CN102465023B - Hydrogenation modification method for coking gasoline and diesel distillates - Google Patents

Hydrogenation modification method for coking gasoline and diesel distillates Download PDF

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CN102465023B
CN102465023B CN201010539086.7A CN201010539086A CN102465023B CN 102465023 B CN102465023 B CN 102465023B CN 201010539086 A CN201010539086 A CN 201010539086A CN 102465023 B CN102465023 B CN 102465023B
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catalyzer
hydrogen
diesel
reaction
hydrogenation
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CN102465023A (en
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张学辉
刘继华
黄新露
刘涛
孙士可
王仲义
崔哲
牛世坤
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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Abstract

The invention discloses a hydrogenation modification method for coking gasoline and diesel distillates. A coking gasoline and diesel raw material is mixed with heated hydrogen and then introduced to pass through a low-temperature hydrorefining reactor and a hydrogenation modification reactor in sequence; a reaction effluent is separated and modified, and obtained liquid is distilled to obtain gas, gasoline, kerosene and diesel. In the method disclosed by the invention, a process flow of mixing hydrogen behind a furnace is adopted, the heating furnace is only used for heating the hydrogen, the mixed raw material does not pass through the heating furnace, and the temperature of the reactor is controlled based on the quantities of hot hydrogen and cold hydrogen. Compared with the prior art, the hydrogenation modification method disclosed by the invention has the advantage of saving equipment investment and being flexible in production scheme, can be used for flexible production by adjusting process conditions and production distribution according to the differences of raw material properties and product schemes; by implementation of hydrogen mixing behind the furnace, the coking raw material can be effectively prevented from being coked at a furnace tube; and by arrangement of a low-temperature protective agent reactor, olefin saturation is performed at lower temperature so as to reduce coking, meanwhile, coke powder is distributed at a protective agent bed as uniform as possible, so that the long-term operation of a hydrogenation device is ensured.

Description

A kind of hydrogenation modification method for coking gasoline/diesel fractions
Technical field
The method that the invention belongs to refining hydrocarbon ils under the condition existing at hydrogen more particularly, is a kind of method that belongs to coking gasoline and diesel fraction hydrogenating modification.
Background technology
At present, oil product market particularly will be to the demand of gasoline the trend that continues rising to the demand of light, middle matter oil product both at home and abroad, on a declining curve to the demand of heavy oil product.Meanwhile, oil property variation increasingly in the world, environmental regulation is increasingly strict.Therefore, how can realize the oil Refining Technologies that heavy oil lighting, resulting product can meet again the petrol and diesel oil product specification of continuous harshness with the rational cost of less expensive and become one of technology of domestic and international oil Refining Technologies developer's focus development.
Adopt conventional hydrofining method and highly active Hydrobon catalyst, under suitable processing condition, can effectively remove the impurity such as sulphur in petrol and diesel oil, nitrogen, colloid, make the color of oil product have certain improvement, but it is limited that treated oil density reduces, diesel oil distillate cetane value increase rate is little, still can not fundamentally solve the problem of vapour, diesel quality.
The delayed coking of residual oil is an important process of heavy oil lighting in refinery, has the refinery of delayed coking all to produce a large amount of coker gasolines and coker gas oil.Coking gasoline and diesel can significantly reduce sulphur, nitrogen and gum level by hydrofining, gained hydrotreated coker gasoline can preparing ethylene by steam cracking raw material, but it is limited that the refined diesel oil cut density of gained reduces, and cetane value increase rate is little, still needs further processing.Diesel oil hydrogenation modification, the upgrading for poor ignition quality fuel by middle pressure hydrocracking or mild hydrocracking technology normally, selecting a kind ofly can have compared with highly selective destructiveness and have the hydrocracking catalyst of better hydrogenation activity dicyclo in diesel oil and polycyclic aromatic hydrocarbons, by saturated to generate cycloalkanes benzene class mononuclear aromatics to the medium-pressure hydrocracking of the above aromatic hydrocarbons of dicyclo, continue with optionally open loop cracking, improve hydrocarbon molecules the aromaticity content in diesel oil is reduced, cetane value improves.Meanwhile, select conventional Hydrobon catalyst to carry out the refining reactions such as desulfurization, denitrogenation.
CN1316485A, US5865988 etc. have proposed a kind of technique of upgrading of gasoline being carried out by isomerizing hydrogenation, and this technique comprises two sections of cascade reactions, and first paragraph carries out olefin isomerization, then at second segment, carries out hydrogenation reaction.First paragraph filling olefin isomerization catalyst, second segment filling olefin hydrogenation catalyst.This two-stage catalytic agent can be contained in respectively two reactors, also can be contained in a reactor.Because isomerization reaction need to be carried out at the temperature higher than hydrogenation reaction temperature, therefore first carrying out isomerization reaction carries out the flow arrangement of hydrogenation reaction again, Btu utilization is unreasonable, and hydrogenator temperature in is wayward, also has the larger shortcoming of hydrogen consumption simultaneously.US6059962 discloses a kind of method of improved thiophenic sulfur and olefin alkylation reaction desulfurization, and the method adopts two-stage alkylation/distil process, can maximally utilise alkene, and restriction olefinic polymerization also reduces by product generation.But this method can only remove the sulphur in gasoline, can not reduce its olefin(e) centent.
CN1415706A discloses a kind of method of producing low-sulfur, low aromatic hydrocarbons clean diesel, the method comprises two reactors, first reactor is hydrofining/cracking case, second reactor is catalysis Gas-lift reactor, middle stripping section, upper reaction section and lower reaction section three parts, consists of.The method can reach the object of producing clean fuel, but the stock oil that the method relates to is lighter, and it is more complicated to change the catalysis air lift pressure-controlling that method mentions, and operation easier is large, the air lift of catalysis simultaneously complex structure, and engineering design difficulty is larger, performance difficulty.CN1417301A discloses a kind of method of desulfurizing and dearomatizing diesel oil deeply, the method comprises two hydrogenators, in first reactor, load catalyst for hydro-upgrading, hydrocracking catalyst or Hydrobon catalyst, in second reactor, load Hydrobon catalyst, between two reactors, be provided with a hydrogen stripped tower, to remove the gaseous impurities such as hydrogen sulfide that first reactor generates, ammonia.The method adopts under middle pressure, adopts non-precious metal catalyst to remove sulphur in diesel raw material, aromaticity content.But the method arranges high pressure hydrogen gas stripping column, facility investment and operation investment are higher.US2004/023840A1 discloses a kind of method that adopts adverse current bed to carry out hydrotreatment poor ignition quality fuel.The method adopts one or two reactor, and one of them is counter-current reactor.The method can effectively reduce sulphur content and the aromaticity content in raw material, and avoids the influence of the gaseous impurities such as hydrogen sulfide to deep desulfuration and aromatic saturation.But the counter-current reactor complex structure of mentioning in the method, operation easier is large, and facility investment is high.
CN200610045708.4 discloses a method by producing high grade of diesel oil by charking full distillate oil.Charking full distillate oil is separated into coking light distillate and coking heavy distillate, wherein in light ends oil, contains part solar oil cut, heavy distillate is to do higher heavy gas oil cut.Coking heavy distillate carries out hydro-upgrading under existing containing β zeolite catalyst for hydro-upgrading, and upgraded product mixes with coking light distillate and carries out hydrofining processing.The method need to arrange two reactors, also catalyst system is not optimized.
Summary of the invention
The technical problem to be solved in the present invention is for the deficiencies in the prior art, and a kind of method of coking gasoline and diesel mixed fraction hydro-upgrading is provided.Present method technological process is simple, and facility investment is low, and hydrogenation is effective, flexible operation.After carrying out stove, mix hydrogen, both process furnace only added hot hydrogen, and mixing raw material heats without process furnace, and each temperature of reactor is controlled by the amount of hot hydrogen and cold hydrogen.
Coking gasoline and diesel hydrogenation modification method of the present invention comprises the following steps:
(1) coking gasoline and diesel raw material mixes with the hydrogen after process furnace heating, enters low temperature hydrogenation refining reaction device and carries out refining reaction;
(2) reaction effluent of step (1), without separation, after mixing, enters hydro-upgrading reactor and carries out upgrading reaction with the hydrogen heating through process furnace;
(3) step (2) gained upgrading reaction effluent enters separator and carries out separation, obtains gas and liquid, after the desulfurization of gas air lift, recycles, and liquid enters fractionating system and carries out fractionation operation, obtains gas products, gasoline, kerosene and diesel oil.
According to hydrogenation modification method of the present invention, it is characterized in that, in step (1), can also pass into cold hydrogen, by adjusting the amount of hot hydrogen and cold hydrogen, control the temperature in of low temperature hydrogenation refining reaction device.Equally, in step (2), can also pass into cold hydrogen, by adjusting the amount of hot hydrogen and cold hydrogen, control the temperature in of hydro-upgrading reactor.
According to method of hydrotreating of the present invention, wherein said low temperature hydrogenation refining reaction device comprises at least three beds: protective material bed, catch silicea bed and Hydrobon catalyst bed.Described in step (1), hydrorefined reaction conditions is: reaction pressure 3.0MPa~12.0MPa, 100 ℃~300 ℃ of temperature of reaction, volume space velocity 0.1h during liquid -1~20.0h -1, hydrogen to oil volume ratio 300~2000.
Described hydro-upgrading reactor comprises at least three beds: Hydrobon catalyst bed, diesel modifying beds and rear catalyst for refining bed.The condition of described upgrading reaction is: reaction pressure 3.0MPa~12.0MPa, 300 ℃~450 ℃ of temperature of reaction, volume space velocity 0.1h during liquid -1~10.0h -1, hydrogen to oil volume ratio 300~2000.
In the inventive method, only have hydrogen to enter process furnace and heat, coking gasoline and diesel mixing raw material does not enter process furnace, carries out mixed hydrogen after stove, and the temperature of low temperature hydrogenation refining reaction actuator temperature and hydro-upgrading reactor is controlled by the amount of hot hydrogen and cold hydrogen.Wherein first hydrogen carried out heat exchange with hydro-upgrading reactor effluent before entering process furnace.
In the inventive method, in step (1), the protective material protective material that bed loads described in low temperature hydrogenation refining reaction device, can be both a kind of protective material, can be also that kinds of protect agent is loaded by grading distribution scheme.The described silicea of catching can be load Mo-Co type catalyzer, Mo-W-Ni type catalyzer or Mo-W-Co-Ni type catalyzer, and catalyzer pore volume is 0.25~0.55mL/g, and specific surface area is 150~300m 2/ g, the oxide compound hydrogenation active metals content of take in catalyzer is 5%~25%, has the functional silicon of catching, Hydrogenation is strong.
In the inventive method, the catalyzer of hydrofining bed filling is loaded catalyst, as being loading type Mo-Co catalyzer, Mo-W-Ni catalyzer or Mo-W-Co-Ni catalyzer.Catalyzer pore volume is 0.25~0.55mL/g, and specific surface area is 150~300m 2/ g, the oxide compound hydrogenation active metals content of take in catalyzer is 15%~45%.Mainly there is desulphurization reaction in this beds, particularly chain sulfocompound, thiophenes, the benzothiophenes etc. that contains one or two aromatic ring.
In the inventive method, diesel modifying beds is used diesel modifying catalyzer, catalyzer generally contains Y zeolite or beta molecular sieve etc., Y zeolite or the beta molecular sieve content in catalyzer is generally 0.5wt%~40.0wt%, be preferably 5.0wt%~20.0wt%, in diesel modifying catalyzer, contain hydrogenation metal component, as W, Ni etc. simultaneously.At diesel modifying beds, further there is diesel modifying reaction and the qualitative response of degree of depth removing impurities.Diesel modifying catalyzer is as 3963 catalyzer of Fushun Petrochemical Research Institute's development and production, FC-18 catalyzer, FC-14 catalyzer etc.Also can prepare by prior art, as prepared by the method as described in the patents such as CN96120988.7, CN200410020797.8.
In the inventive method, described rear catalyst for refining can be loading type Mo-Co catalyzer, Mo-W-Ni catalyzer or Mo-W-Co-Ni catalyzer.The pore volume of catalyzer is 0.25~0.55mL/g, and specific surface area is 150~300m 2/ g, the oxide compound hydrogenation active metals content of take in catalyzer is 15%~45%.
The per-cent that all types of catalyzer account for catalyzer cumulative volume is: take catalyzer cumulative volume as benchmark; protective material bed accounts for 5%~30%; catch silicea beds and account for 5%~30%; Hydrobon catalyst bed accounts for 10%~60%; diesel oil hydrogenation modification beds accounts for 10%~60%, and rear catalyst for refining bed accounts for 5%~20%.
In above-mentioned catalyzer, can contain inorganic refractory oxide carrier, various suitable auxiliary agents etc. by the conventional knowledge in this area, inorganic refractory oxide is as aluminum oxide, silicon oxide, amorphous aluminum silicide etc. simultaneously, and auxiliary agent is as P, B, Ti, Zr, F etc.Required catalyzer can be selected commercial goods catalyzer on demand, also can prepare by this area ordinary method.
In the inventive method, reacted effluent is through gas-liquid separation, and gas phase recycles after removing hydrogen sulfide, and liquid phase enters separation column and obtains various liquid-phase hydrogenatin products.
Described coking gasoline and diesel raw material can be coker gasoline and coker gas oil mixture, also can be the gasoline fraction in coking vapour, diesel oil and other source and/or the mixture of diesel oil distillate, as mixed one or more raw materials in straight-run spirit cut, straight(-run) diesel distillate, catalytic cracking diesel oil cut, pyrolysis gasoline cut, thermo-cracking diesel oil distillate etc.
In the inventive method, the processing condition in hydrogenation process and catalyst loading ratio can require to determine by the conventional specific knowledge in this area according to feedstock property and quality product.
In fraction of coker gas oil, sulfocompound can be divided into two classes according to its hydrogenating desulfurization difficulty or ease: the benzothiophenes that a class is chain sulfocompound, thiophenes, contain one or two aromatic ring, this compounds reaction steric hindrance is less, by conventional hydrofining means, is easy to remove sulphur wherein, an other class contains a plurality of aromatic rings exactly, and on aromatic ring, there are substituent many benzothiophenes, for example 4, 6-dimethyl Dibenzothiophene (4, 6-DMDBT), 4, 6, 8-trimethylammonium dibenzothiophene (4, 6, 8-TMDBT) etc., near sulphur atom, there is substituting group in the feature of this compounds, reaction compartment steric hindrance is larger, sulphur atom contacts difficulty with catalyst activity position, and there is very high boiling point (being generally greater than 350 ℃), these compounds are biggest obstacles of ultra-deep desulfurization, research shows that such sulfide is generally first after the benzene ring hydrogenation closing on containing sulfur heteroatom, C-S bond rupture to occur again and desulfurization.
Organic nitrogen compound is the poisonous substance of hydrogenation catalyst, and hydrodenitrification, hydrogenating desulfurization, hydrogenation dearomatization and hydro-upgrading reaction are had to obvious restraining effect.This restraining effect is mainly that the hydrogenation reaction active centre due to the intermediate reaction product of some nitride and most of nitride and catalyzer has very strong sorptive power, has suppressed the carrying out of other hydrogenation reactions from the angle of competitive adsorption.Research thinks, heterocyclic nitrogen is before C-N key hydrogenolysis, and the hydrogenation that must carry out heterocycle is saturated, even the non-heterocyclic nitrogen compound of phenyl amines, before C-N key hydrogenolysis, aromatic ring is also saturated in advance.Therefore, need the coupling of dissimilar catalyzer could obtain best reaction effect.
The inventive method, by investigating reaction environment and the state of coking gasoline and diesel cut different steps in hydrogenation process, has been optimized being used in conjunction with of different catalysts, has obtained desirable effect, and concrete advantage is as follows:
1, in method provided by the invention, mixed hydrogen after implementation stove, only has hydrogen to enter process furnace heating, and mixing raw material does not enter process furnace, can effectively avoid the coking problem of coking gasoline and diesel raw material in boiler tube.
2, two reactors are set in the inventive method, first reactor for filling protective material, catch that the low temperature of silicea and desulfurization, Hydrobon catalyst that nitrogen removal performance is strong is anti-refining answers device, make alkene first under cold condition hydrogenation saturated; Meanwhile, the mechanical impuritys such as coke powder are evenly distributed on as far as possible protective material and catch in silicea bed, with the long-term operation of assurance device.
3, in the inventive method, the temperature of two reactors is by being controlled by the amount of hot hydrogen and cold hydrogen respectively, and production operation is more flexible.
4,, in the inventive method, the mixed fraction that raw material is coking gasoline and diesel is only carried out hydro-upgrading to gasoline fraction and diesel oil distillate with a covering device simultaneously.
5, method provided by the invention can be used for newly-built or built hydro-refining unit or mid-pressure hydroupgrading unit, is also applicable to old plant modification.Technical process of the present invention is single hop serial flow, and flow process is fairly simple, and catalyzer is non-precious metal catalyst, and therefore, facility investment and process cost are all lower.
6, in the inventive method, in reactor, load successively dissimilar catalyzer, thereby overcome to the full extent all unfavorable factors that coking gasoline and diesel brings, the smooth running of assurance device long period.The highly selective modifying catalyst that the catalyzer that the catalyzer that Hydrogenation is good, desulfurization performance are good and open loop ability are strong matches, realize deep desulfuration, denitrogenation, Tuo Fang and selective opening reaction, simultaneously, there is appropriate lighting reaction in the last running in charging, so just can make the cetane value of diesel oil distillate be greatly improved, obtain quality steam cracking ethylene preparation raw material simultaneously.
7, the inventive method gained petroleum naphtha is quality steam cracking ethylene preparation raw material, also can be as gasoline blend component; Boat coal can be as diesel oil blending component, also can direct production boat product of coal; Diesel oil distillate has the advantages such as low-sulfur, low nitrogen, high-octane rating.The inventive method can produce sulphur and nitrogen content is all less than 1 μ g/g, and cetane value reaches more than 51 diesel oil distillates simultaneously.Simultaneously can be according to the difference of feedstock property and production object, adjusting process condition and product cut point, the mode of production is very flexible.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of hydrogenation modification method for coking gasoline/diesel fractions of the present invention.
Embodiment
Below in conjunction with accompanying drawing, method provided by the present invention is further detailed, but not thereby limiting the invention.
Technical process is described in detail as follows:
After coking gasoline and diesel mixing raw material 1 filters and boosts with hot hydrogen 24, recycle hydrogen 19 mixes, enter low-temperature purifying method reactor 2, contact olefin saturated with beds, remove the impurity such as the sulphur that easily removes in stock oil, nitrogen, deposit the solid mechanical impuritys such as coke powder, effluent 3 mixes with hot hydrogen 23, recycle hydrogen 18, enters reforming reactor 4 simultaneously, contact with catalyzer, the reactions such as desulfurization, denitrogenation, aromatic hydrocarbons open loop occur.Because hydrofining and hydro-upgrading are strong exothermal reaction, cold hydrogen 17 need be introduced in the middle of reforming reactor bed, to control temperature of reaction and temperature rise.The generation oil mixed fraction 7 of hydro-upgrading reactor 4 outlet reaction effluents 5 after interchanger 6 heat exchange enters high-pressure separator 8, carry out gas-liquid separation, it is further separated that isolated liquid phase stream 25 arrives light pressure separator 26 again, isolate gas 27, the separation column 29 of isolated liquid phase stream 28 accesss to plant, isolate overhead gas 30, petroleum naphtha 31, boat coal 32 and diesel oil distillate 33.
The isolated gaseous stream 9 of high-pressure separator enters de-hydrogen sulfide column 10, carries out the processing such as depriving hydrogen sulphide, and after the gaseous stream 11 after depriving hydrogen sulphide enters recycle compressor 12 and boosts, recycle hydrogen 14 provides reaction hydrogen 18,19 and cold hydrogen 17.The new hydrogen supplementing can be introduced after recycle compressor 12, from the mixing hydrogen 16 of circulating hydrogen compressor 12 and new hydrogen machine 13 through interchanger 6 heat exchange, hydrogen 20 after heat exchange enters process furnace 21 and heats, and the hot hydrogen 22 after heating mixes and reacts with raw material.
The following examples will further illustrate method provided by the invention, but not thereby limiting the invention.Stock oil is from the gasoline fraction of atmospheric and vacuum distillation unit and delayed coking unit and diesel oil distillate, and the ratio of gasoline fraction and diesel oil distillate is that 1: 2.2 (quality) its character is listed in table 2.Mixing raw material hydropyrolysis experiment carries out in hydrogenator, and reactor is single hop reactor.In reactor, load successively hydrogenation protecting agent A (the protective material FZC-102 of Fushun Petrochemical Research Institute's development and production) from top to bottom; the catalyst B that Hydrogenation is good (the FHRS-1 catalyzer of Fushun Petrochemical Research Institute's development and production); the catalyzer C that hydrodesulfurization performance is good (the FH-40C catalyzer of Fushun Petrochemical Research Institute's development and production); diesel oil hydrogenation modification catalyzer D (3963 catalyzer of Fushun Petrochemical Research Institute's development and production), catalyst for refining E after hydrogenation (the FH-98 catalyzer of Fushun Petrochemical Research Institute's development and production).The main physico-chemical property of catalyzer is in Table 1.The volume ratio of above-mentioned catalyzer is 1: 2: 3: 3.5: 0.5.
Comparative example 1
This comparative example adopts old process, and coker gasoline and coker gas oil carry out respectively hydrofining.Be that hydrogenating materials is respectively mixing feed naphtha and Medium diesel oil raw material.Table 3, table 5 are respectively catalyzer and processing condition and main products character.
Embodiment 1
This embodiment adopts the method for coking gasoline and diesel fraction hydrogenating modification of the present invention, and table 3, table 4, table 5 are respectively catalyzer and processing condition, product distribute and main products character.
Table 1 catalyzer physico-chemical property
Catalyzer FZC-102B FHRS-1 FH-40C 3963 FH-98
Chemical constitution, m%:
MoO3 5.2 3.5 4.5 - 9.2
WO3 - 6.1 11.1 22.0 19.8
NiO 1.3 2.2 3.2 8.8 5.1
Physical properties:
Pore volume, mL/g ≮0.60 ≮0.50 ≮0.42 ≮0.28 ≮0.25
Specific surface, m 2/g ≮260 ≮300 ≮220 ≮200 ≮120
Table 2 stock oil character
Mix petroleum naphtha (1) Medium diesel oil (2)
Density (20 ℃), g/cm 3 0.7611 0.8742
S, quality % 0.23039 1.13114
N, quality % 0.01115 0.0423
Alkene, quality % 30.1 13.4
Aromatic hydrocarbons, quality % 12.4 25.3
RON 72.0 -
Cetane value - 36.2
Boiling range, ℃
10%/50% 57/129 241/300
95%/do 208/260 365/379
(1) mixing petroleum naphtha is the mixing oil of the petroleum naphtha of atmospheric and vacuum distillation unit and delayed coking unit.
(2) Medium diesel oil is the mixing oil of the diesel oil distillate of atmospheric and vacuum distillation unit and delayed coking unit.
Table 3 catalyzer and processing condition
Figure BSA00000341106200101
Table 4 product distributes, quality %
Title Comparative example 1 diesel oil hydrogenation Embodiment 1
H 2S+NH 3 1.24 1.00
C 1 0.15 0.05
C 2 0.16 0.07
C 3 0.44 0.15
iC 4 0.71 0.21
nC 4 0.43 0.10
170 ℃ of petroleum naphthas of < 4.33 21.13
170~230 ℃ of boat coals 27.12 26.44
230 ℃ of diesel oil of > 67.13 51.76
C 5+Liquid is received 98.55 99.33
Table 5 main products character
Figure BSA00000341106200111
From embodiment 1 and comparative example 1, can find out, compare with coker gas oil hydro-upgrading with conventional coking gasoline hydrogenation refining, the inventive method is except saving facility investment, device operation is more flexible, more flexible for production quality control, under the identical even higher condition of product index, the present invention can avoid device to stop work because pressure drop is unexpected to greatest extent, the long period smooth operation of assurance device.

Claims (8)

1. a hydrogenation modification method for coking gasoline/diesel fractions, comprises the following steps:
(1) coking gasoline and diesel raw material mixes with the hydrogen after process furnace heating, enters low temperature hydrogenation refining reaction device and carries out refining reaction; Low temperature hydrogenation refining reaction device comprises three beds: protective material bed, catch silicea bed and Hydrobon catalyst bed;
(2) reaction effluent of step (1), without separation, after mixing, enters hydro-upgrading reactor and carries out upgrading reaction with the hydrogen heating through process furnace; Hydro-upgrading reactor comprises three beds: Hydrobon catalyst bed, diesel modifying beds and rear catalyst for refining bed;
(3) the upgrading reaction effluent of step (2) enters separator and carries out separation, obtains gas and liquid, and gained liquid enters fractionating system and carries out fractionation, obtains gas products, gasoline, kerosene and diesel oil;
The wherein said silicea of catching is loading type Mo-Co catalyzer, Mo-W-Ni catalyzer or Mo-W-Co-Ni catalyzer, and the pore volume of catalyzer is 0.25~0.55mL/g, and specific surface area is 150~300m 2/ g, the oxide compound hydrogenation active metals content of take in catalyzer is 5%~25%; Described Hydrobon catalyst is loading type Mo-Co catalyzer, Mo-W-Ni catalyzer or Mo-W-Co-Ni catalyzer, and catalyzer pore volume is 0.25~0.55mL/g, and specific surface area is 150~300m 2/ g, the oxide compound hydrogenation active metals content of take in catalyzer is 15%~45%; Described diesel modifying catalyzer contains Y zeolite or beta molecular sieve, and Y zeolite or the beta molecular sieve content in catalyzer is 0.5wt%~40.0wt%; Described rear catalyst for refining is loading type Mo-Co catalyzer, Mo-W-Ni catalyzer or Mo-W-Co-Ni catalyzer, and catalyzer pore volume is 0.25~0.55mL/g, and specific surface area is 150~300m 2/ g, the oxide compound hydrogenation active metals content of take in catalyzer is 15%~45%.
2. according to hydrogenation modification method claimed in claim 1, it is characterized in that, process furnace only adds hot hydrogen in step (1), and mixing raw material heats without process furnace, carries out mixed hydrogen flow process after stove.
3. in accordance with the method for claim 1, it is characterized in that, in step (1), pass into cold hydrogen, by adjusting the amount of hot hydrogen and cold hydrogen, control the temperature in of low temperature hydrogenation refining reaction device.
4. in accordance with the method for claim 1, it is characterized in that, in step (2), pass into cold hydrogen, by adjusting the amount of hot hydrogen and cold hydrogen, control the temperature in of hydro-upgrading reactor.
5. in accordance with the method for claim 1, it is characterized in that, wherein first hydrogen carried out heat exchange with hydro-upgrading reactor effluent before entering process furnace.
6. in accordance with the method for claim 1, it is characterized in that, the refining reaction condition described in step (1) is: reaction pressure 3.0MPa~12.0MPa, 100 ℃~300 ℃ of temperature of reaction, volume space velocity 0.1h during liquid -1~20.0h -1, hydrogen to oil volume ratio 300~2000; Described upgrading reaction conditions is: reaction pressure 3.0MPa~12.0MPa, 300 ℃~450 ℃ of temperature of reaction, volume space velocity 0.1h during liquid -1~10.0h -1, hydrogen to oil volume ratio 300~2000.
7. in accordance with the method for claim 1; it is characterized in that; the cumulative volume of catalyzer of take is benchmark; protective material bed accounts for 5%~30%; catch silicea beds and account for 5%~30%; Hydrobon catalyst bed accounts for 10%~60%, and diesel oil hydrogenation modification beds accounts for 10%~60%, and rear catalyst for refining bed accounts for 5%~20%.
8. in accordance with the method for claim 1, it is characterized in that, in described coking gasoline and diesel feedstock, contain one or more in straight-run spirit cut, straight(-run) diesel distillate, catalytic cracking diesel oil cut, pyrolysis gasoline cut or thermo-cracking diesel oil distillate.
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CN111097552B (en) * 2018-10-29 2022-03-08 中国石油化工股份有限公司 Method for restoring activity of low-activity hydrogenation modified catalyst
CN110041964B (en) * 2019-05-21 2021-03-12 山东京博石油化工有限公司 Production method of crude white oil product
CN114574242B (en) * 2020-11-30 2023-09-26 中国石油天然气股份有限公司 Graded filling method of hydrogenation catalyst and hydrotreating method

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