CN104987886B - The processing method of a kind of coal and system - Google Patents
The processing method of a kind of coal and system Download PDFInfo
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- CN104987886B CN104987886B CN201510400624.7A CN201510400624A CN104987886B CN 104987886 B CN104987886 B CN 104987886B CN 201510400624 A CN201510400624 A CN 201510400624A CN 104987886 B CN104987886 B CN 104987886B
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Abstract
The invention provides the processing method of a kind of coal and system.This processing method at least includes: the dry distillation of coal or coal gasification, coal tar hydrocracking, aromatic hydrocarbons associating, the technique such as light-hydrocarbon aromatized, prepared by dehydrogenating propane, polypropylene, major product has diesel oil, xylol, benzene, heavy aromatics and polypropylene etc..This system at least includes: the dry distillation of coal or coal gasification apparatus, coal tar hydrocracking device, Aromatic Hydrocarbon United Plant, light-hydrocarbon aromatized device, dehydrogenating propane device and polypropylene preparation facilities etc..Processing method provided by the invention and system can produce the high value added products such as diesel oil, gasoline blend component, aromatic hydrocarbons and alkene, overcome the problem that coal tar processing is difficult, are a kind of coal, oil, aromatic hydrocarbons and alkene integral processing method and system.
Description
Technical field
The present invention relates to the processing method of a kind of coal and system, belong to Coal Chemical Industry and technical field of petrochemical industry.
Background technology
The dry distillation of coal and Coal Gasification Technology are the key technologies of Coal Chemical Industry.When middle low temperature distillation, decapacitation generates half afocal, also can generate coal gas and coal tar, and coal tar mass rate of production is typically between 8%～20%.Coal gasification manufactures coal gas or preparing synthetic gas (CO2+H2) when producing other chemical products, also can produce coal tar, coal tar mass rate of production is between 4%～12%.China is the country that rich coal is oil-poor, is also coal production and consumption big country, and China is again maximum in the world coke production state, country of consumption and exported country, the substantial amounts of coal tar of by-product simultaneously.Except semi-coke enterprise can provide substantial amounts of middle coalite tar, multiple method can also be adopted technically to improve the tar yield of low temperature pyrogenation in coal, research shows, on fixed bed reactor, reaction temperature, between 450～650 DEG C, can be increased to 26.5% by the coal tar yield after hydropyrolysis.
Coal tar is the component complex mixture up to up to ten thousand kinds, single compound about more than 500 kind therefrom separating at present and assert, accounts for the 55% of coal tar total amount, including 174 kinds of neutral component such as benzene, dimethylbenzene, naphthalenes；63 kinds of acidic components such as phenol, cresol and 113 kinds of basic components.A lot of compounds in coal tar are the valuable raw materials of plastics, synthetic rubber, pesticide, medicine, exotic material and national defense industry, and also some polycyclic hydrocarbon compounds is that petrochemical industry can not produce and substitute.Coal tar is rich in aromatic component simultaneously, is natural PX raw material.
Trend along with Coal Chemical Industry investment and technical research, increase along with available coal tar yield, China's coal tar processing scale and technology all achieve certain progress, the achievement wherein obtained on coal tar processing isolation technics is researched and developed, and provide technical support for coal tar processing.
At present, the processing of coal tar, domestic and international technique is similar, it is all dehydration, fractional distillation, processing light oil, carbolic oil, naphtalene oil and modified coal tar pitch etc., then through producing the multiple industrial chemicals such as benzene, phenol, naphthalene, anthracene after deep processing, after this coal tar processing, product utilization is worth little, and separates very big with the difficulty of concentration.
Chinese patent CN1205302C and CN102899087A is proposed middle coalite tar fractional distillation, carbolic oil carries out dephenolize, phenol processed, heavy oil carries out the processing scheme of delayed coking, and product mainly has coking dry gas, liquefied petroleum gas, coking naphtha, coker gas oil, wax tailings and petroleum coke etc..This coking scheme can reduce target product liquid and receive, and reduces economic benefit, and the distillate after coking also has more alkene and colloid, affects the heat stability of oil product, bad.Also need further hydrofinishing and hydrogenation cracking.
If coal tar is made directly hydrogenation cracking processing Petroleum and diesel oil distillate, due to colloid substantial amounts of in coal tar, conventional fixed bed hydrogenation cracking and the catalyst of hydro-refining unit are difficult to maintain long-term operation, it is only capable of the light components of reconstructed coal tar, it usually needs the heavy constituent of coal tar is separated and processes separately.
Summary of the invention
The problems such as the coal tar processing obtained for the dry distillation of coal or coal gasification is difficult, added value of product is low, it is an object of the invention to provide the processing method of a kind of coal and system.This processing method can produce the high value added products such as diesel oil, gasoline blend component, aromatic hydrocarbons and alkene, overcomes the problem that coal tar processing is difficult, is a kind of coal, oil, aromatic hydrocarbons and alkene integral processing method.
For reaching above-mentioned purpose, the processing method that the invention provides a kind of coal, the method comprises the following steps:
(1) dry distillation of coal or coal gasification: make coal pass through the dry distillation of coal or coal gasification, at least obtain coal gas and coal tar；
(2) coal tar hydrocracking: the coal tar obtained in step (1) is obtained including the product of light naphthar, heavy naphtha and diesel oil by being hydrogenated with cracking；
(3) aromatic hydrocarbons associating: using the heavy naphtha that obtains in step (2) as raw material, combines the product obtaining including hydrogen, benzene and xylol by aromatic hydrocarbons, and includes liquefied petroleum gas, pentane, raffinates oil and the side-product of heavy aromatics；
(4) light-hydrocarbon aromatized: by the light naphthar obtained in step (2) and/or using the liquefied petroleum gas obtained in step (3), pentane and the combination of one or more in raffinating oil as raw material, by the light-hydrocarbon aromatized product obtaining including hydrogen, propane and BTX aromatics；
(5) dehydrogenating propane and polyacrylic preparation: the propane obtained in step (4) is carried out dehydrogenating propane and polyacrylic preparation, obtains polypropylene and hydrogen product.
In the processing method of above-mentioned coal, step (1) can adopt the dry distillation of coal or the coal gasifying process of this area routine, it is preferred to use the technique that coal tar yield is higher, it is possible to provides more raw material for follow-up processing.The TRIG Coal Gasification Technology (being referred to " KBR transmits integrated form gasification technology summary ", author You Wei, " chemical fertilizer design " December the 50th volume in 2012, the 1st phase) of such as KBR company.
In the processing method of above-mentioned coal, preferably, the hydrogenation cracking of step (2) is to adopt VCC floating bed hydrocracking technique (to be referred to the denomination of invention patent application for " coal tar heavy fractioning suspension bed hydrocracking method and system ", publication number is CN101962571A, apply for artificial Dalian University of Technology), and all or part of recycling in described hydrogenation cracking of the diesel product in step (2).
In the present invention, step (2) preferably employs VCC floating bed hydrocracking technique, and this technique can process full fraction coal tar, and 525 DEG C of fractions of > can reach the conversion ratio of 95%.VCC floating bed hydrocracking adopts the flow process of " suspension bed+fixing bed " reactor.In suspended-bed reactor, carbon residue in raw material, asphalitine, metal etc. are all adsorbed on additive and the reactions such as cracking occur, and the coke of heavy metal and generation finally be deposited on additive, and additive separates subsequently bottom high pressure hot separator.The gaseous product of suspension bed thermal cracking cleaning goes fixed bed reactors to be hydrogenated with cracking and hydrofinishing further again, produces Petroleum and the diesel oil of high-quality.VCC floating bed hydrocracking technology can solve fixed bed hydrogenation cracking cannot the difficult problem of long-term operation, and the diesel oil of this explained hereafter is in harmonious proportion product sulfur content and reaches " light-duty vehicle pollutant emission limit and measuring method (the 5th stage of China) " discharge standard (i.e. state V standard).
And, the all or part of of diesel product in step (2) can recycle in hydrogenation cracking, can pass through to regulate the mode of diesel cycle amount, according to market demand, adjustment product distributes, and then high-yield diesel oil or fecund Petroleum with productive aromatic hydrocarbon and alkene or can not produce diesel oil, full scale production aromatic hydrocarbons and alkene.
In the processing method of above-mentioned coal, preferably, the aromatic hydrocarbons of step (3) is combined and is included CONTINUOUS REFORMER, catalyst regeneration, Aromatics Extractive Project, disproportionation and transalkylation, adsorbing separation, isomerization and xylene distillation, wherein, described CONTINUOUS REFORMER, catalyst regeneration, disproportionation and transalkylation, adsorbing separation, isomerization can adopt American UOP, and (patented technology of American UOP is referred at least following 5 patents: 1, catalytic reforming Technical Reference denomination of invention is the patent application of " method with the catalytic reforming that Petroleum is raw material ", publication number is CN1044488A；2, catalyst regeneration techniques is with reference to the patent application that denomination of invention is " method and apparatus for making regenerated catalyst particles ", and publication number is CN103517761A；3, disproportionation and patent application that transalkylation Technical Reference denomination of invention is " process for selective aromatics disproportionation with the conversion ratio of raising ", publication number is CN101668723A；4, adsorption separation technology is with reference to the patent application that denomination of invention is " utilizing adsorbing separation and fractional distillation to reclaim method and the device of product ", and publication number is CN104159647A；5, isomerization technique is with reference to the patent application that denomination of invention is " selective dimethyl isomerization and ethylbenzene convert ", publication number is CN1342631A) or the patented technology of France Axens (the Axens patented technology of Compagnie Francise des Petroles is referred at least following 5 patents: 1, catalytic reforming Technical Reference denomination of invention is the patent application of " in several districts of moving bed reaction side by side the method for catalytic reforming ", and publication number is CN1042559A；2, catalyst regeneration techniques is with reference to the patent application that denomination of invention is " renovation process of aromatic hydrocarbon preparation or reforming catalyst ", and publication number is CN1045411A；3, disproportionation and transalkylation Technical Reference denomination of invention are the patent application of " under two kinds of zeolite catalysts exist the method for alkylaromatic hydrocarbon disproportionation and transalkylation ", and publication number is CN1164524A；4, adsorption separation technology is with reference to the patent application that denomination of invention is " simulated mobile bed separation process of improvement and equipment ", and publication number is CN1714915A；5, isomerization technique is with reference to the patent application that denomination of invention is " comprising the double zeolite catalyst of group VIII metal and Group IIIA metal and the application in the isomerization of aromatic C 8 compounds thereof ", publication number is CN101340976A), Aromatics Extractive Project can adopt the extractive distillation technology (being referred to the patent application that denomination of invention is " a kind of method of extractive distillation aromatics separation and the double solvents of use ", publication number is CN1393507A) of Shi Ke institute.These above-mentioned Technologies are respectively provided with abundant achievement, and technology maturation is reliable, and the xylol response rate is high, high (> 99.8% of purity).The heavy aromatics side-product and/or the side-product of raffinating oil that obtain in step (3) can as high-knock rating gasoline blend components.
In the processing method of above-mentioned coal, preferably, the light-hydrocarbon aromatized light-hydrocarbon aromatized technology (being referred to the denomination of invention patent application for " process of a kind of lower carbon number hydrocarbons hydroaromatization ", publication number is CN103834437A) adopting Dalian University of Technology of step (4).Utilize the side-product that kind that this technique can obtain in procedure of processing (2) and step (3) is more, such as light naphthar, liquefied petroleum gas, pentane with raffinate oil, obtain hydrogen, BTX aromatics and bromopropane product.
In the present invention, the design that step (4) is light-hydrocarbon aromatized, produces BTX aromatics product with the side-product that abovementioned steps coal tar hydrocracking and aromatic hydrocarbons are combined for Raw material processing, not only improves aromatics yield, also reduce product category, optimize, reduce storage and handling facility, occupation of land and investment.Simultaneously, the light-hydrocarbon aromatized of step (4) is non-hydrogen operation, the coal tar hydrocracking device of step (2) and the Aromatic Hydrocarbon United Plant of step (3) need when driving to operate under facing hydrogen state, so the light-hydrocarbon aromatized device of step (4) first can drive when not having hydrogen to produce hydrogen supply hydrocracking unit and Aromatic Hydrocarbon United Plant driving use, it is not necessary to outsourcing hydrogen is driven.
According to the specific embodiment of the present invention, it is preferable that the processing method of above-mentioned coal is further comprising the steps of: the raw material that the BTX aromatics product obtained in step (4) is combined as the aromatic hydrocarbons in step (3).
In the processing method of above-mentioned coal, the dehydrogenating propane of step (5) and polyacrylic preparation can be the dehydrogenating propane of this area routine and polyacrylic technology of preparing, and its concrete technology step repeats no more in the text.In the present invention, in step (5), what polyacrylic preparation adopted is the light-hydrocarbon aromatized side-product propane of step (4), so low in raw material price, economic benefit is more preferably.
According to the specific embodiment of the present invention, preferably, the processing method of above-mentioned coal is further comprising the steps of: the hydrogen product (this hydrogen product is the gas products comprising hydrogen, is not pure hydrogen) obtained in step (3) and/or step (4) and/or step (5) carried out after pressure-variable adsorption (PSA) purifies as the hydrogen needed for the hydrogenation cracking of step (2).Wherein, the technology of Pressure Swing Adsorption hydrogen is the ordinary skill in the art, and its concrete operation step repeats no more in the text.
According to the specific embodiment of the present invention, preferably, the processing method of above-mentioned coal is further comprising the steps of: the coal gas dry distillation of coal of step (1) or coal gasification obtained is as raw material production hydrogen, and/or using natural gas and/or methanol as raw material production hydrogen, using the hydrogen that obtains as the hydrogen needed for the hydrogenation cracking of step (2).It is highly preferred that the coal gas dry distillation of coal or the coal gasification of step (1) obtained is as raw material production hydrogen, and/or using natural gas and/or methanol as raw material production hydrogen, it is adopt the process for making hydrogen including at least there being pressure-variable adsorption (PSA).Wherein, the process for making hydrogen of the dry distillation of coal or coal gasification coal gas, natural gas or methanol can be all the process for making hydrogen that this area is conventional, and process for making hydrogen preferably employs the hydrogen producing technology comprising pressure-variable adsorption.
In the present invention, hydrogen needed for the hydrogenation cracking of step (2) can be provided by the hydrogen obtained in step (3) and/or step (4) and/or step (5), if the words of deficiency, it is also possible to the coal gas obtained by the dry distillation of coal or coal gasification and/or natural gas and/or methanol provide as raw material production hydrogen.
According to the specific embodiment of the present invention, preferably, the processing method of above-mentioned coal is further comprising the steps of: sulfur-bearing that the coal gas dry distillation of coal of step (1) or coal gasification obtained obtains after raw material production hydrogen, the impurity of nitrogen, is obtained sulfur and liquefied ammonia product by sulphur recovery combined unit；And/or the impurity by the sulfur-bearing obtained after the coal tar hydrocracking of step (2), nitrogen, sulfur and liquefied ammonia product is obtained by sulphur recovery combined unit.Described sulphur recovery combined unit can be the sulphur recovery combined unit that this area is conventional.In the present invention, the impurity such as sulfur in feed coal, nitrogen enter the part of coal tar and convert in coal tar hydrocracking technique, the part entering coal gas separates in process for making hydrogen, then sulfur and liquefied ammonia product all can be made by sulphur recovery combined unit, both add economic worth, decrease again environmental pollution.
In the processing method of coal provided by the invention, the techniques such as processing route includes the dry distillation of coal or coal gasification, coal tar hydrocracking, aromatic hydrocarbons associating, light-hydrocarbon aromatized, prepared by dehydrogenating propane, polypropylene, major product includes meeting the diesel oil of state's V standard, benzene, xylol, heavy aromatics, polypropylene (or propylene) and (high-octane rating) gasoline blend component etc..In work flow, between each technique, raw material and product supply mutually, reduce low-value product kind, optimize storage and handling facility, reduce accumulating investment.Product category is concentrated, and added value is high.Break traditions coal processing mode, extends Coal Chemical Industry work flow, improves product economy and is worth.And manufacturing process is flexible, the distribution of each product can carry out allotment flexibly according to market demand: high-yield diesel oil, fecund gasoline, productive aromatic hydrocarbon or producing in high-yield olefin are achieved such as through fairly simple means.
It addition, applicant specifically introduces the full content of the list of references all mentioned in the disclosure.
nullOn the other hand，Present invention also offers the system of processing of a kind of coal，It at least includes: the dry distillation of coal or coal gasification apparatus、Coal tar hydrocracking device、Aromatic Hydrocarbon United Plant、Light-hydrocarbon aromatized device、Dehydrogenating propane device and polypropylene preparation facilities，Wherein，The coal tar outlet of the described dry distillation of coal or coal gasification apparatus is connected to the feed(raw material)inlet of described coal tar hydrocracking device，The heavy naphtha outlet of described coal tar hydrocracking device is connected to the feed(raw material)inlet of described Aromatic Hydrocarbon United Plant，The light naphthar outlet of described coal tar hydrocracking device and/or the liquefied petroleum gas outlet of described Aromatic Hydrocarbon United Plant、Pentane outlet and raffinate oil in outlet one or several be connected to the feed(raw material)inlet of described light-hydrocarbon aromatized device，The propane outlets of described light-hydrocarbon aromatized device is connected to described dehydrogenating propane device，The propylene outlet of described dehydrogenating propane device is connected to the feed(raw material)inlet of described polypropylene preparation facilities.
In the system of processing of above-mentioned coal, it is preferable that the BTX aromatics outlet of described light-hydrocarbon aromatized device is connected to the feed(raw material)inlet of described Aromatic Hydrocarbon United Plant.
According to the specific embodiment of the present invention, preferably, the system of processing of above-mentioned coal also includes including at least the device for producing hydrogen having variable-pressure adsorption equipment, described including at least there being the device for producing hydrogen of variable-pressure adsorption equipment to include independent variable-pressure adsorption equipment, one or several in the hydrogen outlet of described Aromatic Hydrocarbon United Plant, light-hydrocarbon aromatized device and dehydrogenating propane device is connected to described variable-pressure adsorption equipment, and after the purification of described variable-pressure adsorption equipment, hydrogen outlet is connected to the hydrogen inlet of described coal tar hydrocracking device.
In the system of processing of above-mentioned coal, preferably, described including at least there being the device for producing hydrogen of variable-pressure adsorption equipment to include the dry distillation of coal or coal gasification coal gas device for producing hydrogen, and the gas exit of the described dry distillation of coal or coal gasification apparatus is connected to the described dry distillation of coal or the feed(raw material)inlet of coal gasification coal gas device for producing hydrogen, and the hydrogen outlet of the described dry distillation of coal or coal gasification coal gas device for producing hydrogen is connected to the hydrogen inlet of described coal tar hydrocracking device.
In the system of processing of above-mentioned coal, preferably, described including at least there being the device for producing hydrogen of variable-pressure adsorption equipment to include natural gas hydrogen production plant and/or hydrogen production units by carbinol, and the hydrogen outlet of described natural gas hydrogen production plant and/or hydrogen production units by carbinol is connected to the hydrogen inlet of described coal tar hydrocracking device.
In the system of processing of the coal of the present invention, described including at least there being the device for producing hydrogen of variable-pressure adsorption equipment can include the combination of one or more in the dry distillation of coal or coal gasification coal gas device for producing hydrogen, natural gas hydrogen production plant, hydrogen production units by carbinol, independent variable-pressure adsorption equipment, so that the hydrogen needed for coal tar hydrocracking is combined by aromatic hydrocarbons and/or the hydrogen that obtains in light-hydrocarbon aromatized and/or dehydrogenating propane provides, if the words of deficiency, it is also possible to the coal gas obtained by the dry distillation of coal or coal gasification and/or natural gas and/or methanol provide as raw material production hydrogen.
According to the specific embodiment of the present invention, preferably, the system of processing of above-mentioned coal also includes sulphur recovery combined unit, described sulphur recovery combined unit is connected to the described dry distillation of coal or the impurities outlet of the sulfur-bearing of coal gasification coal gas device for producing hydrogen, nitrogen, and/or is connected to the impurities outlet of the sulfur-bearing of described coal tar hydrocracking device, nitrogen.
In the system of processing of coal provided by the invention, between each device, material is supplied mutually, it is achieved organically combines, it does not have exhaust emission, and all achieves the maximum value of various material.
In sum, the processing method of coal provided by the invention and system can produce the high value added products such as diesel oil, (high-octane rating) gasoline blend component, aromatic hydrocarbons and alkene, overcome the problem that coal tar processing is difficult, and drastically increase the economic worth of Coal Chemical Industry product, simultaneously according to market demand, product can be carried out flexible allocation, be a kind of New type coal, oil, aromatic hydrocarbons, alkene integration processing route and system.
Accompanying drawing explanation
Fig. 1 is the processing method of the coal of the embodiment of the invention and the flow process of system and structural representation.
Primary clustering symbol description:
The dry distillation of coal or coal gasification apparatus 1, coal tar hydrocracking device 2, Aromatic Hydrocarbon United Plant 3, light-hydrocarbon aromatized device 4, dehydrogenating propane device 5, polypropylene preparation facilities 6, including at least having the device for producing hydrogen 7 of variable-pressure adsorption equipment, sulphur recovery combined unit 8
Coal entrance 11, gas exit 12, coal tar outlet 13,
The feed(raw material)inlet 21 of coal tar hydrocracking device, the hydrogen inlet 22 of coal tar hydrocracking device, light naphthar outlet 23, heavy naphtha outlet 24, diesel oil outlet 25, the sulfur-bearing obtained after coal tar hydrocracking, nitrogen impurities outlet 26,
The heavy naphtha feed(raw material)inlet 31 of Aromatic Hydrocarbon United Plant, the BTX aromatics feed(raw material)inlet 32 of Aromatic Hydrocarbon United Plant, the hydrogen outlet 33 of Aromatic Hydrocarbon United Plant, liquefied petroleum gas, pentane and the outlet 34 of one or more in raffinating oil, heavy aromatics outlet 35, benzene outlet 36, xylol outlet 37
The light naphthar feed(raw material)inlet 41 of light-hydrocarbon aromatized device, the liquefied petroleum gas of light-hydrocarbon aromatized device, pentane and one or more feed(raw material)inlets 42 in raffinating oil, the hydrogen outlet 43 of light-hydrocarbon aromatized device, the propane outlets 44 of light-hydrocarbon aromatized device, BTX aromatics outlet 45
The feed(raw material)inlet 51 of dehydrogenating propane device, the hydrogen outlet 52 of dehydrogenating propane device, propylene outlet 53,
The feed(raw material)inlet 61 of polypropylene preparation facilities, polypropylene outlet 62,
Include at least the hydrogen feed entrance 71 of the device for producing hydrogen having variable-pressure adsorption equipment, the coal gas feed(raw material)inlet 72 including at least the device for producing hydrogen having variable-pressure adsorption equipment, the hydrogen outlet 73 including at least the device for producing hydrogen having variable-pressure adsorption equipment, include at least the impurities outlet 74 having the sulfur-bearing of device for producing hydrogen of variable-pressure adsorption equipment, nitrogen
Sulphur recovery combined unit including at least the sulfur-bearing obtained after having the coal tar hydrocracking of sulfur-bearing that the device for producing hydrogen of variable-pressure adsorption equipment obtains, the impurity feed(raw material)inlet 81 of nitrogen, sulphur recovery combined unit, the impurity feed(raw material)inlet 82 of nitrogen, sulfur outlet 83, liquefied ammonia outlet 84.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, existing technical scheme is carried out described further below, but it is not intended that to the present invention can the restriction of practical range.
As it is shown in figure 1, the processing method of coal provided by the invention may comprise steps of:
(1) dry distillation of coal or coal gasification: make coal pass through the dry distillation of coal or coal gasification, at least obtain coal gas and coal tar；
(2) coal tar hydrocracking: the coal tar obtained in step (1) is obtained including the product of light naphthar, heavy naphtha and diesel oil by being hydrogenated with cracking；
(3) aromatic hydrocarbons associating: using the BTX aromatics product that obtains in the heavy naphtha obtained in step (2) and step (4) as raw material, combined the product obtaining including hydrogen, benzene and xylol by aromatic hydrocarbons, and include liquefied petroleum gas, pentane, raffinate oil and the side-product of heavy aromatics；
(4) light-hydrocarbon aromatized: by the light naphthar obtained in step (2) and/or using the liquefied petroleum gas obtained in step (3), pentane and the combination of one or more in raffinating oil as raw material, by the light-hydrocarbon aromatized product obtaining including hydrogen, propane and BTX aromatics；
(5) dehydrogenating propane and polyacrylic preparation: the propane obtained in step (4) is carried out dehydrogenating propane and polyacrylic preparation, obtains polypropylene and hydrogen product；
(6) hydrogen product obtained in step (3) and/or step (4) and/or step (5) is carried out pressure-variable adsorption (PSA) purify after as in step (2) hydrogenation cracking needed for hydrogen；And adopt including at least having coal gas that the dry distillation of coal in step (1) or coal gasification obtain by the process for making hydrogen of pressure-variable adsorption (PSA) as raw material production hydrogen, and using the hydrogen that obtains as the hydrogen needed for the hydrogenation cracking in step (2)；
(7) coal gas dry distillation of coal in step (1) or coal gasification obtained obtains after raw material production hydrogen sulfur-bearing, the impurity of nitrogen, obtain sulfur and liquefied ammonia product by sulphur recovery combined unit；And by the impurity of the sulfur-bearing obtained after the coal tar hydrocracking in step (2), nitrogen, obtained sulfur and liquefied ammonia product by sulphur recovery combined unit.
In the processing method of above-mentioned coal, step (1) can adopt the dry distillation of coal or the coal gasifying process of this area routine, it is preferred to use the technique that coal tar yield is higher, it is possible to provides more raw material for follow-up processing.The TRIG Coal Gasification Technology (being referred to " KBR transmits integrated form gasification technology summary ", author You Wei, " chemical fertilizer design " December the 50th volume in 2012, the 1st phase) of such as KBR company.
In the processing method of above-mentioned coal, preferably, hydrogenation cracking in step (2) is to adopt VCC floating bed hydrocracking technique (to be referred to the denomination of invention patent application for " coal tar heavy fractioning suspension bed hydrocracking method and system ", publication number is CN101962571A, apply for artificial Dalian University of Technology), and all or part of recycling in described hydrogenation cracking of the diesel product in step (2).
In the present invention, step (2) preferably employs VCC floating bed hydrocracking technique, and this technique can process full fraction coal tar, and 525 DEG C of fractions of > can reach the conversion ratio of 95%.VCC floating bed hydrocracking adopts the flow process of " suspension bed+fixing bed " reactor.In suspended-bed reactor, carbon residue in raw material, asphalitine, metal etc. are all adsorbed on additive and the reactions such as cracking occur, and the coke of heavy metal and generation finally be deposited on additive, and additive separates subsequently bottom high pressure hot separator.The gaseous product of suspension bed thermal cracking cleaning goes fixed bed reactors to be hydrogenated with cracking and hydrofinishing further again, produces Petroleum and the diesel oil of high-quality.VCC floating bed hydrocracking technology can solve fixed bed hydrogenation cracking cannot the difficult problem of long-term operation, and the diesel oil of this explained hereafter is in harmonious proportion product sulfur content and reaches " light-duty vehicle pollutant emission limit and measuring method (the 5th stage of China) " discharge standard (i.e. state V standard).
And, the all or part of of diesel product in step (2) can recycle in hydrogenation cracking, can pass through to regulate the mode of diesel cycle amount, according to market demand, adjustment product distributes, and then high-yield diesel oil or fecund Petroleum with productive aromatic hydrocarbon and alkene or can not produce diesel oil, full scale production aromatic hydrocarbons and alkene.
In the processing method of above-mentioned coal, preferably, aromatic hydrocarbons in step (3) is combined and is included CONTINUOUS REFORMER, catalyst regeneration, Aromatics Extractive Project, disproportionation and transalkylation, adsorbing separation, isomerization and xylene distillation, wherein, described CONTINUOUS REFORMER, catalyst regeneration, disproportionation and transalkylation, adsorbing separation, isomerization can adopt American UOP, and (patented technology of American UOP is referred at least following 5 patents: 1, catalytic reforming Technical Reference denomination of invention is the patent application of " method with the catalytic reforming that Petroleum is raw material ", publication number is CN1044488A；2, catalyst regeneration techniques is with reference to the patent application that denomination of invention is " method and apparatus for making regenerated catalyst particles ", and publication number is CN103517761A；3, disproportionation and patent application that transalkylation Technical Reference denomination of invention is " process for selective aromatics disproportionation with the conversion ratio of raising ", publication number is CN101668723A；4, adsorption separation technology is with reference to the patent application that denomination of invention is " utilizing adsorbing separation and fractional distillation to reclaim method and the device of product ", and publication number is CN104159647A；5, isomerization technique is with reference to the patent application that denomination of invention is " selective dimethyl isomerization and ethylbenzene convert ", publication number is CN1342631A) or the patented technology of France Axens (the Axens patented technology of Compagnie Francise des Petroles is referred at least following 5 patents: 1, catalytic reforming Technical Reference denomination of invention is the patent application of " in several districts of moving bed reaction side by side the method for catalytic reforming ", and publication number is CN1042559A；2, catalyst regeneration techniques is with reference to the patent application that denomination of invention is " renovation process of aromatic hydrocarbon preparation or reforming catalyst ", and publication number is CN1045411A；3, disproportionation and transalkylation Technical Reference denomination of invention are the patent application of " under two kinds of zeolite catalysts exist the method for alkylaromatic hydrocarbon disproportionation and transalkylation ", and publication number is CN1164524A；4, adsorption separation technology is with reference to the patent application that denomination of invention is " simulated mobile bed separation process of improvement and equipment ", and publication number is CN1714915A；5, isomerization technique is with reference to the patent application that denomination of invention is " comprising the double zeolite catalyst of group VIII metal and Group IIIA metal and the application in the isomerization of aromatic C 8 compounds thereof ", publication number is CN101340976A), Aromatics Extractive Project can adopt the extractive distillation technology (being referred to the patent application that denomination of invention is " a kind of method of extractive distillation aromatics separation and the double solvents of use ", publication number is CN1393507A) of Shi Ke institute.These above-mentioned Technologies are respectively provided with abundant achievement, and technology maturation is reliable, and the xylol response rate is high, high (> 99.8% of purity).The heavy aromatics side-product and/or the side-product of raffinating oil that obtain in step (3) can as high-knock rating gasoline blend components.
In the processing method of above-mentioned coal, preferably, the light-hydrocarbon aromatized light-hydrocarbon aromatized technology (being referred to the denomination of invention patent application for " process of a kind of lower carbon number hydrocarbons hydroaromatization ", publication number is CN103834437A) adopting Dalian University of Technology in step (4).Utilize the side-product that kind that this technique can obtain in procedure of processing (2) and step (3) is more, such as light naphthar, liquefied petroleum gas, pentane with raffinate oil, obtain hydrogen, BTX aromatics and bromopropane product.
In the present invention, the design that step (4) is light-hydrocarbon aromatized, produces BTX aromatics product with the side-product that abovementioned steps coal tar hydrocracking and aromatic hydrocarbons are combined for Raw material processing, not only improves aromatics yield, also reduce product category, optimize, reduce storage and handling facility, occupation of land and investment.Simultaneously, light-hydrocarbon aromatized in step (4) is non-hydrogen operation, coal tar hydrocracking device in step (2) and the Aromatic Hydrocarbon United Plant in step (3) need when driving to operate under facing hydrogen state, so the light-hydrocarbon aromatized device in step (4) first can drive when not having hydrogen to produce hydrogen supply hydrocracking unit and Aromatic Hydrocarbon United Plant driving use, it is not necessary to outsourcing hydrogen is driven.
In the processing method of above-mentioned coal, dehydrogenating propane and polyacrylic preparation in step (5) can be the dehydrogenating propane of this area routine and polyacrylic technology of preparing, such as dehydrogenating propane technology can adopt the Oleflex dehydrogenating propane Technology of UOP (to be referred to the denomination of invention patent application for " for dehydrogenating propane becomes the new reactor flow process of propylene ", publication number is CN102811985A), polypropylene technology of preparing can adopt the Innovene gas-phase process technology of INEOS company (to be referred to the patent application that denomination of invention is " utilizing the gas-phase propylene polymerization process added stage by stage of alkyl aluminum ", publication number is CN101627058A).In the present invention, what in step (5), polyacrylic preparation adopted is the light-hydrocarbon aromatized side-product propane in step (4), so low in raw material price, economic benefit is more preferably.
In the processing method of above-mentioned coal, the technology of the Pressure Swing Adsorption hydrogen in step (6) is the ordinary skill in the art, the pressure swing adsorption (being referred to the patent application that denomination of invention is " from coke-stove gas the method for purifying hydrogen of hydrogen ", publication number is CN1355131A) of sky, Sichuan one company can be adopted.The dry distillation of coal in step (6) or the process for making hydrogen of coal gasification coal gas can be the process for making hydrogen that this area is conventional, and process for making hydrogen preferably employs the hydrogen producing technology comprising pressure-variable adsorption.The technology of this pressure-variable adsorption can adopt the pressure swing adsorption in above-mentioned CN1355131A.
According to the specific embodiment of the present invention, it is preferable that the processing method of above-mentioned coal is further comprising the steps of: using natural gas or methanol as raw material production hydrogen, using the hydrogen that obtains as the hydrogen needed for the hydrogenation cracking in step (2).It is highly preferred that using natural gas or methanol as raw material production hydrogen, be adopt the process for making hydrogen including at least there being pressure-variable adsorption (PSA).The process for making hydrogen of natural gas or methanol can be the process for making hydrogen that this area is conventional, and process for making hydrogen preferably employs the hydrogen producing technology comprising pressure-variable adsorption.The technology of this pressure-variable adsorption can adopt the pressure swing adsorption in above-mentioned CN1355131A.
In the present invention, the hydrogen needed for hydrogenation cracking in step (2) can be provided by the hydrogen obtained in step (3) and/or step (4) and/or step (5), if the words of deficiency, it is also possible to the coal gas obtained by the dry distillation of coal or coal gasification and/or natural gas and/or methanol provide as raw material production hydrogen.
In the processing method of above-mentioned coal, sulphur recovery combined unit in step (7) can be the sulphur recovery combined unit that this area is conventional, such as being referred to the sulphur recovery combined unit in the patent application that denomination of invention is " SWSR-1 sulfur recovery unit and technique ", publication number is CN103482583A.In the present invention, the impurity such as sulfur in feed coal, nitrogen enter the part of coal tar and convert in coal tar hydrocracking technique, the part entering coal gas separates in process for making hydrogen, then sulfur and liquefied ammonia product all can be made by sulphur recovery combined unit, both add economic worth, decrease again environmental pollution.
As it is shown in figure 1, the system of processing of coal provided by the invention can at least include: the dry distillation of coal or coal gasification apparatus 1, coal tar hydrocracking device 2, Aromatic Hydrocarbon United Plant 3, light-hydrocarbon aromatized device 4, dehydrogenating propane device 5, polypropylene preparation facilities 6, including at least having the device for producing hydrogen 7 of variable-pressure adsorption equipment, sulphur recovery combined unit 8；
Wherein, the described dry distillation of coal or coal gasification apparatus 1 export 13 at least provided with coal entrance 11, gas exit 12 and coal tar,
Described coal tar hydrocracking device 2 is at least provided with the impurities outlet 26 of the sulfur-bearing obtained after the feed(raw material)inlet 21 of coal tar hydrocracking device, the hydrogen inlet 22 of coal tar hydrocracking device, light naphthar outlet 23, heavy naphtha outlet 24, diesel oil outlet 25, coal tar hydrocracking, nitrogen
At least provided with the heavy naphtha feed(raw material)inlet 31 of Aromatic Hydrocarbon United Plant, the BTX aromatics feed(raw material)inlet 32 of Aromatic Hydrocarbon United Plant, the hydrogen outlet 33 of Aromatic Hydrocarbon United Plant, liquefied petroleum gas, pentane and the outlet 34 of one or more in raffinating oil, (outlet of this several prods can be provided separately described Aromatic Hydrocarbon United Plant 3, in order to simplify, in FIG they are plotted as an outlet), heavy aromatics outlet 35, benzene outlet 36, xylol outlet 37
Described light-hydrocarbon aromatized device 4 is at least provided with the light naphthar feed(raw material)inlet 41 of light-hydrocarbon aromatized device, the liquefied petroleum gas of light-hydrocarbon aromatized device, pentane and one or more feed(raw material)inlets 42 in raffinating oil, the hydrogen outlet 43 of light-hydrocarbon aromatized device, the propane outlets 44 of light-hydrocarbon aromatized device, BTX aromatics outlet 45
Described dehydrogenating propane device 5 exports 53 at least provided with the feed(raw material)inlet 51 of dehydrogenating propane device, the hydrogen outlet 52 of dehydrogenating propane device, propylene,
Described polypropylene preparation facilities 6 exports 62 at least provided with the feed(raw material)inlet 61 of polypropylene preparation facilities, polypropylene,
The described device for producing hydrogen 7 having variable-pressure adsorption equipment that includes at least is at least provided with including at least the hydrogen feed entrance 71 of the device for producing hydrogen having variable-pressure adsorption equipment, the coal gas feed(raw material)inlet 72 including at least the device for producing hydrogen having variable-pressure adsorption equipment, the hydrogen outlet 73 including at least the device for producing hydrogen having variable-pressure adsorption equipment, including at least the impurities outlet 74 having the sulfur-bearing of device for producing hydrogen of variable-pressure adsorption equipment, nitrogen
Described sulphur recovery combined unit 8 at least provided with sulphur recovery combined unit including at least the sulfur-bearing obtained after having the coal tar hydrocracking of sulfur-bearing that the device for producing hydrogen of variable-pressure adsorption equipment obtains, the impurity feed(raw material)inlet 81 of nitrogen, sulphur recovery combined unit, the impurity feed(raw material)inlet 82 of nitrogen, sulfur outlet 83, liquefied ammonia outlet 84；
The coal tar outlet 13 of the described dry distillation of coal or coal gasification apparatus 1 is connected to the feed(raw material)inlet 21 of described coal tar hydrocracking device,
The heavy naphtha outlet 24 of described coal tar hydrocracking device 2 is connected to the heavy naphtha feed(raw material)inlet 31 of described Aromatic Hydrocarbon United Plant, the light naphthar outlet 23 of described coal tar hydrocracking device 2 is connected to the light naphthar feed(raw material)inlet 41 of described light-hydrocarbon aromatized device
The liquefied petroleum gas of described Aromatic Hydrocarbon United Plant 3, pentane and the outlet 34 of one or more in raffinating oil be connected to the liquefied petroleum gas of described light-hydrocarbon aromatized device, pentane and raffinate oil in one or more feed(raw material)inlets 42,
The propane outlets 44 of described light-hydrocarbon aromatized device is connected to the feed(raw material)inlet 51 of described dehydrogenating propane device, and the BTX aromatics outlet 45 of described light-hydrocarbon aromatized device 4 is connected to the BTX aromatics feed(raw material)inlet 32 of described Aromatic Hydrocarbon United Plant,
The propylene outlet 53 of described dehydrogenating propane device 5 is connected to the feed(raw material)inlet 61 of described polypropylene preparation facilities,
The described hydrogen outlet 52 being connected to the hydrogen outlet 33 of described Aromatic Hydrocarbon United Plant, the hydrogen outlet 43 of light-hydrocarbon aromatized device and dehydrogenating propane device including at least the hydrogen feed entrance 71 of device for producing hydrogen having variable-pressure adsorption equipment, the described coal gas feed(raw material)inlet 72 including at least the device for producing hydrogen having variable-pressure adsorption equipment is connected to the gas exit 12 of the described dry distillation of coal or coal gasification apparatus 1, the described hydrogen outlet 73 including at least the device for producing hydrogen having variable-pressure adsorption equipment is connected to the hydrogen inlet 22 of coal tar hydrocracking device
Described sulphur recovery combined unit including at least there being sulfur-bearing that the device for producing hydrogen of variable-pressure adsorption equipment obtains, the impurity feed(raw material)inlet 81 of nitrogen be connected to described including at least the impurities outlet 74 having the sulfur-bearing of device for producing hydrogen of variable-pressure adsorption equipment, nitrogen, the sulfur-bearing obtained after the coal tar hydrocracking of described sulphur recovery combined unit, the sulfur-bearing that the impurity feed(raw material)inlet 82 of nitrogen obtains after being connected to described coal tar hydrocracking, nitrogen impurities outlet 26.
nullIn above-mentioned system，Described including at least there being the device for producing hydrogen of variable-pressure adsorption equipment can include the dry distillation of coal or coal gasification coal gas device for producing hydrogen and/or independent variable-pressure adsorption equipment，And described Aromatic Hydrocarbon United Plant、One or several in the hydrogen outlet of light-hydrocarbon aromatized device and dehydrogenating propane device is connected to described independent variable-pressure adsorption equipment，And/or the gas exit of the described dry distillation of coal or coal gasification apparatus is connected to the described dry distillation of coal or the feed(raw material)inlet of coal gasification coal gas device for producing hydrogen，And also natural gas hydrogen production plant and/or hydrogen production units by carbinol can be included，Gas source is connected to described natural gas hydrogen production plant，And/or methanol source is connected to described hydrogen production units by carbinol，And the described hydrogen outlet including at least the device for producing hydrogen having variable-pressure adsorption equipment is connected to the hydrogen inlet of described coal tar hydrocracking device.In FIG, to put it more simply, the dry distillation of coal or coal gasification coal gas device for producing hydrogen and independent variable-pressure adsorption equipment are plotted as a device.
With a specific embodiment, technical scheme is described in detail below.Following embodiment adopts above-mentioned method and system.Specifically, coal gasification is the TRIG Coal Gasification Technology adopting KBR company, coal tar hydrocracking is to adopt VCC floating bed hydrocracking Technology, aromatic hydrocarbons is combined the complete set technology at least a part of which being to adopt Axens company and is included above-mentioned five patented technology, the light-hydrocarbon aromatized light-hydrocarbon aromatized technology being to adopt Dalian University of Technology, dehydrogenating propane is the Oleflex dehydrogenating propane Technology adopting UOP, the polyacrylic Innovene gas-phase process technology being prepared by adopting INEOS company.
With brown coal for raw material, obtain coal tar through the dry distillation of coal.Using 2,000,000 tons/year of coal tar as the raw material of VCC floating bed hydrocracking, the major product of coal tar hydrocracking device has light naphthar, heavy naphtha and diesel oil.Wherein heavy naphtha is as the raw material of Aromatic Hydrocarbon United Plant, and light naphthar is as the raw material of light-hydrocarbon aromatized device, and diesel oil is as diesel oil blending component product carrying device.
Heavy naphtha enters the continuous reformer of Aromatic Hydrocarbon United Plant and carries out catalytic reforming reaction, and major product is reformed oil (C6+).Major product BTX aromatics from light-hydrocarbon aromatized device enters Aromatic Hydrocarbon United Plant as raw material, converge with reformed oil (C6+), through other devices and aromatic extraction unit, disproportionation and benzene toluene segregation apparatus, adsorption separation device and the isomerization unit processing of Aromatic Hydrocarbon United Plant.The product of Aromatic Hydrocarbon United Plant includes: hydrogen-containing gas, liquefied petroleum gas, pentane, raffinate oil, benzene, xylol and heavy aromatics product.Wherein, heavy aromatics product delivers to coal tar hydrocracking device freshening；Liquefied petroleum gas, pentane and product of raffinating oil are supplied to light-hydrocarbon aromatized device as raw material.The product of light-hydrocarbon aromatized device has hydrogen-containing gas, propane and BTX aromatics, and BTX aromatics is again as the raw material of Aromatic Hydrocarbon United Plant.The bromopropane product of light-hydrocarbon aromatized device enters dehydrogenating propane device and polypropylene preparation facilities as raw material, produces and obtains polypropylene product.
The hydrogen-containing gas of Aromatic Hydrocarbon United Plant, supplies VCC suspension bed coal tar hydrocracking device together with low point of gas (hydrogeneous) of sulfur-bearing of the hydrogen-containing gas of light-hydrocarbon aromatized device and suspension bed coal tar hydrocracking device after Pressure Swing Adsorption and uses.
Owing in coal tar, impurity content is high, C/Hratio is high, it is necessary to consuming substantial amounts of hydrogen, the hydrogen deficient that said apparatus produces is with the needs of satisfied hydrogenation cracking, it is necessary to arrange device for producing hydrogen hydrogen manufacturing again and supplement needs, device for producing hydrogen adopts natural gas to be raw material.
The final products of whole processing route are diesel oil, benzene, xylol and polypropylene product.If being up to principle to produce xylol, not producing diesel oil, xylol 800,000 tons/year, benzene 410,000 tons/year, polypropylene 200,000 tons/year can be produced at most.
Diesel product character:
Table 1 diesel product character
Benzaldehyde product character:
Product meets the technology requirement of petrobenzene GB/T3405-2011, and its quality index is shown in following table.
Table 2 petrobenzene (GB/T3405-2011) quality index
Para-xylene product character:
Meet the index request of high-class product in People's Republic of China (PRC) petroleum chemical industry standard SH1486.1-2008.Oil xylol (SH1486.1-2008) choicest quality figureofmerit is as follows.
Table 3 oil xylol (SH1486.1-2008) choicest quality figureofmerit
The processing method of coal provided by the invention and system can produce the high value added products such as diesel oil, (high-octane rating) gasoline blend component, aromatic hydrocarbons and alkene, overcome the problem that coal tar processing is difficult, and drastically increase the economic worth of Coal Chemical Industry product, simultaneously according to market demand, product can be carried out flexible allocation, be a kind of New type coal, oil, aromatic hydrocarbons, alkene integration processing route and system.
Claims (7)
1. a processing method for coal, it at least comprises the following steps:
(1) dry distillation of coal or coal gasification: make coal pass through the dry distillation of coal or coal gasification, at least obtain coal gas and coal tar；
(2) coal tar hydrocracking: the coal tar obtained in step (1) is obtained including the product of light naphthar, heavy naphtha and diesel oil by being hydrogenated with cracking；
(3) aromatic hydrocarbons associating: using the heavy naphtha that obtains in step (2) as raw material, combines the product obtaining including hydrogen, benzene and xylol by aromatic hydrocarbons, and includes liquefied petroleum gas, pentane, raffinates oil and the side-product of heavy aromatics；
(4) light-hydrocarbon aromatized: by the light naphthar obtained in step (2) and/or using the liquefied petroleum gas obtained in step (3), pentane and the combination of one or more in raffinating oil as raw material, by the light-hydrocarbon aromatized product obtaining including hydrogen, propane and BTX aromatics；
(5) dehydrogenating propane and polyacrylic preparation: the propane obtained in step (4) is carried out dehydrogenating propane and polyacrylic preparation, obtains polypropylene and hydrogen product.
2. the processing method of coal according to claim 1, wherein, the hydrogenation cracking of step (2) is to adopt VCC floating bed hydrocracking technique, and all or part of of the diesel product in step (2) recycles in described hydrogenation cracking.
3. the processing method of coal according to claim 1, it is further comprising the steps of: the raw material combined as the aromatic hydrocarbons of step (3) by the BTX aromatics product obtained in step (4).
4. the processing method of coal according to claim 1, it is further comprising the steps of: the hydrogen product obtained in step (3) and/or step (4) and/or step (5) is carried out after Pressure Swing Adsorption as step (2) hydrogenation cracking needed for hydrogen.
5. the processing method of coal according to claim 1, it is further comprising the steps of: the coal gas dry distillation of coal of step (1) or coal gasification obtained is as raw material production hydrogen, and/or using natural gas and/or methanol as raw material production hydrogen, using the hydrogen that obtains as the hydrogen needed for the hydrogenation cracking of step (2).
6. the processing method of coal according to claim 5, wherein, the coal gas dry distillation of coal of step (1) or coal gasification obtained is as raw material production hydrogen, and/or using natural gas and/or methanol as raw material production hydrogen, is adopt the process for making hydrogen including at least there being pressure-variable adsorption.
7. the processing method of coal according to claim 1 or 5, it is further comprising the steps of: sulfur-bearing that the coal gas dry distillation of coal of step (1) or coal gasification obtained obtains after raw material production hydrogen, the impurity of nitrogen, is obtained sulfur and liquefied ammonia product by sulphur recovery combined unit；And/or the impurity by the sulfur-bearing obtained after the coal tar hydrocracking of step (2), nitrogen, sulfur and liquefied ammonia product is obtained by sulphur recovery combined unit.
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