fuel of claim 1, it is characterized in that the specific embodiments of this method comprises the steps:
(1) at first reaction zone, have under hydrogen and the catalyzer existence condition, hydrocarbon raw material carries out hydrotreatment under the hydrofining/cracking reaction condition of routine, obtain the intermediate oil logistics;
(2) at second section reaction zone, will directly deliver to the middle stripping stage of second section reaction zone catalysis gas extracting reactor from the reactant flow of step (1), carry out the weight cut and separate, obtain light ends and last running;
(3) upper reaction section that will enter catalysis gas extracting reactor with gas phase at the light ends that step (2) obtain further removes wherein remaining sulphur, aromatic hydrocarbons and other impurity, the gained reactant is separated obtaining hydrogen-rich gas and high pressure hydrocarbon liquid through high pressure;
(4) heavy ends that step (2) the is obtained lower reaction section that enters catalysis gas extracting reactor downwards with new hydrogen that enters from reactor bottom or the recycle hydrogen counter current contact through purifying, is carried out deep desulfuration, is taken off aromatic hydrocarbons, obtains reacting overhead product;
(5) will remove H from the hydrogen-rich gas of step (3) through washing or alkali cleaning
2S and NH
3After, send into circulating hydrogen compressor, enter first section reaction zone or second section reaction zone bottom as recycle hydrogen with hydrocarbon raw material;
(6) the reaction overhead product that will obtain in step (4) is through cooling, and after high pressure hydrocarbon liquid from step (3) mixed, separation was sent into the steam gas stripping column again and separated through low pressure, obtains gas, petroleum naphtha and diesel product.
3. according to the method for the described production clean fuel of claim 2, the cut scope that it is characterized in that said intermediate oil logistics in the step (1) is 150 ℃～420 ℃, and the organosulfur weight content is～500 μ g/g.
4. according to the method for the described production clean fuel of claim 2, it is characterized in that the middle stripping stage of catalysis gas extracting reactor described in the step (2) adopts hydrogen stripped, pressure is 0.1MPa-15MPa, and temperature is 100 ℃-500 ℃.
5. according to the method for the described production clean fuel of claim 2, it is characterized in that the middle stripping stage of catalysis gas extracting reactor described in the step (2) adopts hydrogen stripped, pressure is 4MPa-12MPa, and temperature is 250 ℃-380 ℃.
6. according to the method for the described production clean fuel of claim 2, it is characterized in that the upper reaction section of the described catalysis gas of step (3) extracting reactor comprises at least one reaction bed, under the hydrofining condition, react that reactant flow contacts with the hydrogen concurrent; Reaction conditions is: pressure is 0.1MPa-15MPa, and temperature is 100 ℃-500 ℃, volume space velocity 0.2h during liquid
-1-6.0h
-1, hydrogen to oil volume ratio is 100-3000.
7. according to the method for the described production clean fuel of claim 6, it is characterized in that said reaction conditions is: pressure 4MPa-12MPa; 250 ℃-380 ℃ of temperature; Air speed 1.0h
-1-3.5h
-1Hydrogen to oil volume ratio is 300-1000.
8. according to the method for the described production clean fuel of claim 2, the lower reaction section that it is characterized in that the described catalysis gas of step (4) extracting reactor comprises at least-individual reaction bed, its operational condition: pressure is 0.1MPa-15MPa, and temperature is 100 ℃-500 ℃, and volume space velocity is 0.1h during liquid
-1-3.0h
-1, hydrogen to oil volume ratio is 100-3000.
9. according to the method for the described production clean fuel of claim 8, it is characterized in that described operational condition is: pressure 4MPa-12MPa; 250 ℃-380 ℃ of temperature; Volume space velocity 0.8h during liquid
-1-2.0h
-1Hydrogen to oil volume ratio 500-800.
10. according to the method for the described production clean fuel of claim 2, it is characterized in that described upper and lower two conversion zones of step (3) and step (4), for control reaction temperature, improve the distribution of catalyst bed interlayer temperature, inject cold hydrogen or quenching oil at the catalyst bed interlayer.
11., it is characterized in that said quenching oil is the described reaction overhead product of step (4) according to the method for the described production clean fuel of claim 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011333782A CN1175090C (en) | 2001-10-30 | 2001-10-30 | Method for producing the clean diean diesel oil with low sulfur and low arene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011333782A CN1175090C (en) | 2001-10-30 | 2001-10-30 | Method for producing the clean diean diesel oil with low sulfur and low arene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1415706A true CN1415706A (en) | 2003-05-07 |
| CN1175090C CN1175090C (en) | 2004-11-10 |
Family
ID=4671761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011333782A Expired - Lifetime CN1175090C (en) | 2001-10-30 | 2001-10-30 | Method for producing the clean diean diesel oil with low sulfur and low arene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1175090C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313574C (en) * | 2003-05-31 | 2007-05-02 | 中国石油化工股份有限公司 | Deep desulphurizing and dearomating process for diesel oil |
| CN100381542C (en) * | 2004-10-29 | 2008-04-16 | 中国石油化工股份有限公司 | One-stage tandem combined process for hydrocracking- aryl removal |
| CN100478425C (en) * | 2004-07-29 | 2009-04-15 | 中国石油化工股份有限公司 | Method for rectifying qualities of fractions of diesel oil |
| CN101892076A (en) * | 2010-07-21 | 2010-11-24 | 广西大学 | Method for producing clean diesel oil |
| CN101747936B (en) * | 2008-11-28 | 2012-12-12 | 中国石油化工股份有限公司 | Hydrogenation method for producing high-quality low-sulfur diesel fraction |
| CN103509598A (en) * | 2012-06-15 | 2014-01-15 | 中国石油化工集团公司 | Hydrogenation system for producing ultralow-sulfur diesel oil, and method thereof |
| CN105219433A (en) * | 2014-05-30 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of method of diesel oil ultra-deep hydrodesulfuration and decolouring |
| CN105273754A (en) * | 2014-05-30 | 2016-01-27 | 中国石油化工股份有限公司 | Diesel oil deep hydrodesulfurization method |
| CN105713655A (en) * | 2012-08-03 | 2016-06-29 | 鲁姆斯科技公司 | Residue hydrocracking |
| CN111518588A (en) * | 2019-02-05 | 2020-08-11 | Ifp 新能源公司 | Novel process scheme for producing low-sulfur marine fuel |
| CN115785995A (en) * | 2021-09-10 | 2023-03-14 | 中国石油化工股份有限公司 | Inferior diesel oil hydrotreating method and device |
-
2001
- 2001-10-30 CN CNB011333782A patent/CN1175090C/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1313574C (en) * | 2003-05-31 | 2007-05-02 | 中国石油化工股份有限公司 | Deep desulphurizing and dearomating process for diesel oil |
| CN100478425C (en) * | 2004-07-29 | 2009-04-15 | 中国石油化工股份有限公司 | Method for rectifying qualities of fractions of diesel oil |
| CN100381542C (en) * | 2004-10-29 | 2008-04-16 | 中国石油化工股份有限公司 | One-stage tandem combined process for hydrocracking- aryl removal |
| CN101747936B (en) * | 2008-11-28 | 2012-12-12 | 中国石油化工股份有限公司 | Hydrogenation method for producing high-quality low-sulfur diesel fraction |
| CN101892076A (en) * | 2010-07-21 | 2010-11-24 | 广西大学 | Method for producing clean diesel oil |
| CN103509598B (en) * | 2012-06-15 | 2016-01-13 | 中国石油化工集团公司 | A kind of hydrogenation system and method for producing ultra-low-sulphur diesel |
| CN103509598A (en) * | 2012-06-15 | 2014-01-15 | 中国石油化工集团公司 | Hydrogenation system for producing ultralow-sulfur diesel oil, and method thereof |
| CN105713655A (en) * | 2012-08-03 | 2016-06-29 | 鲁姆斯科技公司 | Residue hydrocracking |
| CN105273754A (en) * | 2014-05-30 | 2016-01-27 | 中国石油化工股份有限公司 | Diesel oil deep hydrodesulfurization method |
| CN105219433A (en) * | 2014-05-30 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of method of diesel oil ultra-deep hydrodesulfuration and decolouring |
| CN111518588A (en) * | 2019-02-05 | 2020-08-11 | Ifp 新能源公司 | Novel process scheme for producing low-sulfur marine fuel |
| CN111518588B (en) * | 2019-02-05 | 2023-05-12 | Ifp 新能源公司 | Novel technological scheme for producing low-sulfur marine fuel |
| CN115785995A (en) * | 2021-09-10 | 2023-03-14 | 中国石油化工股份有限公司 | Inferior diesel oil hydrotreating method and device |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1175090C (en) | 2004-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101045884B (en) | Process of producing clean diesel oil and low carbon olefin with residual oil and heavy fraction oil | |
| CN100590182C (en) | Method for producing cleaning oil from coal-tar oil | |
| CN100558863C (en) | A kind of combined method of producing cleaning oil from coal-tar oil | |
| CN101294107B (en) | Method for preparing fuel oil with coal oil hydrogenation | |
| CN101307257B (en) | Coal tar hydrogenating modified method by two-stage method | |
| CN101117594B (en) | Hydrogenation method for producing clean diesel oil | |
| CN101307256B (en) | Coal tar hydrogenating modified method by single-stage method | |
| CN1175090C (en) | Method for producing the clean diean diesel oil with low sulfur and low arene | |
| CN109777509A (en) | A kind of two-segment hydrocracking method | |
| CN105273745B (en) | Low-grade diesel oil selective hydrogenation aromatic hydrocarbon removing method | |
| CN1986748B (en) | Diesel oil fraction overhydrogenating modification process | |
| CN104004541B (en) | A kind of preparation method of coal-based high arene underwater content stock oil | |
| CN103525461A (en) | Hydrocracking method | |
| CN1343758A (en) | Process for preparing jet fuel and/or diesel oil or tail oil | |
| CN102311782B (en) | Method for producing diesel oil by purifying coal tar through hydrogenating | |
| CN100351346C (en) | Medium pressure hydrocracking process for preparing jet fuel | |
| CN1197940C (en) | Method for producing good quality diesel oil | |
| CN103059974A (en) | Hydrotreatment method for producing food grade solvent naphtha | |
| CN100594232C (en) | Inferior fraction oil upgrading process | |
| CN1233797C (en) | Hydrogenating modifying process for direct liquefying diesel oil of coal | |
| CN1331989C (en) | Method of hydro up grading isomerizing pour point depression to produce diesel oil | |
| CN102465015A (en) | Shale oil processing method | |
| CN102453536B (en) | Integrated hydrogenation method for producing clean diesel | |
| CN1986747B (en) | Diesel oil fraction hydrogenating modification process | |
| CN114736708B (en) | Wax oil liquid phase hydrotreating method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20041110 |