CN103305269A - 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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- CN103305269A CN103305269A CN2013102568556A CN201310256855A CN103305269A CN 103305269 A CN103305269 A CN 103305269A CN 2013102568556 A CN2013102568556 A CN 2013102568556A CN 201310256855 A CN201310256855 A CN 201310256855A CN 103305269 A CN103305269 A CN 103305269A
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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 the method that a kind of middle coalite tar direct hydrogenation is produced gasoline and diesel oil, more particularly, be that a kind of centering coalite tar adopts the method for raw materials pretreatment, hydrofining and three kinds of technique combinations of PSA purification to produce clean gasoline and diesel product.
Background technology
Coal tar is resulting a kind of product liquid in the dry distillation of coal process, can be divided into coal-tar heavy oil, coal-tar middle oil and coalite tar by the temperature of destructive distillation, and their composition and character have very big-difference.China's yielding poorly owing to individual enterprise's coal tar, and the enterprise that produces coal tar disperses in the region, tar resource never is fully used for a long time, except the part coal-tar heavy oil is used for extracting the lighting end of Chemicals, a small amount of coalite tar for the production of the motor spirit, remaining most of coal tar all is used as heavy fuel oil (HFO) and low-end product, causes the wasting of resources and environmental pollution.Along with the in recent years development of Chinese large-sized Chemical Industry, fixed bed, In The Fluidized Bed Coal Gasification Technology and brown coal destructive distillation upgrading technology have been applied in the 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 the byproduct in gasification, production semicoke and the low-rank coal processing upgrading process.Along with the gradually increase of the continuous newly-built and semicoke production capacity of coal gasification apparatus, the annual production of coalite tar has reached more than 6,000,000 tons in China at present.The chemical composition concentration degree is lower in the middle coalite tar, and the massfraction less than 1% of most of component should not adopt traditional separation method.It is generally acknowledged that middle coalite tar relatively is suitable for changing its composition, stability, color, smell, combustionproperty etc. by the mode of shortening, make it be converted into automotive fuel (vapour, diesel oil) and by-product related chemicals.
Adopt the method for hydrogenation to come the technology of production Chemicals to exist to coal tar, and utilize hydrogen addition technology coal tar processing to be become the method for oil fuel research was also arranged in last century, but be limited to technical qualification at that time, process conditions needs High Temperature High Pressure, there is no successfully.In recent years, be subjected to 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 constantly improvement of perfect, catalyst activity of hydrofining technology also provides technological possibility for it.The method of present coal tar hydrogenating, wherein:
Chinese invention patent CN1464031A discloses the method that a kind of coal tar hydrogenating is produced diesel oil.What the method was described mainly is that coal tar at first passes through fractionation, the last running that obtains is not as the raw material of hydrotreatment, just the light ends in the coal tar is carried out hydrotreatment, owing to not using hydrocracking catalyst, the diesel oil distillate that the course of processing obtains can only be as the blend component of diesel product, and coal tar is not utilized fully, cause the whole yield of light-end products greatly to reduce.
Chinese invention patent CN1464031A discloses a kind of coal tar hydrogenation process and catalyzer.This patent requires the special special-purpose catalyst of exploitation, flow process is common processing process, and only raw material has been carried out upgrading, contain molecular sieve in its catalyst for hydro-upgrading in addition, very responsive to the water that coal tar hydrogenating generates, because the existence of water vapor or water can make catalyzer be destroyed, reduced like this work-ing life of catalyzer, seriously destroy the performance of catalyzer and caused bed pressure drop to rise, caused device to stop work.
US Patent No. 4,855,037 discloses catalyzer and the method that a kind of coal tar hydrogenating is processed.The method is that the coal tar after the hydrotreatment is used for delayed coking.Hydrogenation technique is to occur as the pretreatment technology of delay coking of coal tar, not the purpose product such as direct production light-end products.And the method mainly is to process mink cell focus, and working pressure is high, invests larger.
Therefore, this area is more suitable in deep processing coal tar existing hydrogenation technique in the urgent need to improving existing hydrogenation technique, thereby 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 objective of the invention is on the prior art basis, provide a kind of take middle coalite tar as raw material, adopt the method for raw materials pretreatment, hydrofining and three kinds of technique combinations of PSA purification to produce clean gasoline and diesel product to it.The method can take full advantage of tar resource, and coal tar is converted into light-end products to greatest extent, improves the utilization ratio of coal tar, thereby has solved problems of the prior art.
Another object of the present invention provides a kind of device that is applied to aforesaid method.
Purpose of the present invention can reach by following measures:
A kind of middle coalite tar direct hydrogenation is produced the method for gasoline and diesel oil, and it comprises the steps:
A, middle coalite tar are processed through the slag that dewaters, takes off first, and liquid phase afterwards is through being separated into heavy oil and hydrogenating materials oil after the fractionation;
B, described hydrogenating materials oil mixed with hydrogen afterwards carry out hydrotreatment by the hydrofining unit, the processing product is carried out the Oil, Water, Gas three phase separation, obtain respectively hydrogen-rich gas, sulfur-bearing, contain ammonium sewage and hydrofined oil; Wherein said hydrofining unit comprises guard reactor, hydrofining reaction device and the hydrocracking reaction device that is connected in series successively; The purity of the hydrogen that uses in this step is greater than 96%(v);
C, described hydrofined oil is carried out fractionation, obtain respectively dry gas, gasoline fraction, diesel oil distillate and liquefied gas;
D, send into the PSA purifier units after described hydrogen-rich gas and dry gas mixed and process, the purity that obtains after the purification is greater than 99.9%(v) hydrogen return described hydrofining unit recycle.
Among the 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 among the step a is mainly finished in the raw materials pretreatment unit, the raw materials pretreatment unit mainly comprises mechanical centrifugal and preliminary fractionator, middle coalite tar dewaters, takes off slag through emchanically centrifugal separation first, enters afterwards preliminary fractionator and is separated into heavy oil and hydrogenating materials oil.Wherein hydrogenating materials oil is the cut of the final boiling point that fractionates out through separation column＜480 ℃, and the heavy oil that tower reactor obtains can not be used for hydro-upgrading, is sent to the tank field.
The hydrofining unit comprises guard reactor, hydrofining reaction device and the hydrocracking reaction device that is connected in series successively; wherein the hydrofining reaction device mainly is made of many hydrofining reactors that are connected in series; described hydrocracking reaction device mainly is made of many hydrocracking reactors that are connected in series; wherein the top of non-first hydrofining reactor and non-first hydrocracking reactor is equipped with cold hydrogen inlet, and cold hydrogen inlet all is set between each reactor bed.
Adding guard catalyst in guard reactor is mainly used in removing metal etc. and can causes the impurity that hydrogenation catalyst is poisoned.Guard catalyst can adopt existing protective material, is characterized in large pore volume, the wide aperture.Guard catalyst is made different pore volumes and shape filling of classification from top to bottom in reactor according to processing requirement, and its shape can be sphere, microballoon, bar shaped, annular, cylinder, trifolium etc.Guard catalyst is made carrier take the metallic sulfide of VIII family and VI B family as active metal component with aluminum oxide and titania mixture, its further with the non-metallic element of V A family and VII A family as auxiliary agent.Further, guard catalyst is made carrier with the mixture that aluminum oxide adds the titanium oxide of 1wt%～40wt%, take the metallic sulfide of the VIII families such as molybdenum, nickel, cobalt and VI B family as active metal component and add V A family and/some non-metallic element of VII A family is as auxiliary agent.Contain the active metal component of the nickel oxide of the molybdenum oxide of 5.0wt%～20.0wt% and 1.0wt%～10.0wt% in the 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
2It is strong that/g, this protective material hold dirty thing ability, and suitable reactive behavior is arranged.
The reaction conditions of guard reactor is: temperature of reaction is 200 ℃～450 ℃, preferred 220 ℃～400 ℃; the hydrogen dividing potential drop is 4.0MPa～25.0MPa, preferred 15.0MPa～25.0MPa; hydrogen to oil volume ratio 400:1～3000:1, preferred 600:1～1500:1, volume space velocity is 0.1h
-1～5.0h
-1, preferred 0.1h
-1～3.0h
-1
Hydrobon catalyst in the hydrofining reactor (or hydrofining reaction device) preferably loads on and contains the non-noble metal catalyzer of VI B family's metal and/or VIII family on unformed aluminum oxide and/or the silica-alumina supports, wherein VI B family metal is selected from molybdenum and/or tungsten, and VIII family metal is selected from cobalt and/or nickel.Consisting of of a kind of preferred Hydrobon catalyst: Tungsten oxide 99.999 15wt%～25wt%, molybdenum oxide 6wt%～12wt%, nickel oxide 2wt%～8wt%, all the other are aluminum oxide.The 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 the hydrofining reactor (or hydrofining reaction device) is: temperature of reaction is 300 ℃～450 ℃, preferred 340 ℃～410 ℃, the hydrogen dividing potential drop is 4.0MPa～25.0MPa, preferred 15.0MPa～25.0MPa, hydrogen to oil volume ratio is 400:1～2000:1, preferred 600:1～1500:1, air speed 0.2h
-1～2.0h
-1, preferred 0.2h
-1～1.5h
-1
Hydrocracking catalyst in the hydrocracking reactor (or hydrocracking reaction device) is preferably take the metallic sulfide of VIII family and VI B family as active metal component, mixture with aluminum oxide and titanium oxide is made carrier, and the non-metallic element that further adds V A family and/or VII A family is auxiliary agent and adds molecular sieve as promotor; Further preferred, this catalyzer is to make carrier with the mixture of the titanium oxide of aluminum oxide adding 1wt%～20wt%, take the metallic sulfide of the VIII families such as molybdenum, nickel, cobalt and VI B family as active metal component and add V A family and/some non-metallic element of VII A family adds the molecular sieve of 5wt%～30wt% as promotor as auxiliary agent in catalyst for hydro-upgrading.Its shape can be sphere, microballoon, bar shaped, annular, wheel shape etc.A kind of preferred hydrocracking catalyst is take 5.0wt%～20.0wt% molybdenum oxide and 10.0wt%～30.0wt% Tungsten oxide 99.999 as active metal component, and the 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 the hydrocracking reactor (or hydrocracking reaction device) is: temperature of reaction is 300 ℃～440 ℃, preferred 320 ℃～400 ℃, the hydrogen dividing potential drop is 4.0MPa～25.0MPa, preferred 15.0MPa～25.0MPa, hydrogen to oil volume ratio is 400:1～2000:1, preferred 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 the hydrofining unit is greater than 96%(v), the hydrogen purity after the PSA purifier units is purified is greater than 99.9%(v).PSA purifier units among the 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, CO in the dry gas
2Behind impurity, obtain respectively hydrogen and discharge gas.The hydrogen purity that obtains is greater than 99.9%(v), mix rear raw material as the hydrofining unit with new hydrogen, release gas is then delivered to the hydrofining process furnace and is acted as a fuel.Adopting molecular sieve in the PSA purifier units is sorbent material, and adsorptive pressure is 1.0MPa～3.0MPa.
The dehydration of centering coalite tar among the present invention, take off slag, fractionation pre-treatment, there is no particular requirement to the fractionation of hydrofined oil and to the PSA purification that hydrogen-containing gas carries out, only need to adopt the known existing common process of those of ordinary skill and conventional equipment to get final product.
The invention also discloses a kind of device that is applied to aforesaid method, this device comprises the raw materials pretreatment unit, the hydrofining unit, the high score tank, separating unit, PSA purifier units and circulating hydrogen compressor, the distilled oil outlet of described raw materials pretreatment unit 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 top gaseous phase outlet of the gaseous phase outlet of described high score tank and separating unit communicates by the entrance of pipeline with described PSA purifier units, the hydrogen outlet of described PSA purifier units links to each other with described circulating hydrogen compressor, and described circulating hydrogen compressor links to each other with the entrance of described hydrofining unit; Wherein said hydrofining unit comprises guard reactor, hydrofining reaction device and the hydrocracking reaction device that is connected in series successively; Described hydrofining reaction device mainly is made of many hydrofining reactors that are connected in series, described hydrocracking reaction device mainly is made of many hydrocracking reactors that are connected in series, and wherein the top of non-first hydrofining reactor and non-first hydrocracking reactor is equipped with cold hydrogen inlet.
The present invention utilizes the purify method of three kinds of technique combinations of raw materials pretreatment, hydrofining and PSA to produce clean gasoline and diesel product, has realized the cleaning fully of non-pitch heavy tar, lighting and product increment, produces to greatest extent light-end products.
Beneficial effect of the present invention:
(1) the present invention makes up raw materials pretreatment, hydrofining and three kinds of techniques of PSA purification, reasonably optimizing the coal tar hydrogenating operating method, not only can take full advantage of tar resource, and can carry out comprehensive hydro-upgrading to it, make it produce to greatest extent cleaning vapour, diesel product.The hydrofining unit comprises guard reactor, hydrofining reactor and hydrocracking reactor.Wherein, arranging of guard reactor mainly is can cause the impurity that hydrogenation catalyst is poisoned in order to remove metal in the distillate etc.; effluent further removes the impurity such as sulphur, nitrogen 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 to greatest extent quality of production gasoline and diesel product up to standard.
(2) the present invention has farthest utilized the system internal product, and the hydrogen that obtains returns the hydrofining unit, has saved hydrogen usage, discharges gas as the fuel of hydrofining unit feed process furnace, has reduced energy consumption.One timing of hydrogen dividing potential drop, higher hydrogen purity can reduce working pressure, so that initial cost significantly reduces; Highly purified hydrogen is so that catalyzer has long life cycle; Higher hydrogen dividing potential drop can significantly promote the carrying out of the reactions such as hydrodenitrification, hydrogenating desulfurization and aromatic saturation; General hydrogenation unit has been installed the high pressure blowdown system, can be used to limit the accumulation of hydrogen sulfide, light hydrocarbon gas and rare gas element in the circulating current, and the present invention all sends high score gas into the PSA purifier units, and the hydrogen purity that makes is up to 99.9%(v) more than; Reduced the pollution to environment.
(3) compared with prior art, the method has the characteristics such as good product quality, device length running period.
(4) be becoming tight in oil supply day, in the situation that vapour, diesel oil demand go up, provide new vapour, the source of diesel oil supply.
Description of drawings
Fig. 1 is a kind of process flow sheet of the present invention.
Wherein, coalite tar among the 1-, 2-raw materials pretreatment unit, 3-oily(waste)water; the 4-waste residue, 5-heavy oil, 6-hydrogenating materials oil, the new hydrogen of 7-; the 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; the 19-hydrogen-rich gas, the 20-PSA purifier units, 21-discharges gas.
Embodiment
Further specify the technological process that a kind of middle coalite tar direct hydrogenation of the present invention is produced gasoline and diesel oil below in conjunction with accompanying drawing.
As shown in Figure 1; the device that middle coalite tar direct hydrogenation is produced gasoline and diesel oil comprises raw materials pretreatment unit 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 raw materials pretreatment unit 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 top gaseous phase outlet of the gaseous phase outlet of described high score tank and separating unit communicates by the entrance of pipeline with described PSA purifier units; the hydrogen outlet of described PSA purifier units links to each other with described circulating hydrogen compressor, and described circulating hydrogen compressor links to each other with the material inlet of described guard reactor.Wherein, guard reactor is the reactor of the changeable use of a preparation and a use; the hydrofining reaction device mainly is made of two hydrofining reactors that are connected in series; the hydrocracking reaction device mainly is made of two hydrocracking reactors that are 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 is removed oily(waste)water 3 and the waste residue 4 in the material in raw materials pretreatment unit 2, and the remaining fluid phase composition is separated into heavy oil 5 and hydrogenating materials oil 6(final boiling point＜480 ℃).With hydrogenating materials oil 6; new hydrogen 7 and the recycle hydrogen after circulating hydrogen compressor 8 boosts mix sends into guard reactor 9; remove the impurity that metal etc. can cause poisoning of catalyst; effluent is sent to hydrofining reaction device 10 and further removes sulphur; the impurity such as nitrogen are to improve the quality of lightweight oil; the hydrofining reaction product enters and carries out hydrocracking reaction in the hydrocracking reaction device 11; reaction product enters carries out oil in the high score tank 12; water; the gas three phase separation; the water that obtains is sulfur-bearing; the waste water 13 of ammonium; oil phase enters follow-up separating unit 14 to be separated; obtain dry gas 15; liquefied petroleum gas (LPG) (LPG) 16; gasoline fraction 17 and diesel oil distillate 18; the hydrogen-rich gas 19 of telling from the high score tank with enter PSA purifier units 20 after the dry gas 15 that separating unit is told mixes; the release gas 21 that obtains is as the fuel of hydrofining unit feed process furnace; the hydrogen that obtains mixes raw material as the hydrofining unit, a part of hydrogen make-up as hydrofining and hydrocracking reactor through circulating hydrogen compressor 8 rear portion of boosting with new hydrogen 7.
Further specify process of the present invention and effect below in conjunction with embodiment, embodiment 1 used coal tar oil properties sees Table 1, and the character of the employed catalyzer in hydrofining unit sees Table 2.
Table 1 coal tar character
Table 2 catalyzer main character
Embodiment 1
Middle coalite tar adopts the method for raw materials pretreatment-hydrofining-three kinds of technique combinations of PSA purification to produce clean gasoline and diesel product.Middle coalite tar is removed oily(waste)water and waste residue in the material through pretreatment unit first, and the remaining fluid phase composition is separated into heavy oil and hydrogenating materials oil (final boiling point＜480 ℃).Heavy oil is sent to the tank field, and hydrogenating materials oil is sent to the hydrofining unit.In the presence of hydrogen, hydrogenating materials 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 (being high score tank 12), the dry gas that gas phase in the tank and later separation unit produce mixes by PAS purifies, a hydrogen part that obtains is mixed the raw material as the hydrofining unit with additional new hydrogen, another part is as the hydrogen make-up of hydrofining and hydrocracking reactor, and the release gas that obtains can be used as the fuel of hydrofining unit feed process furnace; Oil phase is that hydrofined oil is sent to later separation unit (being separation column) and separates in the tank, and obtaining product has dry gas, gasoline fraction, diesel oil distillate, and by-product liquefied gas (LPG) etc.; Water is sulfur-bearing, ammonium sewage in the tank, is sent to device and processes outward.Reaction process condition sees Table 3, and gasoline property sees Table 4, and diesel oil character sees Table 5.
The raw material, technical process and the corresponding catalyzer that adopt are identical with embodiment 1, selected processing condition as different from Example 1, and reaction process condition sees Table 3, and gasoline property sees Table 4, and diesel oil character sees Table 5.
Comparative Examples 1
The raw material, the catalyzer that adopt are identical with embodiment 1, as different from Example 1, this example centering coalite tar adopts the method for two kinds of technique combinations of raw materials pretreatment-hydrofining to produce gasoline and diesel product, the hydrogen-rich gas that obtains through the high score tank with after the dry gas that the later separation unit is told mixes without the PSA purifier units, but use as recycle hydrogen after passing through the digester desulfurization.Reaction process condition sees Table 3, and gasoline property sees Table 4, and diesel oil character sees Table 5.
Comparative Examples 2
The raw material embodiment 1 that adopts is identical, also is to adopt the method for raw materials pretreatment-hydrofining-three kinds of technique combinations of PSA purification to produce gasoline and diesel product to raw material.As different from Example 1, the hydrofining unit among this embodiment includes only hydrofining reactor and hydrocracking reactor, and does not have guard reactor.The used Hydrobon catalyst of this example is identical with embodiment 1 with hydrocracking catalyst, and the processing condition of reaction see Table 3, and gasoline property sees Table 4, and diesel oil character sees Table 5.
Table 3 main technologic parameters
Table 4 gasoline product quality index
Remarks: feed throughput is 200,000 ton/years
Table 5 diesel product quality index
Remarks: feed throughput is 200,000 ton/years
Claims (10)
1. the method that the coalite tar direct hydrogenation is produced gasoline and diesel oil in a kind is characterized in that comprising the steps:
A, middle coalite tar are processed through the slag that dewaters, takes off first, and liquid phase afterwards is through being separated into heavy oil and hydrogenating materials oil after the fractionation;
B, described hydrogenating materials oil mixed with hydrogen afterwards carry out hydrotreatment by the hydrofining unit, the processing product is carried out the Oil, Water, Gas three phase separation, obtain respectively hydrogen-rich gas, sulfur-bearing, contain ammonium sewage and hydrofined oil; Wherein said hydrofining unit comprises guard reactor, hydrofining reaction device and the hydrocracking reaction device that is connected in series successively; The purity of the hydrogen that uses in this step is greater than 96%(v);
C, described hydrofined oil is carried out fractionation, obtain respectively dry gas, gasoline fraction, diesel oil distillate and liquefied gas;
D, send into the PSA purifier units after described hydrogen-rich gas and dry gas mixed and process, the purity that obtains after the purification is greater than 99.9%(v) hydrogen return described hydrofining unit recycle.
2. method according to claim 1 is characterized in that described middle coalite tar is selected from the full cut of the full cut of coalite tar, coal-tar middle oil or their mixture; Described hydrogenating materials oil is the cut of the final boiling point that fractionates out through separation column＜480 ℃.
3. method according to claim 1, it is characterized in that described hydrofining reaction device mainly is made of many hydrofining reactors that are connected in series, described hydrocracking reaction device mainly is made of many hydrocracking reactors that are connected in series, 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; it is characterized in that guard catalyst in the guard reactor is take the metallic sulfide of VIII family and VI B family as active metal component; make carrier with aluminum oxide and titania mixture; its further with the non-metallic element of V A family and VII A family as auxiliary agent; the active metal component that contains the nickel oxide of the molybdenum oxide of 5.0wt%～20.0wt% and 1.0wt%～10.0wt% in the preferred guard catalyst; its pore volume is 0.20ml/g～0.80ml/g, and specific surface area is 70m
2/ g～260m
2/ g.
5. method according to claim 1; it is characterized in that the reaction conditions in the guard reactor is: temperature of reaction is 200 ℃～450 ℃, preferred 220 ℃～400 ℃; the hydrogen dividing potential drop is 4.0MPa～25.0MPa, preferred 15.0MPa～25.0MPa; hydrogen to oil volume ratio 400:1～3000:1, preferred 600:1～1500:1, volume space velocity is 0.1h
-1～5.0h
-1, preferred 0.1h
-1～3.0h
-1
6. method according to claim 1, it is characterized in that Hydrobon catalyst in the hydrofining reaction device is to load on to contain the non-noble metal catalyzer of VI B family's metal and/or VIII family on unformed aluminum oxide and/or the silica-alumina supports, wherein VI B family metal is selected from molybdenum and/or tungsten, and VIII family 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, and this catalyzer pore volume is 0.20ml/g～0.50ml/g, and specific surface area is 110m
2/ g～160m
2/ g.
7. method according to claim 1, the hydrofining reaction condition in the hydrofining reaction device that it is characterized in that is: temperature of reaction is 300 ℃～450 ℃, preferred 340 ℃～410 ℃, the hydrogen dividing potential drop is 4.0MPa～25.0MPa, preferred 15.0MPa～25.0MPa, hydrogen to oil volume ratio is 400:1～2000:1, preferred 600:1～1500:1, air speed 0.2h
-1～2.0h
-1, preferred 0.2h
-1～1.5h
-1
8. method according to claim 1, it is characterized in that hydrocracking catalyst in the hydrocracking reaction device is that metallic sulfide take VIII family and VI B family is as active metal component, mixture with aluminum oxide and titanium oxide is made carrier, and the non-metallic element that further adds V A family and/or VII A family is auxiliary agent and adds molecular sieve as promotor; Preferred hydrocracking catalyst is take 5.0wt%～20.0wt% molybdenum oxide and 10.0wt%～30.0wt% Tungsten oxide 99.999 as active metal component, and this catalyzer pore volume is 0.20ml/g～0.80ml/g, and specific surface area is 70m
2/ g～260m
2/ g.
9. method according to claim 1, the hydrocracking reaction condition in the hydrocracking reactor that it is characterized in that is: temperature of reaction is 300 ℃～440 ℃, preferred 320 ℃～400 ℃, the hydrogen dividing potential drop is 4.0MPa～25.0MPa, preferred 15.0MPa～25.0MPa, hydrogen to oil volume ratio is 400:1～2000:1, preferred 600:1～1500:1, volume space velocity 0.2h
-1～4.0h
-1, preferred 0.1h
-1～1.5h
-1
10. device that is applied to method described in the claim 1, it is characterized in that this device comprises the raw materials pretreatment unit, the hydrofining unit, the high score tank, separating unit, PSA purifier units and circulating hydrogen compressor, the hydrogenating materials oil export of described raw materials pretreatment unit 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 top gaseous phase outlet of the gaseous phase outlet of described high score tank and separating unit communicates by the entrance of pipeline with described PSA purifier units, the hydrogen outlet of described PSA purifier units links to each other with described circulating hydrogen compressor, and described circulating hydrogen compressor links to each other with the entrance of described hydrofining unit; Wherein said hydrofining unit comprises guard reactor, hydrofining reaction device and the hydrocracking reaction device that is connected in series successively; Described hydrofining reaction device mainly is made of many hydrofining reactors that are connected in series, described hydrocracking reaction device mainly is made of many hydrocracking reactors that are connected in series, and wherein the top of non-first hydrofining reactor and non-first hydrocracking reactor is equipped with cold hydrogen inlet.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310256855.6A CN103305269B (en) | 2013-06-25 | 2013-06-25 | Method for producing gasoline and diesel by directly hydrogenating medium and low temperature coal tar |
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|---|---|---|---|
| CN201310256855.6A CN103305269B (en) | 2013-06-25 | 2013-06-25 | Method for producing gasoline and diesel by directly hydrogenating medium and low temperature coal tar |
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| Publication Number | Publication Date |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104498090A (en) * | 2014-12-17 | 2015-04-08 | 王树宽 | System and method for preparing naphthenic base oil and low freezing point diesel oil through all-hydrogen coal tar |
| CN105062590A (en) * | 2015-07-31 | 2015-11-18 | 赛鼎工程有限公司 | Comprehensive utilization technology used for production of gasoline and liquefied natural gas through methanol synthesis of coke coal gas and used for deep processing of tar |
| CN105586087A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Hydrocracking method |
| CN106350111A (en) * | 2016-10-18 | 2017-01-25 | 山东宝塔新能源有限公司 | Coal tar deep processing method based on hydrofining reaction and modification reaction |
| CN110291177A (en) * | 2017-02-03 | 2019-09-27 | 环球油品有限责任公司 | It is classified hydrotreating and hydrocracking process and equipment |
| CN111647429A (en) * | 2019-03-04 | 2020-09-11 | 中国石油化工股份有限公司 | Processing method and system of inferior oil |
| EA039600B1 (en) * | 2018-05-11 | 2022-02-15 | Иннер Монголия Шэнюань Текнолоджи Ко. Лтд. | Combined method using hydrogenation process for producing high-quality fuel by medium-low-temperature coal tar |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033409A (en) * | 2006-03-06 | 2007-09-12 | 何巨堂 | Method of hydrogenation conversion for anthracene oil |
| CN101307256A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Coal tar hydrogenating modified method by single-stage method |
| CN101781577A (en) * | 2009-12-21 | 2010-07-21 | 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 |
-
2013
- 2013-06-25 CN CN201310256855.6A patent/CN103305269B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101033409A (en) * | 2006-03-06 | 2007-09-12 | 何巨堂 | Method of hydrogenation conversion for anthracene oil |
| CN101307256A (en) * | 2007-05-16 | 2008-11-19 | 中国石油化工股份有限公司 | Coal tar hydrogenating modified method by single-stage method |
| CN101781577A (en) * | 2009-12-21 | 2010-07-21 | 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 |
Non-Patent Citations (1)
| Title |
|---|
| 张晓静: "中低温煤焦油加氢技术", 《煤炭学报》 * |
Cited By (12)
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| CN105586087A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Hydrocracking method |
| 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 |
| CN104498090A (en) * | 2014-12-17 | 2015-04-08 | 王树宽 | System and method for preparing naphthenic base oil and low freezing point diesel oil through all-hydrogen coal tar |
| CN104498090B (en) * | 2014-12-17 | 2017-03-08 | 王树宽 | Perhydro moulded coal tar naphthenic base oils and the system and method for low-coagulation diesel oil |
| CN105062590A (en) * | 2015-07-31 | 2015-11-18 | 赛鼎工程有限公司 | Comprehensive utilization technology used for production of gasoline and liquefied natural gas through methanol synthesis of coke coal gas and used for deep processing of tar |
| 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 |
| CN106350111A (en) * | 2016-10-18 | 2017-01-25 | 山东宝塔新能源有限公司 | Coal tar deep processing method based on hydrofining reaction and modification reaction |
| CN106350111B (en) * | 2016-10-18 | 2018-05-29 | 山东宝塔新能源有限公司 | A kind of coal tar deep processing method based on hydrofining reaction, modification reaction |
| CN110291177A (en) * | 2017-02-03 | 2019-09-27 | 环球油品有限责任公司 | It is classified hydrotreating and hydrocracking process and equipment |
| EA039600B1 (en) * | 2018-05-11 | 2022-02-15 | Иннер Монголия Шэнюань Текнолоджи Ко. Лтд. | Combined method using hydrogenation process for producing high-quality fuel by medium-low-temperature coal tar |
| CN111647429A (en) * | 2019-03-04 | 2020-09-11 | 中国石油化工股份有限公司 | Processing method and system of inferior oil |
| CN111647429B (en) * | 2019-03-04 | 2022-01-04 | 中国石油化工股份有限公司 | Processing method and system of inferior oil |
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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. |