A kind of refinery gas hydrogenation combination technique
Technical field
The invention belongs to the hydrogenation techniques of oil Refining Technologies, are related to a kind of REFINERY GAS group technology, relate in particular to one
The combined hydrogenation method of the processing of kind REFINERY GAS and production plus hydrogen wax oil.
Background technique
The energy in global range is mainly derived from fossil energy at present, and wherein petroleum is the main next of automotive fuel
Source.Petroleum belongs to non-renewable energy resources, and not only resource is increasingly depleted, and heaviness and the aggravation of in poor quality trend, and the world passes through
Ji sustainable development, environmental regulation is increasingly strict needs to produce a large amount of light clean fuels, these are required to existing oil refining skill
Increase new oil substitutes while art is improved, satisfactory product is produced with minimum cost.It urges
Changing cracking is one of the important means of light materialization of heavy oil, but with the in poor quality and heaviness of catalyzed cracking processing raw material,
Its operating condition is more and more harsher, and light-end products yield and product property are deteriorated, and hydrotreating of FCC feedstock technology is not
Only can remove sulphur, nitrogen, metal impurities content, can also improve the cracking performance of charging, reduce FCC operating severity;Change
Kind product distribution, improves purpose product selectivity;Dry gas and coke yield are reduced, the economy of FCC apparatus is improved;Reduce purpose
Product sulfur content;Reduce SOx and NOx content etc. in regenerated flue gas.
Wax oil hydrogenation technology is to improve the most important means of catalytic cracking product quality and clean manufacturing, liquid phase wax oil hydrogenation
Technology can reach the requirement of cleaning diesel production in the case where energy consumption is greatly lowered.US6213835 and US6428686 is public
A kind of hydrogenation technique of molten hydrogen in advance has been opened, CN104560132A discloses a kind of Continuous Liquid Phase wax oil hydrogenation processing method,
CN104927902A discloses a kind of wax oil hydrogenation processing method, and this method is more focused on hydrogen and is dissolved in wax oil raw material, this
A little methods be all be to be dissolved in hydrogen in wax oil raw material carrying out hydrogenation reaction, there is no carry out benefit to reacting remaining hydrogen
With directly in addition processing after separation.
Refinery gas generally comprises dry gas and liquefied gas etc., and there are many paths for its utilization.Wherein main purposes includes dry
Gas adds the raw material after hydrogen as preparing ethylene by steam cracking, and liquefied gas adds suitable as the raw material of preparing ethylene by steam cracking, synthesis after hydrogen
Raw material, motor liquified gas of acid anhydride etc..In existing REFINERY GAS technology, it is dry that CN201410271572.3 discloses a kind of coking
Gas hydrogenation catalyst and grading method of catalyst.This method is to solve the controlling party of reaction temperature when coking dry gas adds hydrogen
Method, but reaction process temperature rise is larger.CN201010221244.4 discloses a kind of hydrogenation of liquefied petroleum gas and prepares cracking of ethylene
The method of material is arranged two reactors, cooling facility is arranged between reactor, and CN201310628425.2 discloses a kind of liquefaction
The high-temperature hydrogenation purification process of gas material, by adding the method for hydrogen to carry out alkene saturation and hydrogenation and removing impurity.It is well known that alkene
The hydrogenation reaction of the unsaturated hydrocarbons such as hydrocarbon, alkadienes, alkynes is strong exothermal reaction, and temperature rise is all very big in gas hydrogenation process, is led to
Normal 100 ~ 200 DEG C, the balance of hydrogenation reaction is destroyed as the temperature rises, and seriously increases the generation of carbon distribution, thus
Reduce the service life of catalyst.
CN201010221263.7 discloses a kind of liquefied petroleum gas-coke gasoline hydrogenation combined process method, this method
It for combined method, but is not the method using liquid-phase hydrogenatin, coker gasoline mixes that carry out fixed bed hydrogenation anti-with hydrogen first
It answers, is hydrogenated to object and liquefied gas is mixed into other reactor, only address only the problem of liquefied gas adds hydrogen temperature rise.
In conclusion REFINERY GAS treatment process is gas phase reaction in the prior art, wax oil hydrogenation is liquid phase reactor,
The two reaction type is entirely different, and therefore, REFINERY GAS processing and wax oil liquid-phase hydrogenatin combined method are rarely reported.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of hydrogenation combination technique.This method being capable of hydrotreating simultaneously
Refinery gas and production plus hydrogen wax oil.Under the premise of not influencing to add the even raising of hydrogen wax oil product quality plus hydrogen wax oil product quality
It improves the utilization efficiency of hydrogen and efficiently solves the problem of temperature rise in REFINERY GAS treatment process, it is overall to reduce equipment investment
With reduction operation energy consumption.
REFINERY GAS group technology of the present invention, including following content:
(a) wax oil feedstock oil mixes in molten hydrogen storage equipment with hydrogen with recycle oil, urges subsequently into hydrogenator plus hydrogen
Agent bed is reacted under Hydroprocessing conditions, and the catalyst bed is set as multilayer, and preferably 2-8 layers, adjacent catalyst
Molten gas equipment is set between agent bed;
(b) enter the molten gas equipment that any adjacent catalyst bed interlayer is arranged after refinery gas and/or hydrogen mixing, with from upper one
Enter next catalyst bed after the reaction stream mixing of catalyst bed to be reacted;
(c) enter supplement plus hydrogen after the hydrogenation reaction logistics that step (b) obtains mixes in molten gas equipment with refinery gas and hydrogen
Hydrogenation catalyst bed in reactor is reacted under liquid-phase hydrogenatin operating condition;
(d) hydrogenation reaction effluent that step (c) obtains is separated into gas phase and liquid phase, after isolated gas phase removal hydrogen sulfide
Refinery gas after continuing isolated hydrogen, hydrotreating, isolated liquid phase are fractionated to obtain naphtha, diesel oil and add hydrogen wax
Oil product, hydrogenation reaction effluent that the isolated liquid phase of partial high pressure separator and/or part steps (b) obtain and/or
The hydrogenation reaction logistics that part steps (c) obtain returns in molten hydrogen storage equipment as recycle oil.
In the above method, the wax oil feedstock oil used may include straight-run gas oil, wax tailings, thermal cracking wax oil, visbreaking
One of wax oils fractions such as cracking wax oil, synthesis wax oil, coal tar wax oil fraction, DCL/Direct coal liquefaction wax oil, shale oil wax oil
Or it is several, a part of catalytic cracking light cycle oil, naphthenic base straight-run diesel oil, coal tar bavin can also be mixed in wax oil feedstock oil
The poor-quality diesel-oil by cut fraction such as oil distillate.
In the above method, Hydroprocessing conditions are generally reaction pressure 3.0MPa ~ 20.0MPa, and wax oil raw material oil volume is empty
Speed is 0.2h-1~8.0h-1, 180 DEG C ~ 450 DEG C of average reaction temperature, the ratio of recycle oil and wax oil feedstock oil is 0.5:1 ~ 10:
1;Preferred operating condition is reaction pressure 4.0MPa ~ 18.0MPa, and wax oil feedstock oil volume space velocity is 0.5h-1~6.0h-1, put down
The ratio of equal 200 DEG C ~ 440 DEG C of reaction temperature, recycle oil and wax oil feedstock oil is 0.6:1 ~ 8:1.
In the above method, supplement Hydroprocessing conditions are generally reaction pressure 3.0MPa ~ 20.0MPa, wax oil raw material oil body
Product air speed is 0.3h-1~40.0h-1, 180 DEG C ~ 450 DEG C of average reaction temperature;Preferred operating condition be reaction pressure 4.0MPa ~
18.0MPa, wax oil feedstock oil volume space velocity are 0.5h-1~30.0h-1, 200 DEG C ~ 440 DEG C of average reaction temperature.
In the above method, hydrogenation active component is one or more of CO, Mo, W, Ni in hydrogenation catalyst, with oxidation
The weight content of object meter is 5%~70%, and the carrier of hydrogenation catalyst is generally aluminium oxide, amorphous silicon aluminium, silica, titanium oxide
Deng, while other auxiliary agents, such as P, Si, B, Ti, Zr can be contained.Commercial catalyst can be used, it can also be existing by this field
There is method preparation.Hydrogenation active component is the catalyst of oxidation state, carries out conventional vulcanizing treatment before the use, makes plus hydrogen is living
Property component is converted into sulphided state.Business hydrogenation catalyst mainly has, as Fushun Petrochemical Research Institute (FRIPP) is developed
3926、3936、CH-20、FF-14、FF-18、FF-24、FF-26、FF-36、FF-46、FF-56、FH-98、FH-UDS、FZC-41
Equal hydrogenation catalysts, the hydrogenation catalysts such as HR-406, HR-416, HR-448 of Inst Francais Du Petrole, the ICR154 of CLG company,
The hydrogenation catalysts such as ICR174, ICR178, ICR179, Uop Inc. HC-P, HC-K UF-210/220 newly developed, Topsor are public
The hydrogenation catalysts such as TK-525, TK-555, TK-557 of department, KF-752, KF-756 of AKZO company, KF-757, KF-840,
The hydrogenation catalysts such as KF-848, KF-901, KF-907.
In the above method, preferably wax oil feedstock oil mixes in molten hydrogen storage equipment with hydrogen after mixing with recycle oil, then into
Enter hydrogenation catalyst bed to be reacted under Hydroprocessing conditions, the hydrogenation catalyst that reaction mass passes through first accounts for all add
The 30% ~ 80% of hydrogen catalyst volume, preferably 35% ~ 75% introduce refinery gas after best 40% ~ 65%.
In the above method, wax oil feedstock oil enters after mixing with recycle oil from the top of hydrogenator, dissolves at this time
Hydrogen/or hydrogen-refinery gas mixture flow downlink can pass through catalyst bed, wax oil feedstock oil and recycle oil from up to down
It can also enter from the bottom of hydrogenator after mixing, having dissolved hydrogen/or hydrogen-refinery gas mixture flow at this time can be with
Bottom-up uplink passes through catalyst bed.
In the above method, a upper catalyst bed or next catalyst bed are with the flow direction of reaction stream
Benchmark, either up flow type or downflow system hydrogenation reaction, the bed first contacted with reaction stream in adjacent bed be it is upper, be followed by
Under touching is.
In the above method, the refinery gas may include one of gases such as dry gas, liquefied gas or several.Gas
Source can be coking, catalytic cracking, thermal cracking, visbreaking etc. reaction one or more of.
In the above method, dry gas and liquefied gas in step (b) and step (c) refinery gas are distinguished after individually mixing with hydrogen
The molten gas equipment being arranged into different adjacent catalyst bed interlayers.
A kind of specific preferred embodiment is as follows: three catalyst beds, adjacent catalyst being arranged in hydrogenator
Molten gas equipment is set between bed, the molten gas of the second catalyst bed and third catalyst bed interlayer is entered after dry gas and hydrogen mixing
Enter the molten gas equipment between supplement hydrogenator bed after equipment, liquefied gas and hydrogen mixing, into the dry of hydrogenator
Gas accounts for the 50% ~ 100% of whole dry gas raw material volumes.
In the above method, the hydrogen and refinery gas volume ratio introduced in step (b) is 2:1 ~ 200:1, preferably 5:1 ~ 150:
1, further preferred 10:1 ~ 100:1.
In the above method, hydrogenation reaction effluent separation uses high-pressure separator and/or low pressure separator.The high pressure
Separator is conventional gas-liquid separator.The hydrogenation reaction logistics isolated gas and liquid in high-pressure separator.
The low pressure separator is conventional gas-liquid separator.Isolated liquid is separated in high-low pressure in the high-pressure separator
Isolated gas and liquid in device.
In the above method, the fractionating system for being fractionated use includes stripper and/or fractionating column.In the low pressure separator
Isolated liquid, which is stripped and/or is fractionated in fractionating system, obtains naphtha, diesel oil and plus hydrogen wax oil product.
In the above method, gas separator used by gas separates is conventional separator.The high-pressure separator
In isolated hydrogen, dry in gas separator after isolated gas mixing in isolated gas and low pressure separator
Gas and liquefied gas etc. are directly entered stripper and/or fractionating column if having product liquid.
The hydrogen dissolved in wax oil liquid-phase hydrogenatin technique be it is excessive, can be dissolved in hydrogenated oil after the reaction was completed big
The hydrogen of amount increases energy consumption to cause the invalid use of hydrogen;In gas hydrogenation process, because exothermic heat of reaction amount is big
So that the temperature rise of catalyst bed is big, cause hydrogenation reaction temperature range big, not only affects the effect of hydrogenation reaction, Er Qiejia
The speed generation of catalyst carbon deposition, reduces the service life of catalyst.Result of study surface, refinery gas do not add completely with wax oil
Hydrogen handles material solubility with higher and the saturation degree of refinery gas in the liquid phase is higher, and refinery gas can effectively dissolve
Hydrogenation reaction is carried out in wax oil logistics.In wax oil liquid phase circulation hydrogenation plant, gas raw material and hydrogen are mixed into dress
Several catalyst beds behind setting, using higher reaction pressure, the hydrogenation catalyst of greater activity and the hydrogen for incorporating liquid phase
Atmosphere encloses to achieve the purpose that production plus hydrogen purification gas, and hydrogen is improved under the premise of not influencing wax oil product quality
Utilization efficiency, it is overall to reduce equipment investment and reduce operation energy consumption.
Wax oil raw material can add the method for hydrogen to produce cleaning wax oil by liquid phase circulation in the prior art, and dry gas raw material passes through
The method of fixed bed hydrogenation produces dry gas product, and liquefied gas raw material produces liquefied gas product by the method for fixed bed hydrogenation.Gas
Body has certain solubility in a liquid, the principle of this namely wax oil liquid phase circulation hydrogen addition technology exploitation, i.e., using being dissolved in
Hydrogen in wax oil realizes hydrogenation reaction, wherein the first bed catalyst undertakes maximum effect, it is a large amount of incidental plus
Hydrogen desulphurization reaction all occurs in this bed.But the hydrogen of dissolution can not react completely, can remain in reaction product a large amount of
Hydrogen, usually remaining can dissolve in the 20% ~ 70% of hydrogen.The dissolution as organic gas in wax oil such as dry gas and liquefied gas
Spend it is bigger, and with the meltage that can increase hydrogen in the presence of hydrogen.And dissolve dry gas, liquefied gas is in catalyst and hydrogen
Atmosphere be easy to occur hydrogenation reaction, realize production clean gas purpose.The present invention is by making full use of wax oil liquid phase to follow
Ring hydrogenation technique needs the characteristics of dissolving hydrogen, in order to reduce influence of the gas of dissolution to original wax oil hydrogenation to the greatest extent, by gas
Body raw material mixing hydrogen enters the catalyst bed after the first catalyst bed, completes gas using the atmosphere of hydrogen and catalyst
The hydrogenation reaction of body, and hydrogen can also be more dissolved into wax oil raw material, promote wax oil hydrogenation reaction;Or further
By in mixed gas part dry gas or whole dry gas raw material and hydrogen be mixed into the second catalyst bed, this is mainly
Olefin(e) centent is low in dry gas, and hydrogen consumption is smaller, and required activated centre quantity is few, and it is short to react the desorption process time, to wax oil plus
The influence of hydrogen reaction minimizes, and hydrogen is consumed relatively large gas and introduces the opposite catalysis lowered of subsequent wax oil hydrogenation consumption hydrogen
Agent bed, the overall influence reduced to wax oil hydrogenation effect.
The present invention further still dissolves a large amount of hydrogen by making full use of wax oil liquid phase circulation hydrogenation technique to generate in oil
The characteristics of, a supplement hydrogenator is set wax oil hydrogenation reactor is subsequent again, refinery gas dissolution of raw material is added in wax oil
In hydrogen reactant stream and enter supplement hydrogenator catalyst bed, completes gas using the hydrogen of dissolution and the atmosphere of catalyst
The hydrogenation reaction of body not only solves the problem that gas adds hydrogen temperature rise big, and the hydrogen dissolved in wax oil is used for gas and is added
Hydrogen reaction reduces hydrogen consumption;Or multiple catalyst beds are arranged in further supplement hydrogenator, it will be in mixed gas
Part dry gas or whole dry gas raw material and wax oil hydrogenation generate oil and be mixed into the first catalyst bed, by remaining gas
And/or hydrogen blend mixture enters subsequent catalyst bed, this mainly allows hydrogen consumption low, cuts the dry gas for being easiest to react first
Hydrogenation reaction is carried out, then allows hydrogen to consume slightly higher liquefied gas and is reacted into subsequent catalyst bed, and require supplementation with
It is supplemented into when hydrogen in subsequent catalyst bed entrance.Combined method aggregate performance is not influence wax oil product matter
Gas hydrogenation process is completed under the premise of amount, is obtained wax oil product and gas products, and two kinds of technical optimization combinations, is saved
Equipment investment and operating cost.
Detailed description of the invention
Fig. 1 is the flow chart of hydrogenation combination technique of the present invention.
Wherein: 1- feedstock oil, 2- raw oil pump, 3- recycle oil, 4- hydrogen-dissolving device, the new hydrogen of 5-, 6- gas raw material, 6-1- dry gas
Raw material, 6-2- liquefied gas raw material, 7- hydrogenator, 8- exhaust valve, 9- hydrofining reaction logistics, 10- high-pressure separator,
11- low pressure separator, 12- stripping/fractionating system, 13- stripping gas, 14- naphtha product, 15- diesel product, 16- add hydrogen wax
Oil product, 17- high-pressure separator gas, 18- low pressure separator gas, 19- gas separator, 20- hydrogen, 21- dry gas product,
22- liquefied gas product, 23- gas dissolver, 24- post-reactor, 25- hydrogenation reaction logistics.
Specific embodiment
The process and effect of combined hydrogenation method of the present invention, but following embodiment are further illustrated below with reference to embodiment
The limitation to the method for the present invention is not constituted.
A kind of combined hydrogenation method specific embodiment of the present invention is as follows: feedstock oil 1 is mixed with recycle oil 3, mixed
Material enters hydrogenator 7 after mixing in hydrogen-dissolving device 4 with hydrogen, and passes through the first catalyst bed, the first catalyst bed
Hydrogen is dissolved in layer effluent, and passes through the second catalyst bed, dissolves in hydrogen and gas in the second catalyst bed effluent
Raw material 6, and mixed in gas dissolver 23 by third catalyst bed, third catalyst bed reaction effluent 9 and gas raw material 6
Enter post-reactor 24 after conjunction, and pass through the first catalyst bed, dissolves in gas raw material in the first catalyst bed effluent
6, and by the second catalyst bed, the second catalyst bed effluent 25 enters high-pressure separator 10, in high-pressure separator 10
In isolated gas 17 and liquid, liquid enters low pressure separator 11, isolated 18 He of gas in low pressure separator 11
Liquid, the liquid liquid component isolated with gas separator 19 enters stripping/fractionating system 12 after mixing, in fractionating system
In after fractionation obtains naphtha 14, diesel oil 15 and hydrogen wax oil 16, gas 17 and gas 18 is added to mix under the action of stripping gas 13
Into gas separator 19, isolated hydrogen, dry gas and liquefied gas product in gas separator 19.Recycle oil 3 can be straight
It connects and is obtained from 9, can also be obtained in the isolated liquid of high-pressure separator 10.
Concrete condition of the invention is further illustrated below by embodiment.It is developed and is produced using FRIPP
FF-24 catalyst has carried out experimental study.
1 wax oil raw material main character of table
2 gas raw material main character of table
3 embodiment process conditions of table and major product property
Wax oil raw material and gas raw material can be produced directly by the combined hydrogenation method of this technology it can be seen from embodiment adds
Hydrogen wax oil product and clean gas product.