CN103305269B - Method for producing gasoline and diesel by directly hydrogenating medium and low temperature coal tar - Google Patents
Method for producing gasoline and diesel by directly hydrogenating medium and low temperature coal tar Download PDFInfo
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- CN103305269B CN103305269B CN201310256855.6A CN201310256855A CN103305269B CN 103305269 B CN103305269 B CN 103305269B CN 201310256855 A CN201310256855 A CN 201310256855A CN 103305269 B CN103305269 B CN 103305269B
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Abstract
The invention discloses a method for producing gasoline and diesel by directly hydrogenating medium and low temperature coal tar. The method comprises the steps that the medium and low temperature coal tar is firstly subjected to dehydration and deslagging, and then the liquid phase is separated into heavy oil and hydrogenated raw oil after undergoing fractionation; the hydrogenated raw oil and hydrogen are hydrogenated by a hydrofining unit after being mixed, and the treated product is subjected to oil, water and gas three-phase separation to obtain a hydrogen-rich gas, sulfur and ammonium containing sewage and hydrofined oil; the hydrofined oil is fractionated to obtain a dry gas, a gasoline fraction, a diesel fraction and a liquefied gas; and the hydrogen-rich gas and the dry gas are sent to a PSA (pressure swing adsorption) purification unit to be treated after being mixed, and the hydrogen obtained after purification is returned to the hydrofining unit to be recycled. By adopting the method, coal tar resources can be fully utilized, and the coal tar is furthest converted to the light oil products, thus improving the utilization rate of the coal tar.
Description
Technical field
The invention belongs to oil refining, petrochemical complex, coal chemical technology, be specifically related to a kind of method that middle coalite tar direct hydrogenation produces gasoline and diesel oil, more particularly, the method that combines of the three kinds of techniques that are that a kind of centering coalite tar adopts raw materials pretreatment, hydrofining and PSA purify is to produce clean gasoline and diesel product.
Background technology
Coal tar is a kind of product liquid obtained in dry distillation of coal process, and can be divided into coal-tar heavy oil, coal-tar middle oil and coalite tar by the temperature of destructive distillation, their composition and character have very big-difference.China's yielding poorly due to individual enterprise's coal tar, and the enterprise producing coal tar geographically disperses, tar resource is never fully used for a long time, except part coal-tar heavy oil is for extracting the lighting end of Chemicals, on a small quantity middle coalite tar for the production of except motor spirit, remaining most of coal tar is all used as heavy fuel oil (HFO) and low-end product, causes the wasting of resources and environmental pollution.Along with the development of Chinese large-sized Chemical Industry in recent years, fixed bed, In The Fluidized Bed Coal Gasification Technology and brown coal destructive distillation upgrading technology have been applied in multiple production process, the output of middle coalite tar also increases thereupon, up to the present, the processing and utilization of middle coalite tar has become one of important component part of Chemical Industry technology.
Middle coalite tar is gasification, the byproduct produced in semicoke and low-rank coal processing upgrading processes.Along with the constantly newly-built of coal gasification apparatus and the increase gradually of semicoke production capacity, in current China, the annual production of coalite tar has reached more than 6,000,000 tons.In middle coalite tar, chemical composition concentration degree is lower, and the massfraction of most of component, less than 1%, should not adopt traditional separation method.It is generally acknowledged that middle coalite tar compares to be suitable for changing its composition, stability, color, smell, combustionproperties etc. by the mode of shortening, make it be converted into automotive fuel (vapour, diesel oil) and by-product related chemicals.
Exist the technology that coal tar adopts the method for hydrogenation to carry out production Chemicals, and utilize hydrogen addition technology to be become by coal tar processing the method for oil fuel also to have research in last century, but the technical qualification be limited at that time, process conditions needs High Temperature High Pressure, there is no successfully.In recent years, by the impact of petroleum resources and the restriction of crude charging capacity and working ability, the output of light-end products can not be met the need of market far away, and this provides economic possibility for coal tar hydrorefining.And the improvement of continuous perfect, the catalyst activity of hydrofining technology, also for which providing technological possibility.The method of current coal tar hydrogenating, wherein:
Chinese invention patent CN1464031A discloses a kind of method that coal tar hydrogenating produces diesel oil.The mainly coal tar that the method describes is first through fractionation, the last running obtained is not as the raw material of hydrotreatment, just hydrotreatment is carried out to the light ends in coal tar, owing to not using hydrocracking catalyst, the diesel oil distillate that the course of processing obtains can only as the blend component of diesel product, and coal tar is not utilized completely, cause the overall yield of light-end products greatly to reduce.
Chinese invention patent CN1464031A discloses a kind of coal tar hydrogenation process and catalyzer.This patent requirements develops special special-purpose catalyst, flow process is common processing process, and only upgrading has been carried out to raw material, molecular sieve is contained in addition in its catalyst for hydro-upgrading, the water generated coal tar hydrogenating is very responsive, because the existence of water vapor or water can make catalyzer be destroyed, which decreases the work-ing life of catalyzer, seriously destroy the performance of catalyzer and cause bed pressure drop to rise, causing device to stop work.
US Patent No. 4,855,037 a kind of catalyzer and the method disclosing coal tar hydrogenating process.The method be by hydrotreatment after coal tar be used for delayed coking.Hydrogenation technique occurs as the pretreatment technology of delay coking of coal tar, the not object product such as direct production light-end products.And the method mainly processes mink cell focus, working pressure is high, invests larger.
Therefore, this area, in the urgent need to improving existing hydrogenation technique, makes existing hydrogenation technique be more suitable for deep processing coal tar, thus provides a kind of feasible scheme to improve the utilization ratio of tar resource for the full use of coal tar.
Summary of the invention
The object of the invention is on prior art basis, provide a kind of with middle coalite tar for raw material, to its adopt raw materials pretreatment, hydrofining and PSA to purify method that three kinds of techniques combine to produce clean gasoline and diesel product.The method can make full use of tar resource, and coal tar is converted into light-end products to greatest extent, improves the utilization ratio of coal tar, thus solves problems of the prior art.
Another object of the present invention is to provide a kind of device being applied to aforesaid method.
Object of the present invention can be reached by following measures:
Middle coalite tar direct hydrogenation produces a method for gasoline and diesel oil, and it comprises the steps:
A, middle coalite tar are first through dehydration, de-Slag treatment, and liquid phase is afterwards separated into heavy oil and Hydrogenation raw oil after fractionation;
B, described Hydrogenation raw oil is mixed with hydrogen after carry out hydrotreatment by hydrofining unit, Oil, Water, Gas three phase separation is carried out to process product, obtains hydrogen-rich gas respectively, sulfur-bearing, containing ammonium sewage and hydrofined oil; Wherein said hydrofining unit comprises the guard reactor, hydrofining reaction device and the hydrocracking reaction device that are sequentially connected in series; The purity of the hydrogen used in this step is greater than 96%(v);
C, fractionation is carried out to described hydrofined oil, obtain dry gas, gasoline fraction, diesel oil distillate and liquefied gas respectively;
D, process sending into PSA purifier units after described hydrogen-rich gas and dry gas mixing, the purity obtained after purification is greater than 99.9%(v) hydrogen return the recycle of described hydrofining unit.
In step a of the present invention, coal tar is selected from the full cut of coalite tar, the full cut of coal-tar middle oil or their mixture; Process in step a mainly completes in feed material preparation units, feed material preparation units mainly comprises mechanical centrifugal and preliminary fractionator, middle coalite tar first through emchanically centrifugal separation dehydration, de-slag, enters preliminary fractionator afterwards and is separated into heavy oil and Hydrogenation raw oil.Wherein Hydrogenation raw oil is the cut of the final boiling point < 480 DEG C fractionated out through separation column, and the heavy oil that tower reactor obtains can not be used for hydro-upgrading, is sent to tank field.
Hydrofining unit comprises the guard reactor, hydrofining reaction device and the hydrocracking reaction device that are sequentially connected in series; the hydrofining reactor that wherein hydrofining reaction device is connected in series primarily of multiple stage is formed; the hydrocracking reactor that described hydrocracking reaction device is connected in series primarily of multiple stage is formed; wherein the top of non-first hydrofining reactor and non-first hydrocracking reactor is equipped with cold hydrogen inlet, all arranges cold hydrogen inlet between each reactor bed.
In guard reactor, add guard catalyst be mainly used in removing the impurity that metal etc. can cause hydrogenation catalyst poisoning.Guard catalyst can adopt existing protective material, is characterized in large pore volume, wide aperture.Guard catalyst makes the filling of classification from top to bottom in reactor of different pore volume and shape according to processing requirement, and its shape can be spherical, microballoon, bar shaped, annular, cylinder, trifolium etc.Guard catalyst for active metal component, makes carrier with aluminum oxide and titania mixture with the metallic sulfide of VIII race and VI B race, and it is further using the non-metallic element of V A race and VII A race as auxiliary agent.Further, guard catalyst adds the titanium oxide of 1wt% ~ 40wt% mixture with aluminum oxide makes carrier, with the metallic sulfide of VIII races such as molybdenum, nickel, cobalt and VI B race for active metal component and some non-metallic element adding V A race and/VII A race for auxiliary agent.Contain the active metal component of the molybdenum oxide of 5.0wt% ~ 20.0wt% and the nickel oxide of 1.0wt% ~ 10.0wt% in preferred guard catalyst, the pore volume of described hydrogenation protecting agent is 0.20ml/g ~ 0.80ml/g, and specific surface area is 70m
2/ g ~ 260m
2/ g, it is strong that this protective material holds dirty thing ability, and have suitable reactive behavior.
The reaction conditions of guard reactor is: temperature of reaction is 200 DEG C ~ and 450 DEG C, preferably 220 DEG C ~ 400 DEG C; hydrogen dividing potential drop is 4.0MPa ~ 25.0MPa, preferably 15.0MPa ~ 25.0MPa; hydrogen to oil volume ratio 400:1 ~ 3000:1, preferably 600:1 ~ 1500:1, volume space velocity is 0.1h
-1~ 5.0h
-1, preferred 0.1h
-1~ 3.0h
-1.
Hydrobon catalyst in hydrofining reactor (or hydrofining reaction device) be preferably load on unformed aluminum oxide and/or silica-alumina supports containing the non-noble metal catalyzer of VI B race metal and/or VIII race, wherein VI B race metal is selected from molybdenum and/or tungsten, and VIII race's metal is selected from cobalt and/or nickel.Consisting of of preferred Hydrobon catalyst: Tungsten oxide 99.999 15wt% ~ 25wt%, molybdenum oxide 6wt% ~ 12wt%, nickel oxide 2wt% ~ 8wt%, all the other are aluminum oxide.Catalyzer pore volume is 0.20ml/g ~ 0.50ml/g, and specific surface area is 110m
2/ g ~ 160m
2/ g.This catalyzer is highly active Hydrobon catalyst, can effectively remove the impurity such as sulphur, nitrogen, improves the quality of light-end products.
Hydrorefined reaction conditions in hydrofining reactor (or hydrofining reaction device) is: temperature of reaction is 300 DEG C ~ and 450 DEG C, preferably 340 DEG C ~ 410 DEG C, hydrogen dividing potential drop is 4.0MPa ~ 25.0MPa, preferably 15.0MPa ~ 25.0MPa, hydrogen to oil volume ratio is 400:1 ~ 2000:1, preferably 600:1 ~ 1500:1, air speed 0.2h
-1~ 2.0h
-1, preferred 0.2h
-1~ 1.5h
-1.
Hydrocracking catalyst in hydrocracking reactor (or hydrocracking reaction device) preferably with the metallic sulfide of VIII race and VI B race for active metal component, make carrier with the mixture of aluminum oxide and titanium oxide, the non-metallic element adding V A race and/or VII A race is further auxiliary agent and adds molecular sieve as promotor; Preferred further, this catalyzer is that the mixture adding the titanium oxide of 1wt% ~ 20wt% with aluminum oxide makes carrier, with the metallic sulfide of VIII races such as molybdenum, nickel, cobalt and VI B race for active metal component and some non-metallic element adding V A race and/VII A race for auxiliary agent, in catalyst for hydro-upgrading, add the molecular sieve of 5wt% ~ 30wt% as promotor.Its shape can be spherical, microballoon, bar shaped, annular, wheel shape etc.A kind of preferred hydrocracking catalyst is with 5.0wt% ~ 20.0wt% molybdenum oxide and 10.0wt% ~ 30.0wt% Tungsten oxide 99.999 for active metal component, and catalyzer pore volume is 0.20ml/g ~ 0.80ml/g, and specific surface area is 70m
2/ g ~ 260m
2/ g.
The reaction conditions of the hydrocracking in hydrocracking reactor (or hydrocracking reaction device) is: temperature of reaction is 300 DEG C ~ and 440 DEG C, preferably 320 DEG C ~ 400 DEG C, hydrogen dividing potential drop is 4.0MPa ~ 25.0MPa, preferably 15.0MPa ~ 25.0MPa, hydrogen to oil volume ratio is 400:1 ~ 2000:1, preferably 600:1 ~ 1500:1, volume space velocity 0.2h
-1~ 4.0h
-1, preferred 0.1h
-1~ 1.5h
-1.
The hydrogen purity that the present invention uses before hydrofining unit is greater than 96%(v), the hydrogen purity after PSA purifier units is purified is greater than 99.9%(v).PSA purifier units in above-mentioned steps d of the present invention can adopt 10-2-4 flow process (10 adsorption beds, 2 air inlets are all pressed for 4 times), absorbs CO, the CO in dry gas
2after impurity, obtain hydrogen and release gas respectively.The hydrogen purity obtained is greater than 99.9%(v), as the raw material of hydrofining unit after mixing with new hydrogen, release gas then delivers to hydrofining process furnace as fuel.Adopt molecular sieve to be sorbent material in PSA purifier units, adsorptive pressure is 1.0MPa ~ 3.0MPa.
The dehydration of centering coalite tar in the present invention, de-slag, fractionation pre-treatment, to the fractionation of hydrofined oil and purify to the PSA that hydrogen-containing gas carries out and there is no particular requirement, the existing common process known by those of ordinary skill and conventional equipment only need be adopted.
The invention also discloses a kind of device being applied to aforesaid method, this device comprises feed material preparation units, hydrofining unit, high score tank, separating unit, PSA purifier units and circulating hydrogen compressor, the distilled oil outlet of described feed material preparation units connects the material inlet of described hydrofining unit, the material outlet of described hydrofining unit connects the material inlet of described high score tank, the oil phase outlet of described high score tank connects the material inlet of described separating unit, the gaseous phase outlet of described high score tank and the top gas phase outlet of separating unit are communicated by the entrance of pipeline with described PSA purifier units, the hydrogen outlet of described PSA purifier units is connected with described circulating hydrogen compressor, described circulating hydrogen compressor is connected with the entrance of described hydrofining unit, wherein said hydrofining unit comprises the guard reactor, hydrofining reaction device and the hydrocracking reaction device that are sequentially connected in series, the hydrofining reactor that described hydrofining reaction device is connected in series primarily of multiple stage is formed, the hydrocracking reactor that described hydrocracking reaction device is connected in series primarily of multiple stage is formed, and wherein the top of non-first hydrofining reactor and non-first hydrocracking reactor is equipped with cold hydrogen inlet.
The present invention's utilize raw materials pretreatment, hydrofining and PSA to purify method that three kinds of techniques combine, to produce clean gasoline and diesel product, achieves the cleaning completely of non-bituminous heavy tar, lighting and product increment, produces light-end products to greatest extent.
Beneficial effect of the present invention:
(1) the present invention's three kinds of techniques of raw materials pretreatment, hydrofining and PSA being purified combine, reasonably optimizing coal tar hydrogenating operating method, not only tar resource can be made full use of, and comprehensive hydro-upgrading can be carried out to it, make it produce clean vapour, diesel product to greatest extent.Hydrofining unit comprises guard reactor, hydrofining reactor and hydrocracking reactor.Wherein, the setting of guard reactor is mainly in order to impurity that the metal etc. removed in distillate can cause hydrogenation catalyst poisoning; effluent removes the impurity such as sulphur, nitrogen further to improve the quality of lightweight oil in hydrofining reactor; main hydrocracking and the isomerization reaction that hydrofined oil occurs in hydrocracking reactor; and be translated into lightweight oil, make its gasoline that quality of production is up to standard to greatest extent and diesel product.
(2) the present invention farthest make use of system internal product, and the hydrogen obtained returns hydrofining unit, saves hydrogen usage, and release gas, as the fuel of hydrofining unit feed process furnace, reduces energy consumption.Hydrogen dividing potential drop one timing, higher hydrogen purity can reduce working pressure, and initial cost is significantly reduced; Highly purified hydrogen makes catalyzer have longer life cycle; Higher hydrogen dividing potential drop significantly can promote the carrying out of the reactions such as hydrodenitrification, hydrogenating desulfurization and aromatic saturation; High pressure blowdown system installed by general hydrogenation unit, and can be used to the accumulation of hydrogen sulfide, light hydrocarbon gas and the rare gas element limited in circulating current, and high score gas is all sent into PSA purifier units by the present invention, obtained hydrogen purity is up to 99.9%(v) more than; Decrease the pollution to environment.
(3) compared with prior art, the method has the feature such as good product quality, device length running period.
(4) be becoming tight in oil supply day, when vapour, diesel oil demand go up, provide the source of new vapour, diesel oil supply.
Accompanying drawing explanation
Fig. 1 is a kind of process flow sheet of the present invention.
Wherein, coalite tar in 1-, 2-feed material preparation units, 3-oily(waste)water; 4-waste residue, 5-heavy oil, 6-Hydrogenation raw oil, the new hydrogen of 7-; 8-circulating hydrogen compressor, 9-guard reactor, 10-hydrofining reaction device, 11-hydrocracking reaction device; 12-high score tank, 13-sulfur-bearing, ammonium waste water, 14-separating unit, 15-dry gas; 16-liquefied petroleum gas (LPG) (LPG), 17-gasoline fraction, 18-diesel oil distillate; 19-hydrogen-rich gas, 20-PSA purifier units, 21-discharges gas.
Embodiment
The technological process that a kind of middle coalite tar direct hydrogenation of the present invention produces gasoline and diesel oil is further illustrated below in conjunction with accompanying drawing.
As shown in Figure 1, the device that middle coalite tar direct hydrogenation produces gasoline and diesel oil comprises feed material preparation units 2, guard reactor 9, hydrofining reaction device 10, hydrocracking reaction device 11, high score tank 12, separating unit 14, PSA purifier units 20 and circulating hydrogen compressor 8, the hydrogenating materials oil export of described feed material preparation units connects the material inlet of described guard reactor, the material outlet of described guard reactor connects the material inlet of described hydrofining reaction device, the material outlet of described hydrofining reaction device connects the material inlet of described hydrocracking reaction device, the material outlet of described hydrocracking reaction device connects the material inlet of described high score tank, the oil phase outlet of described high score tank connects the material inlet of described separating unit, the gaseous phase outlet of described high score tank and the top gas phase outlet of separating unit are communicated by the entrance of pipeline with described PSA purifier units, the hydrogen outlet of described PSA purifier units is connected with described circulating hydrogen compressor, described circulating hydrogen compressor is connected with the material inlet of described guard reactor.Wherein, guard reactor is the reactor of the changeable use of a preparation and a use; hydrofining reaction device is formed primarily of two hydrofining reactors be connected in series; hydrocracking reaction device is formed primarily of two hydrocracking reactors be connected in series, and wherein the top of non-first hydrofining reactor and non-first hydrocracking reactor is equipped with cold hydrogen inlet.
When producing, middle coalite tar 1 removes oily(waste)water 3 in material and waste residue 4 in feed material preparation units 2, and remaining fluid phase composition is separated into heavy oil 5 and Hydrogenation raw oil 6(final boiling point < 480 DEG C).By Hydrogenation raw oil 6, guard reactor 9 is sent in new hydrogen 7 and the mixing of the recycle hydrogen after circulating hydrogen compressor 8 boosts, remove the impurity that metal etc. can cause poisoning of catalyst, effluent is sent to hydrofining reaction device 10 and removes sulphur further, the impurity such as nitrogen are to improve the quality of lightweight oil, hydrofining reaction product enters in hydrocracking reaction device 11 and carries out hydrocracking reaction, reaction product enters in high score tank 12 carries out oil, water, gas three phase separation, the aqueous phase obtained is sulfur-bearing, the waste water 13 of ammonium, oil phase enters follow-up separating unit 14 and is separated, obtain dry gas 15, liquefied petroleum gas (LPG) (LPG) 16, gasoline fraction 17 and diesel oil distillate 18, PSA purifier units 20 is entered after the hydrogen-rich gas 19 separated from high score tank mixes with the dry gas 15 that separating unit separates, the release gas 21 obtained is as the fuel of hydrofining unit feed process furnace, the hydrogen obtained to mix raw material as hydrofining unit through circulating hydrogen compressor 8 rear portion of boosting with new hydrogen 7, a part is as the hydrogen make-up of hydrofining and hydrocracking reactor.
Further illustrate process of the present invention and effect below in conjunction with embodiment, embodiment 1 coal tar oil properties used is in table 1, and the character of the catalyzer that hydrofining unit uses is in table 2.
Table 1 coal tar character
Table 2 catalyzer main character
Embodiment 1
Middle coalite tar adopt raw materials pretreatment-hydrofining-PSA to purify method that three kinds of techniques combine is to produce clean gasoline and diesel product.Middle coalite tar first removes oily(waste)water in material and waste residue through pretreatment unit, and remaining fluid phase composition is separated into heavy oil and Hydrogenation raw oil (final boiling point < 480 DEG C).Heavy oil is sent to tank field, and Hydrogenation raw oil is sent to hydrofining unit.In the presence of hydrogen gas, Hydrogenation raw oil enters the guard reactor that corresponding catalyst is housed successively, hydrofining reaction device and hydrocracking reaction device react, reaction product is sent to three-phase high-voltage separating tank (i.e. high score tank 12), purify through PAS after the dry gas that gas phase in tank and later separation unit produce mixes, the hydrogen part obtained mixes the raw material as hydrofining unit with supplementary new hydrogen, another part is as the hydrogen make-up of hydrofining and hydrocracking reactor, the release gas obtained can be used as the fuel of hydrofining unit feed process furnace, in tank, oil phase is that hydrofined oil is sent to later separation unit (i.e. separation column) and is separated, and obtaining product has dry gas, gasoline fraction, diesel oil distillate, and by-product liquefied gas (LPG) etc., in tank, aqueous phase is sulfur-bearing, ammonium sewage, is sent to outside device and processes.Reaction process condition is in table 3, and gasoline property is in table 4, and diesel oil character is in table 5.
Embodiment 2
The raw material adopted, technical process and corresponding catalyzer are identical with embodiment 1, and processing condition selected as different from Example 1, reaction process condition is in table 3, and gasoline property is in table 4, and diesel oil character is in table 5.
Comparative example 1
The raw material adopted, catalyzer are identical with embodiment 1, as different from Example 1, the method that this routine centering coalite tar adopts raw materials pretreatment-hydrofining two kinds of techniques to combine produces gasoline and diesel product, without PSA purifier units after the hydrogen-rich gas obtained through high score tank mixes with the dry gas that later separation unit separates, and use as recycle hydrogen after being through digester desulfurization.Reaction process condition is in table 3, and gasoline property is in table 4, and diesel oil character is in table 5.
Comparative example 2
The Materials Example 1 adopted is identical, is also to produce gasoline and diesel product to raw material adopt raw materials pretreatment-hydrofining-PSA to purify method that three kinds of techniques combine.As different from Example 1, the hydrofining unit in this embodiment only includes hydrofining reactor and hydrocracking reactor, and does not have guard reactor.This example Hydrobon catalyst used is identical with embodiment 1 with hydrocracking catalyst, and the processing condition of reaction are in table 3, and gasoline property is in table 4, and diesel oil character is in table 5.
Table 3 main technologic parameters
Table 4 gasoline product quality index
Remarks: feed throughput is 200,000 tons/year
Table 5 diesel product quality index
Remarks: feed throughput is 200,000 tons/year
Claims (10)
1. in, coalite tar direct hydrogenation produces a method for gasoline and diesel oil, it is characterized in that comprising the steps:
A, middle coalite tar are first through dehydration, de-Slag treatment, and liquid phase is afterwards separated into heavy oil and Hydrogenation raw oil after fractionation;
B, described Hydrogenation raw oil is mixed with hydrogen after carry out hydrotreatment by hydrofining unit, Oil, Water, Gas three phase separation is carried out to process product, obtains hydrogen-rich gas respectively, sulfur-bearing, containing ammonium sewage and hydrofined oil; Wherein said hydrofining unit comprises the guard reactor, hydrofining reaction device and the hydrocracking reaction device that are sequentially connected in series; The purity of the hydrogen used in this step is greater than 96%(v); Described Hydrogenation raw oil is the cut of the final boiling point < 480 DEG C fractionated out through separation column;
Contain the active metal component of the molybdenum oxide of 5.0 wt % ~ 20.0 wt % and the nickel oxide of 1.0 wt % ~ 10.0 wt % in guard catalyst in guard reactor, its pore volume is 0.20 ml/g ~ 0.80 ml/g, and specific surface area is 70m
2/ g ~ 260 m
2/ g, makes carrier with aluminum oxide and titania mixture, using the non-metallic element of V A race and VII A race as auxiliary agent;
Consisting of of Hydrobon catalyst in hydrofining reaction device: Tungsten oxide 99.999 15 wt % ~ 25 wt %, molybdenum oxide 6 wt % ~ 12 wt %, nickel oxide 2 wt % ~ 8 wt %, all the other are aluminum oxide, this catalyzer pore volume is 0.20 ml/g ~ 0.50 ml/g, and specific surface area is 110 m
2/ g ~ 160 m
2/ g;
Hydrocracking catalyst in hydrocracking reaction device is for active metal component with 5.0 wt % ~ 20.0 wt % molybdenum oxides and 10.0 wt % ~ 30.0 wt % Tungsten oxide 99.999s, carrier is made with the mixture of aluminum oxide and titanium oxide, the non-metallic element simultaneously adding V A race and/or VII A race is auxiliary agent and adds molecular sieve as promotor, this catalyzer pore volume is 0.20 ml/g ~ 0.80 ml/g, and specific surface area is 70 m
2/ g ~ 260 m
2/ g;
C, fractionation is carried out to described hydrofined oil, obtain dry gas, gasoline fraction, diesel oil distillate and liquefied gas respectively;
D, process sending into PSA purifier units after described hydrogen-rich gas and dry gas mixing, the purity obtained after purification is greater than 99.9%(v) hydrogen return the recycle of described hydrofining unit.
2. method according to claim 1, is characterized in that described middle coalite tar is selected from the full cut of coalite tar, the full cut of coal-tar middle oil or their mixture.
3. method according to claim 1, it is characterized in that the hydrofining reactor that described hydrofining reaction device is connected in series primarily of multiple stage is formed, the hydrocracking reactor that described hydrocracking reaction device is connected in series primarily of multiple stage is formed, and wherein the top of non-first hydrofining reactor and non-first hydrocracking reactor is equipped with cold hydrogen inlet.
4. method according to claim 1, is characterized in that the reaction conditions in guard reactor is: temperature of reaction is 200 DEG C ~ 450 DEG C, and hydrogen dividing potential drop is 4.0MPa ~ 25.0MPa, hydrogen to oil volume ratio 400:1 ~ 3000:1, and volume space velocity is 0.1h
-1~ 5.0 h
-1.
5. method according to claim 4, is characterized in that the reaction conditions in guard reactor is: temperature of reaction is 220 DEG C ~ 400 DEG C, and hydrogen dividing potential drop is 15.0MPa ~ 25.0MPa, hydrogen to oil volume ratio 600:1 ~ 1500:1, and volume space velocity is 0.1h
-1~ 3.0 h
-1.
6. method according to claim 1, is characterized in that the hydrofining reaction condition in hydrofining reaction device is: temperature of reaction is 300 DEG C ~ 450 DEG C, and hydrogen dividing potential drop is 4.0MPa ~ 25.0MPa, and hydrogen to oil volume ratio is 400:1 ~ 2000:1, air speed 0.2h
-1~ 2.0h
-1.
7. method according to claim 6, is characterized in that the hydrofining reaction condition in hydrofining reaction device is: temperature of reaction is 340 DEG C ~ 410 DEG C, and hydrogen dividing potential drop is 15.0MPa ~ 25.0MPa, and hydrogen to oil volume ratio is 600:1 ~ 1500:1, air speed 0.2 h
-1~ 1.5 h
-1.
8. method according to claim 1, is characterized in that the hydrocracking reaction condition in hydrocracking reactor is: temperature of reaction is 300 DEG C ~ 440 DEG C, and hydrogen dividing potential drop is 4.0MPa ~ 25.0MPa, and hydrogen to oil volume ratio is 400:1 ~ 2000:1, volume space velocity 0.2 h
-1~ 4.0 h
-1.
9. method according to claim 8, the hydrocracking reaction condition in hydrocracking reactor that it is characterized in that is: temperature of reaction is 320 DEG C ~ 400 DEG C, hydrogen dividing potential drop is 15.0MPa ~ 25.0MPa, and hydrogen to oil volume ratio is 600:1 ~ 1500:1, volume space velocity 0.1 h
-1~ 1.5 h
-1.
10. one kind is applied to the device of method described in claim 1, it is characterized in that this device comprises feed material preparation units, hydrofining unit, high score tank, separating unit, PSA purifier units and circulating hydrogen compressor, the hydrogenating materials oil export of described feed material preparation units connects the material inlet of described hydrofining unit, the material outlet of described hydrofining unit connects the material inlet of described high score tank, the oil phase outlet of described high score tank connects the material inlet of described separating unit, the gaseous phase outlet of described high score tank and the top gas phase outlet of separating unit are communicated by the entrance of pipeline with described PSA purifier units, the hydrogen outlet of described PSA purifier units is connected with described circulating hydrogen compressor, described circulating hydrogen compressor is connected with the entrance of described hydrofining unit, wherein said hydrofining unit comprises the guard reactor, hydrofining reaction device and the hydrocracking reaction device that are sequentially connected in series, the hydrofining reactor that described hydrofining reaction device is connected in series primarily of multiple stage is formed, the hydrocracking reactor that described hydrocracking reaction device is connected in series primarily of multiple stage is formed, and wherein the top of non-first hydrofining reactor and non-first hydrocracking reactor is equipped with cold hydrogen inlet.
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| CN105586087B (en) * | 2014-10-24 | 2017-06-30 | 中国石油化工股份有限公司 | A kind of method being hydrocracked |
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| CN105062590B (en) * | 2015-07-31 | 2017-07-11 | 赛鼎工程有限公司 | A kind of comprehensive utilization process of coke-stove gas through methanol synthesized gasoline, co-production of liquefied natural gas and tar deep processing |
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| CN101033409A (en) * | 2006-03-06 | 2007-09-12 | 何巨堂 | Method of hydrogenation conversion for anthracene oil |
| CN101307256B (en) * | 2007-05-16 | 2013-01-09 | 中国石油化工股份有限公司 | Coal tar hydrogenating modified method by single-stage method |
| CN101781577B (en) * | 2009-12-21 | 2013-05-15 | 曲靖众一精细化工股份有限公司 | Method for producing lightweight fuel oil by utilizing mixed coal tar |
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Address after: No. 3 horses horses Science Park Avenue in Qixia District of Nanjing City, Jiangsu province 210049 Patentee after: SINOPEC NANJING ENGINEERING & CONSTRUCTION Inc. Patentee after: Sinopec Engineering (Group) Co.,Ltd. Address before: 211112 No. 1189, Jian Jian Road, Jiangning District, Jiangsu, Nanjing Patentee before: SINOPEC NANJING ENGINEERING & CONSTRUCTION Inc. Patentee before: Sinopec Engineering (Group) Co.,Ltd. |