CN106190289B - A kind of method and system of diversification raw material aromatic hydrocarbons - Google Patents
A kind of method and system of diversification raw material aromatic hydrocarbons Download PDFInfo
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- CN106190289B CN106190289B CN201610825663.6A CN201610825663A CN106190289B CN 106190289 B CN106190289 B CN 106190289B CN 201610825663 A CN201610825663 A CN 201610825663A CN 106190289 B CN106190289 B CN 106190289B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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Abstract
The present invention provides a kind of method and systems of diversification raw material aromatic hydrocarbons, and this approach includes the following steps：H-G hydrocracking technique：It converts diesel oil to fuel gas, liquefied gas, light naphthar and heavy naphtha by being hydrocracked；Aromatic hydrocarbons process integration：Using the heavy naphtha of naphtha, BTX aromatics and H-G hydrocracking technique productions as raw material, by petroleum naphtha hydrogenation, CONTINUOUS REFORMER, catalyst regeneration, Aromatics Extractive Project, disproportionation and transalkylation, adsorbing separation, isomerization and xylene fractionation technique, obtains hydrogen-containing gas, fuel gas, liquefied gas, pentane, light naphthar, raffinates oil, heavy aromatics, benzene and paraxylene；Light-hydrocarbon aromatized technique：One or both of light naphthar that H-G hydrocracking technique is obtained, liquefied gas, and/or light naphthar, liquefied gas, pentane and the combination one or more of raffinated oil that aromatic hydrocarbons process integration obtains are as raw material, by light-hydrocarbon aromatized, hydrogen-containing gas, propane and BTX aromatics are obtained.
Description
Technical field
The present invention relates to a kind of method and systems of diversification raw material aromatic hydrocarbons, belong to technical field of petrochemical industry.
Background technology
Currently, Domestic Oil Products ' Market speedup slows down, consumption diesel and gasoline ratio is declining year by year, higher than supply diesel and gasoline ratio, diesel oil
It is expected to be 2018 using peak period original, has just been come in advance within 2014 in fact, gasoline original reaches peak value in estimated 2025, can
The year two thousand twenty can be advanceed to.With the implementation of VI standard of petrol and diesel oil state in future, alkene and arene content in gasoline will be further
It reduces, will there is that partly has more than needed to be rich in aromatic hydrocarbons oil product at that time.And the country still exists to the supply requirement of benzene and paraxylene in recent years
Increase year by year, and there is also supply notches at present.Under above-mentioned market situation, finished product oil yield is reduced, and by part price phase
To cheap intermediate product diesel oil, such as：Catalytic diesel oil, straight-run diesel oil or poor ignition quality fuel obtain Gao Fangqian by being hydrocracked production
Naphtha product, mating part naphtha and/or rich in aromatic naphtha (such as reform C7+ oil or reform C8+ oily) plurality of raw materials,
To further produce aromatic hydrocarbons, higher economic benefit can be obtained and alleviate the imbalance between supply and demand of product oil.
Invention content
In order to solve above-mentioned disadvantage and deficiency, the purpose of the present invention is to provide a kind of sides of diversification raw material aromatic hydrocarbons
Method.
The present invention also aims to provide a kind of system of the method for realizing above-mentioned diversification raw material aromatic hydrocarbons.
In order to achieve the above objectives, on the one hand, the present invention provides a kind of method of diversification raw material aromatic hydrocarbons comprising following
Step：
(1) H-G hydrocracking technique：By diesel oil by be hydrocracked be converted into fuel gas, liquefied gas, light naphthar and
Heavy naphtha；
(2) aromatic hydrocarbons process integration：With naphtha, the scheelite of BTX aromatics and step (1) H-G hydrocracking technique productions
Cerebrol is raw material, passes through petroleum naphtha hydrogenation, CONTINUOUS REFORMER, catalyst regeneration, Aromatics Extractive Project, disproportionation and transalkylation, absorption point
From, isomerization and xylene fractionation technique, obtains hydrogen-containing gas, fuel gas, liquefied gas, light naphthar, pentane, raffinates oil, again
Aromatic hydrocarbons, benzene and paraxylene；
(3) light-hydrocarbon aromatized technique：In light naphthar that step (1) H-G hydrocracking technique is obtained, liquefied gas
Light naphthar that one or two and/or step (2) aromatic hydrocarbons process integration obtain, liquefied gas, pentane and one kind in raffinating oil
Or several combinations is as raw material, by light-hydrocarbon aromatized, obtains hydrogen-containing gas, propane and BTX aromatics.
Method according to the present invention, it is preferable that the H-G hydrocracking technique described in step (1) is added using fixed bed
Hydrogen process, the unconverted diesel oil of one way are all recycled back to fixed bed hydrogenation cracking system to continue to be hydrocracked, with
Maximize the components such as production liquefied gas, light naphthar and heavy naphtha.
Method according to the present invention, it is preferable that this method is further comprising the steps of：
The heavy aromatics that step (2) aromatic hydrocarbons process integration is obtained is as raw material return to step (1) bavin of H-G hydrocracking
Oily hydrocracking process, to reduce manufacture product category.
Method according to the present invention, it is preferable that this method is further comprising the steps of：
The BTX aromatics that step (3) light-hydrocarbon aromatized technique is obtained are as the raw material return to step of aromatic hydrocarbons process integration
(2) aromatic hydrocarbons process integration.
Method according to the present invention, it is preferable that this method is further comprising the steps of：
Hydrogen-containing gas obtained by step (2) aromatic hydrocarbons process integration and step (3) light-hydrocarbon aromatized technique is subjected to transformation suction
It is used as H-G hydrocracking hydrogen return to step (1) H-G hydrocracking technique, hydrogen-containing gas pressure-variable adsorption after attached (PSA) purification
Gained tail gas is used as fuel gas after purification.Wherein, the technology of Pressure Swing Adsorption hydrogen is ordinary skill in the art means,
Concrete operation step repeats no more in the text.
Method according to the present invention " obtains step (1) H-G hydrocracking technique light described in step (3)
Light naphthar that one or both of naphtha, liquefied gas and/or step (2) aromatic hydrocarbons process integration obtain, liquefied gas, penta
Alkane and the combination one or more of raffinated oil are as raw material " include following several situations：
1, any one of the light naphthar that obtains step (1) H-G hydrocracking technique, liquefied gas and step (2) virtue
Light naphthar that hydrocarbon process integration obtains, liquefied gas, pentane and the combination one or more of raffinated oil are as raw material；
2, two kinds and step (2) aromatic hydrocarbons in the light naphthar that obtains step (1) H-G hydrocracking technique, liquefied gas
Light naphthar that process integration obtains, liquefied gas, pentane and the combination one or more of raffinated oil are as raw material；
3, any one of the light naphthar that obtains step (1) H-G hydrocracking technique, liquefied gas are used as raw material；
4, two kinds in the light naphthar that obtains step (1) H-G hydrocracking technique, liquefied gas are used as raw material；
5, light naphthar that step (2) aromatic hydrocarbons process integration obtains, liquefied gas, pentane and any one of raffinate oil are made
For raw material；
6, by light naphthar that step (2) aromatic hydrocarbons process integration obtains, liquefied gas, pentane and several groups in raffinating oil
Cooperation is raw material.
Method according to the present invention, aromatic hydrocarbons process integration and the produced hydrogen of light-hydrocarbon aromatized technique and diesel oil hydrogenation
The required hydrogen of process keeps balance, can effectively improve the utilization rate of hydrogen product in this way, and provided by the invention
Diversification raw material aromatic hydrocarbons method does not need additional organizational system hydrogen production device, further reduces project investment.
Method according to the present invention, it is preferable that this method further includes sulfur recovery technology：
Sulphur impurity in raw material is after step (1) H-G hydrocracking technique and step (2) aromatic hydrocarbons process integration, then passes through
Sulfur recovery technology obtains sulphur or sulfuric acid.
Method according to the present invention, specifically, this method is further comprising the steps of：
By step (1) H-G hydrocracking technique and step (2) aromatic hydrocarbons process integration (petroleum naphtha hydrogenation unit therein)
The hydrogen sulfide (in rich amine solution and acid water) of generation obtains sulphur or sulfuric acid through sulfur recovery technology.Sulfur recovery of the present invention
Technique is ordinary skill in the art means, and the present invention does not make specific requirement to sulfur recovery technology, and those skilled in the art can be with
It is needed to select suitable sulfur recovery technology according to field operation, as long as ensureing that the object of the invention may be implemented.In the present invention
In one specific embodiment, sulfur recovery technology used is Clause recovery technology of sulfur.
Method according to the present invention, it is preferable that this method is further comprising the steps of：
Under non-hydrogen operating condition, light-hydrocarbon aromatized technique, institute are carried out as raw material using outsourcing liquefied gas or light naphthar
Obtain the hydrogen that goes into operation that hydrogen is used separately as H-G hydrocracking technique and aromatic hydrocarbons process integration.I.e.：Lighter hydrocarbons are used when project kickoff
Aromatisation takes the lead in going into operation, this device is to be operated under conditions of non-hydrogen, and H-G hydrocracking device and aromatic hydrocarbons joint fill
It needs to operate in the case where facing hydrogen state when setting driving, so light-hydrocarbon aromatized device can be original with outsourcing liquefied gas or light naphthar
Material is preferential to drive, and production hydrogen supply hydrocracking unit and Aromatic Hydrocarbon United Plant drive to use, and drive without outsourcing hydrogen.
Method according to the present invention, the diesel oil used in step (1) H-G hydrocracking technique include catalytic diesel oil, split
Solve diesel oil, straight-run diesel oil.
Method according to the present invention, the outsourcing feed naphtha used in step (2) aromatic hydrocarbons process integration includes straight run
Naphtha, hydrocracked naphtha.
Method according to the present invention, the outsourcing BTX aromatics used in step (2) aromatic hydrocarbons process integration include reforming C7+
Oil reforms C8+ oil.
Method according to the present invention, this method specifically include following steps：
H-G hydrocracking technique：It is diesel oil and the produced heavy aromatics of aromatic hydrocarbons process integration that its is raw materials used.Wherein, diesel oil
The diesel oil with respect to low price such as catalytic diesel oil, pyrolysis gas oil, straight-run diesel oil can be used, hydrogen is by aromatic hydrocarbons process integration and lighter hydrocarbons aromatization
Change process by-product hydrogen-containing gas to provide after Pressure Swing Adsorption.By fixed bed hydrogenation cracking reaction after raw material and hydrogen mixing
Afterwards, isolated fuel gas, liquefied gas, light naphthar, heavy naphtha and unconverted diesel oil, unconverted diesel cycle return fixed bed
Hydrocracking reaction system further participates in cracking reaction.Light naphthar and liquefaction pneumatic transmission to light-hydrocarbon aromatized technique, scheelite brain
Oil is sent to aromatic hydrocarbons process integration；
Aromatic hydrocarbons process integration：Its raw material has naphtha (outsourcing), BTX aromatics (outsourcing), H-G hydrocracking heavy naphtha
With the BTX aromatics of light-hydrocarbon aromatized device production.Straight-run naphtha, hydrocracked naphtha etc. can be used in outsourcing feed naphtha,
The BTX aromatics raw material of outsourcing can be to reform C7+ oil or reform C8+ oil etc..Aromatic hydrocarbons process integration includes petroleum naphtha hydrogenation, connects
The techniques such as continuous reformation, catalyst regeneration, Aromatics Extractive Project, disproportionation and transalkylation, isomerization, adsorbing separation, dimethylbenzene separation, respectively
Process stream is interrelated, is conventional machining flow, is not described further in detail herein.Different raw materials enters the difference of Aromatic Hydrocarbon United Plant
Unit, in specific embodiment of the present invention, if the impurity contents such as sulphur meet reforming process in the hydrotreated naphtha of outsourcing
Feed needs if, then can to outsourcing naphtha carry out simple dehydration, removing light naphthar after, be directly sent to reformation
Otherwise device needs to be introduced into Naphtha hydrofining unit；
The produced H-G hydrocracking heavy naphtha of H-G hydrocracking technique can be directly into reformer in this method；But
Straight-run naphtha enters reformer after need to first passing through petroleum naphtha hydrogenation；And reform C7+ oil or C8+ oil need not move through naphtha
Add hydrogen and reformation, dimethylbenzene separative element can be fed directly to.Above-mentioned raw materials obtain hydrogen-containing gas, fuel after Aromatic Hydrocarbon United Plant
Air-liquid gas light naphthar, pentane, is raffinated oil, benzene and para-xylene product；Light naphthar, pentane, is raffinated oil at liquefied gas
It send to light-hydrocarbon aromatized device, benzene and paraxylene manufacture are sold outside；
The hydrogen sulfide that hydrocracking process and aromatic hydrocarbons process integration generate is sent to sulphur to return (in rich amine solution and acid water)
Receiving apparatus.Sulfur recovery unit combination market situation may be selected different process routes and convert the sulphur brought in charging to sulphur
Or sulfuric acid, meet environmental requirement.
Light-hydrocarbon aromatized technique：Its raw material has light naphthar, liquefied gas, pentane and raffinates oil, and is all from diesel oil hydrogenation and splits
Chemical industry skill and aromatic hydrocarbons process integration.Product is hydrogen-containing gas, propane and BTX aromatics, and hydrogen-containing gas is produced with aromatic hydrocarbons process integration
Hydrogen-containing gas send together to pressure-variable adsorption and extracts high-purity hydrogen, and BTX aromatics are used as the raw material of Aromatic Hydrocarbon United Plant, and propane goes out
It is sold outside factory.
Method according to the present invention, light naphthar that H-G hydrocracking technique obtains, one kind in liquefied gas or
Light naphthar that two kinds and aromatic hydrocarbons process integration obtain, liquefied gas, pentane and whole, one or more of in raffinating oil also may be used
As product export.
Method according to the present invention, in aromatic hydrocarbons process integration, the CONTINUOUS REFORMER, catalyst regeneration, disproportionation and
The patented technology of UOP (UOP) may be used in transalkylation, adsorbing separation, isomerization, which can
With with reference at least following 5 patents：
1, catalytic reforming technology can refer to the special of entitled " using naphtha as the method for the catalytic reforming of raw material "
Profit application, Publication No. CN1044488A；
2, catalyst regeneration techniques can refer to entitled " method and apparatus for making regenerated catalyst particles "
Patent application, Publication No. CN103517761A；
3, disproportionation and transalkylation technology can refer to entitled " the aromatic compounds choosing with the conversion ratio improved
The patent application of selecting property disproportionation process ", Publication No. CN101668723A；
4, adsorption separation technology " can utilize the method and dress of adsorbing separation and fractionation recovery product with reference to entitled
Set " patent application, Publication No. CN104159647A；
5, isomerization technique can refer to the patent Shen of entitled " selective dimethyl isomerization and ethylbenzene conversion "
Please, Publication No. CN1342631A；
The CONTINUOUS REFORMER, catalyst regeneration, disproportionation and transalkylation, adsorbing separation, isomerization can also use France
The patented technology of Axens, the patented technology can refer at least following 5 patents：
1, catalytic reforming technology can refer to entitled " in several areas of the moving bed reaction side by side side of catalytic reforming
The patent application of method ", Publication No. CN1042559A；
2, catalyst regeneration techniques can refer to entitled " aromatic hydrocarbon prepares or the regeneration method of reforming catalyst "
Patent application, Publication No. CN1045411A；
3, disproportionation and transalkylation technology can refer to entitled " in the presence of two kinds of zeolite catalysts alkylaromatic hydrocarbon
The patent application of the method for disproportionation and transalkylation ", Publication No. CN1164524A；
4, adsorption separation technology can refer to the special of entitled " improved simulated mobile bed separation process and equipment "
Profit application, Publication No. CN1714915A；
5, isomerization technique " can include double zeolite catalysises of group VIII metal and Group IIIA metal with reference to entitled
The patent application of agent and its application in the isomerization of aromatic C 8 compounds ", Publication No. CN101340976A.
Method according to the present invention, in aromatic hydrocarbons process integration, the pumping of Shi Keyuan may be used in the Aromatics Extractive Project
Distillation technique is carried, which can refer to entitled " a kind of method of extractive distillation aromatics separation and use compound molten
The patent application of agent ", Publication No. CN1393507A.These above-mentioned technologies all have abundant achievement, technology at
It is ripe reliable.
The lighter hydrocarbons aromatization of Dalian University of Technology may be used in method according to the present invention, the light-hydrocarbon aromatized technique
Change technology, the technology can refer to the patent application of entitled " a kind of process of lower carbon number hydrocarbons hydroaromatization ",
Publication No. CN103834437A.Can process H-G hydrocracking using the technique and kind that Aromatic Hydrocarbon United Plant obtains compared with
More light hydrocarbon products, such as：It light naphthar, liquefied gas, pentane and raffinates oil, obtains hydrogen-containing gas, BTX aromatics and bromopropane product.
Method according to the present invention, in aromatic hydrocarbons process integration, the petroleum naphtha hydrogenation technique and xylene fractionation
Technique is also this field common process.
Method according to the present invention, light-hydrocarbon aromatized technique is with H-G hydrocracking technique and aromatic hydrocarbons process integration institute
It is raw material to obtain product, processes BTX aromatics product, which can not only improve aromatics yield, also reduce
Product category, optimizes, reduces storage and handling facility, floor space and cost of investment.
In the method for diversification raw material aromatic hydrocarbons provided by the invention, the ratio of various external sources is limited by hydrogen and puts down
Weighing apparatus should determine the raw material proportioning for comparing optimization according to hydrogen output in factory and raw material hydrogen-consuming volume, avoid building device for producing hydrogen increase
Investment, while also avoiding rich a large amount of hydrogen that from can not utilizing, and fuel can only be used as to burn up.I.e.：The various raw material proportionings of the present invention
It is influenced by raw material type and property, the present invention does not make specific requirement to various raw material proportionings, and those skilled in the art can basis
Field operation needs to reasonably select adjustment raw material proportioning, as long as ensureing that the object of the invention may be implemented.
On the other hand, the present invention also provides a kind of system of the method for realizing above-mentioned diversification raw material aromatic hydrocarbons,
Including：
H-G hydrocracking device, Aromatic Hydrocarbon United Plant and light-hydrocarbon aromatized device；
Wherein, the H-G hydrocracking device is provided with that hydrogen inlet, diesel oil entrance, fuel gas outlet, liquefied gas goes out
Mouth, light naphthar outlet, heavy naphtha outlet；
Aromatic Hydrocarbon United Plant includes petroleum naphtha hydrogenation unit, CONTINUOUS REFORMER unit, catalyst regeneration units, Aromatics Extractive Project list
Member, disproportionation and transalkylation, adsorption separation unit, isomerization unit and xylene fractionation unit；
The Aromatic Hydrocarbon United Plant includes naphtha entrance, the first BTX aromatics entrance, heavy naphtha entrance, hydrogen-containing gas
Outlet, fuel gas outlet, liquefied gas outlet, pentane outlet, light naphthar outlet, the outlet of raffinate oil export, heavy aromatics, benzene outlet
It is exported with paraxylene；
The light-hydrocarbon aromatized device is provided with liquefied gas entrance, and pentane is raffinated oil and light naphthar entrance, BTX aromatics
Outlet, hydrogen-containing gas outlet, propane outlets；
The heavy naphtha outlet is connected by pipeline with the CONTINUOUS REFORMER unit of the Aromatic Hydrocarbon United Plant；
The light naphthar outlet of the H-G hydrocracking device, the light naphthar outlet of Aromatic Hydrocarbon United Plant pass through respectively
Pipeline and the pentane are raffinated oil and light naphthar entrance is connected；
The liquefied gas outlet of the H-G hydrocracking device, the liquefied gas outlet of Aromatic Hydrocarbon United Plant pass through pipeline respectively
It is connected with the liquefied gas entrance；
Pentane outlet, raffinate oil export respectively by pipeline and the pentane, raffinate oil and light naphthar entrance phase
Even.
System according to the present invention, it is preferable that the system further includes sulfur recovery unit, which passes through pipe
Road is connected with the H-G hydrocracking device.
System according to the present invention, it is preferable that the H-G hydrocracking device is additionally provided with heavy aromatics entrance, should
Heavy aromatics entrance is connected by pipeline with the outlet of the heavy aromatics of Aromatic Hydrocarbon United Plant.
System according to the present invention, it is preferable that the Aromatic Hydrocarbon United Plant is additionally provided with the second BTX aromatics entrance,
The second BTX aromatics entrance is connected by pipeline with the outlet of the BTX aromatics of light-hydrocarbon aromatized device.
System according to the present invention, it is preferable that the system further includes pressure-swing absorption apparatus, the Aromatic Hydrocarbon United Plant
Hydrogen-containing gas outlet, light-hydrocarbon aromatized device hydrogen-containing gas outlet respectively by pipeline via pressure-swing absorption apparatus with it is described
The hydrogen inlet of H-G hydrocracking device is connected.
System according to the present invention, wherein the first BTX aromatics entrance, the second BTX aromatics of Aromatic Hydrocarbon United Plant
Entrance is respectively used to the BTX aromatics for being passed through outsourcing BTX aromatics and being generated by light-hydrocarbon aromatized device.Both BTX aromatics are equal
It is to enter xylene fractionation unit.
System according to the present invention, petroleum naphtha hydrogenation unit, CONTINUOUS REFORMER unit included by Aromatic Hydrocarbon United Plant,
Catalyst regeneration units, Aromatics Extractive Project unit, disproportionation and transalkylation, adsorption separation unit, isomerization unit and diformazan
Material has cycle between benzene fractionation unit, and therefore, the present invention finally separates product from which specific unit not to be made specifically
Requirement, those skilled in the art can need to carry out reasonable selection adjustment according to field operation, as those skilled in the art can
It is reasonably selected with the technology according to UOP and Axens, as long as ensureing that the purpose of the present invention may be implemented.
In method provided by the invention, processing route includes H-G hydrocracking, petroleum naphtha hydrogenation, CONTINUOUS REFORMER, urges
The techniques such as agent regeneration, Aromatics Extractive Project, disproportionation and transalkylation, isomerization, adsorbing separation and xylene fractionation technique, it is main to produce
Product include benzene, paraxylene and propane.First, raw material and product mutually supply, reduce low value between each technique in the processing flow
Product category, optimization storage and handling facility reduce storage and transportation investment；Secondly, product category is concentrated, and added value is high.In addition, the processing hand
Flexibly, the distribution of each product can need flexibly to be allocated section according to market：Light naphthar, pentane, is raffinated oil at liquefied gas
One or more of intermediate products can also be used as product export, and the storage and handling facility under this operating mode relies on normal work as possible
Condition should not additionally increase too many investment because considering various working.
In conclusion the method and system of diversification raw material aromatic hydrocarbons provided by the present invention can produce benzene, to diformazan
The high value added products such as benzene, and raw material proportioning and product structure can be neatly adjusted according to market situation, it overcomes and adopts merely
With naphtha be raw material aromatic hydrocarbons existing for it is of high cost, benefit is low, hydrogen is more than needed the problems such as, and using present in processing of heavy oil
Investment it is big, the problems such as difficulty of processing is big, method provided by the present invention is a kind of novel aromatics production processing route.
Description of the drawings
Fig. 1 is flow and the structural representation of the method and system of diversification raw material aromatic hydrocarbons provided in an embodiment of the present invention
Figure.
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, in conjunction in detail below
Embodiment and Figure of description carry out following detailed description to technical scheme of the present invention, but should not be understood as can to of the invention
The restriction of practical range.
Embodiment 1
A kind of system of the method for realizing diversification raw material aromatic hydrocarbons is present embodiments provided, structural schematic diagram is such as
Shown in Fig. 1, from figure 1 it appears that the system includes：
H-G hydrocracking device, Aromatic Hydrocarbon United Plant and light-hydrocarbon aromatized device；
Wherein, the H-G hydrocracking device is provided with that hydrogen inlet, diesel oil entrance, fuel gas outlet, liquefied gas goes out
Mouth, light naphthar outlet, heavy naphtha outlet；
Aromatic Hydrocarbon United Plant includes petroleum naphtha hydrogenation unit, CONTINUOUS REFORMER unit, catalyst regeneration units, Aromatics Extractive Project list
Member, disproportionation and transalkylation, adsorption separation unit, isomerization unit and xylene fractionation unit；
The Aromatic Hydrocarbon United Plant includes naphtha entrance, the first BTX aromatics entrance, heavy naphtha entrance, hydrogen-containing gas
Outlet, fuel gas outlet, liquefied gas outlet, pentane outlet, light naphthar outlet, the outlet of raffinate oil export, heavy aromatics, benzene outlet
It is exported with paraxylene；
The light-hydrocarbon aromatized device is provided with liquefied gas entrance, and pentane is raffinated oil and light naphthar entrance, BTX aromatics
Outlet, hydrogen-containing gas outlet, propane outlets；
The heavy naphtha outlet is connected by pipeline with the CONTINUOUS REFORMER unit of the Aromatic Hydrocarbon United Plant；
The light naphthar outlet of the H-G hydrocracking device, the light naphthar outlet of Aromatic Hydrocarbon United Plant pass through respectively
Pipeline and the pentane are raffinated oil and light naphthar entrance is connected；
The liquefied gas outlet of the H-G hydrocracking device, the liquefied gas outlet of Aromatic Hydrocarbon United Plant pass through pipeline respectively
It is connected with the liquefied gas entrance；
Pentane outlet, raffinate oil export respectively by pipeline and the pentane, raffinate oil and light naphthar entrance phase
Even.
The system further includes sulfur recovery unit, which passes through pipeline and the H-G hydrocracking device phase
Even.
The H-G hydrocracking device is additionally provided with heavy aromatics entrance, which is combined by pipeline with aromatic hydrocarbons
The heavy aromatics outlet of device is connected.
The Aromatic Hydrocarbon United Plant is additionally provided with the second BTX aromatics entrance, the second BTX aromatics entrance by pipeline with
The BTX aromatics outlet of light-hydrocarbon aromatized device is connected.
The system further includes pressure-swing absorption apparatus, the hydrogen-containing gas outlet of the Aromatic Hydrocarbon United Plant, light-hydrocarbon aromatized dress
The hydrogen-containing gas set exports the hydrogen inlet by pipeline via pressure-swing absorption apparatus and the H-G hydrocracking device respectively
It is connected.
Embodiment 2
Present embodiments provide a kind of method of diversification raw material aromatic hydrocarbons comprising step in detail below：
(1) H-G hydrocracking technique：By diesel oil by be hydrocracked be converted into fuel gas, liquefied gas, light naphthar and
Heavy naphtha；
(2) aromatic hydrocarbons process integration：With naphtha, the scheelite of BTX aromatics and step (1) H-G hydrocracking technique productions
Cerebrol is raw material, by petroleum naphtha hydrogenation, CONTINUOUS REFORMER, catalyst regeneration, Aromatics Extractive Project, disproportionation and transalkylation, isomerization,
Adsorbing separation and xylene fractionation technique obtain hydrogen-containing gas, fuel gas, liquefied gas, pentane, raffinate oil, heavy aromatics, benzene and right
Dimethylbenzene；
(3) light-hydrocarbon aromatized technique：In light naphthar that step (1) H-G hydrocracking technique is obtained, liquefied gas
Light naphthar that one or two and/or step (2) aromatic hydrocarbons process integration obtain, liquefied gas, pentane and one kind in raffinating oil
Or several combinations is as raw material, by light-hydrocarbon aromatized, obtains hydrogen-containing gas, propane and BTX aromatics.
Specifically, H-G hydrocracking technique is using fixed bed hydrogenation process technology, aromatic hydrocarbons process integration is
Wherein at least include five above-mentioned patented technologies using the complete set technology of Axens companies, light-hydrocarbon aromatized technique is using big
The even light-hydrocarbon aromatized technology of Polytechnics, sulfur recovery use Clause sulphur recoveries+tail gas treatment process.
This example is hydrocracked stone brain with 900,000 tons/year of catalytic diesel oils of outsourcing, 200,000 tons/year of DCC light oil, 110,000 tons/year
Oil, 250,000 tons/year of reformation C7+ oil are raw material, obtain benzene, paraxylene, propane, sulfur product.
Using catalytic diesel oil and DCC light oil as the raw material of H-G hydrocracking technique, H-G hydrocracking device it is main
Product has fuel gas, liquefied gas, light naphthar and heavy naphtha.Wherein, raw material of the heavy naphtha as Aromatic Hydrocarbon United Plant, liquid
Change the raw material of gas and light naphthar as light-hydrocarbon aromatized device.
This example outsourcing hydrocracked naphtha quality is higher, and the impurity contents such as sulphur meet reformer charging, through simple
After dehydration, removing light naphthar component, the CONTINUOUS REFORMER of Aromatic Hydrocarbon United Plant is mixed into H-G hydrocracking heavy naphtha
Device carries out catalytic reforming reaction, and major product is reformed oil (C6+).Major product from light-hydrocarbon aromatized device is mixed
It closes aromatic hydrocarbons and enters Aromatic Hydrocarbon United Plant as raw material, reform C7+ oil with reformed oil (C6+), outsourcing and converge, join by aromatic hydrocarbons
Attach together other devices set, i.e., aromatic extraction unit, disproportionation and transalkylation unit, adsorption separation device, isomerization unit and
Xylene fractionation device is processed.The product of Aromatic Hydrocarbon United Plant includes：Hydrogen-containing gas, fuel gas, liquefied gas, light naphthar, penta
Alkane is raffinated oil, benzene, paraxylene and heavy aromatics product.Wherein, heavy aromatics product is sent to H-G hydrocracking device freshening；Liquid
Changing gas, light naphthar, pentane and raffinate oil product is supplied to light-hydrocarbon aromatized device as raw material.Benzene and para-xylene product go out
Factory sells.
The product of light-hydrocarbon aromatized device has hydrogen-containing gas, propane and BTX aromatics, BTX aromatics to be used as aromatic hydrocarbons to combine again
The raw material of device.The bromopropane product manufacture sale of light-hydrocarbon aromatized device.The hydrogen-containing gas of Aromatic Hydrocarbon United Plant and lighter hydrocarbons aromatization
Disguise the hydrogen-containing gas set and supplies the use of H-G hydrocracking device after Pressure Swing Adsorption together.
In this example, the hydrogen of Aromatic Hydrocarbon United Plant and the production of light-hydrocarbon aromatized device can meet H-G hydrocracking device
It uses, substantially without hydrogen more than needed, device for producing hydrogen is built without additional.
In this example, if when light-hydrocarbon aromatized device is stopped work or when other device product prices are advantageous, diesel oil hydrogenation
Cracking unit and the produced light naphthar of Aromatic Hydrocarbon United Plant, liquefied gas, pentane and whole, one or more of in raffinating oil
It can be used as product export.
The final products of entire processing route are benzene, paraxylene and bromopropane product.If most to produce paraxylene
For principle, 700,000 tons/year of paraxylene, 310,000 tons/year of benzene, 150,000 tons/year of propane can be at most produced.
Benzaldehyde product property：
Product meets the technology requirement of petrobenzene GB/T3405-2011, and quality index see the table below shown in 1.
1 petrobenzene of table (GB/T3405-2011) quality index
Para-xylene product property：
It meets the index about high-class product in People's Republic of China (PRC) petroleum chemical industry standard SH1486.1-2008
It is required that.
Oil paraxylene (SH1486.1-2008) choicest quality figureofmerit is as shown in table 2 below.
Table 2 oil paraxylene (SH1486.1-2008) choicest quality figureofmerit
Bromopropane product property is as shown in table 3 below：
3 bromopropane product quality index of table
In conclusion processing method provided by the invention can produce the high value added products such as benzene, paraxylene with system,
And which overcome simple the problems such as use naphtha to be of high cost, benefit is low, hydrogen is had more than needed present in raw material, and use
The problems such as investment present in processing of heavy oil is big, and difficulty of processing is big, method provided by the present invention are a kind of novel aromatic hydrocarbons lifes
Produce processing route.
Claims (6)
1. a kind of method of diversification raw material aromatic hydrocarbons comprising following steps：
(1) H-G hydrocracking technique：It converts diesel oil to fuel gas, liquefied gas, light naphthar and scheelite by being hydrocracked
Cerebrol；
H-G hydrocracking technique described in step (1) uses fixed bed hydrogenation process, the unconverted diesel oil of one way whole
Fixed bed hydrogenation cracking system is recycled back to continue to be hydrocracked；
(2) aromatic hydrocarbons process integration：With naphtha, the heavy naphtha of BTX aromatics and step (1) H-G hydrocracking technique productions
For raw material, pass through petroleum naphtha hydrogenation, CONTINUOUS REFORMER, catalyst regeneration, Aromatics Extractive Project, disproportionation and transalkylation, isomerization, absorption
Separation and xylene fractionation technique, obtain hydrogen-containing gas, fuel gas, liquefied gas, pentane, light naphthar, raffinate oil, heavy aromatics,
Benzene and paraxylene；
This method is further comprising the steps of：The heavy aromatics that step (2) aromatic hydrocarbons process integration is obtained is as H-G hydrocracking
Raw material return to step (1) H-G hydrocracking technique；
(3) light-hydrocarbon aromatized technique：One kind in light naphthar that step (1) H-G hydrocracking technique is obtained, liquefied gas
Or light naphthar, liquefied gas, pentane and one kind or several in raffinating oil that two kinds and/or step (2) aromatic hydrocarbons process integration obtain
Kind combination as raw material, by light-hydrocarbon aromatized, obtain hydrogen-containing gas, propane and BTX aromatics；
The diesel oil is catalytic diesel oil, pyrolysis gas oil, straight-run diesel oil；
This method is further comprising the steps of：
Hydrogen-containing gas obtained by step (2) aromatic hydrocarbons process integration and step (3) light-hydrocarbon aromatized technique is carried out pressure-variable adsorption to carry
H-G hydrocracking hydrogen return to step (1) H-G hydrocracking technique is used as after pure, institute after hydrogen-containing gas Pressure Swing Adsorption
It obtains tail gas and is used as fuel gas；
Under non-hydrogen operating condition, light-hydrocarbon aromatized technique, gained hydrogen are carried out as raw material using outsourcing liquefied gas or light naphthar
Gas is used separately as the hydrogen that goes into operation of H-G hydrocracking technique and aromatic hydrocarbons process integration；
This method further includes sulfur recovery technology：
Sulphur impurity in raw material returns after step (1) H-G hydrocracking technique and step (2) aromatic hydrocarbons process integration, then by sulphur
Skill of knocking off obtains sulphur or sulfuric acid.
2. according to the method described in claim 1, it is characterized in that, this method is further comprising the steps of：
The BTX aromatics that step (3) light-hydrocarbon aromatized technique is obtained are as the raw material return to step (2) of aromatic hydrocarbons process integration virtue
Hydrocarbon process integration.
3. a kind of system for realizing the method for diversification raw material aromatic hydrocarbons described in claims 1 or 2 comprising：Diesel oil adds
Hydrogen cracking unit, Aromatic Hydrocarbon United Plant and light-hydrocarbon aromatized device；
Wherein, the H-G hydrocracking device is provided with hydrogen inlet, diesel oil entrance, fuel gas outlet, liquefied gas outlet, light
Naphtha outlet, heavy naphtha outlet；
The H-G hydrocracking device is additionally provided with heavy aromatics entrance, which passes through pipeline and Aromatic Hydrocarbon United Plant
Heavy aromatics outlet be connected；
Aromatic Hydrocarbon United Plant include petroleum naphtha hydrogenation unit, CONTINUOUS REFORMER unit, catalyst regeneration units, Aromatics Extractive Project unit,
Disproportionation and transalkylation, adsorption separation unit, isomerization unit and xylene fractionation unit；
The Aromatic Hydrocarbon United Plant includes that naphtha entrance, the first BTX aromatics entrance, heavy naphtha entrance, hydrogen-containing gas go out
Mouth, fuel gas outlet, liquefied gas outlet, pentane outlet, light naphthar outlet, raffinate oil export, heavy aromatics outlet, benzene outlet and
Paraxylene exports；
The light-hydrocarbon aromatized device is provided with liquefied gas entrance, and pentane is raffinated oil and light naphthar entrance, BTX aromatics go out
Mouth, hydrogen-containing gas outlet, propane outlets；
The heavy naphtha outlet is connected by pipeline with the CONTINUOUS REFORMER unit of the Aromatic Hydrocarbon United Plant；
The light naphthar outlet of the H-G hydrocracking device, the light naphthar outlet of Aromatic Hydrocarbon United Plant pass through pipeline respectively
With the pentane, raffinate oil and light naphthar entrance is connected；
The liquefied gas outlet of the H-G hydrocracking device, the liquefied gas outlet of Aromatic Hydrocarbon United Plant pass through pipeline and institute respectively
Liquefied gas entrance is stated to be connected；
Pentane outlet, raffinate oil export respectively by pipeline and the pentane, raffinate oil and light naphthar entrance is connected.
4. system according to claim 3, which is characterized in that the system further includes sulfur recovery unit, the sulfur recovery unit
It is connected with the H-G hydrocracking device by pipeline.
5. system according to claim 3, which is characterized in that the system further includes pressure-swing absorption apparatus, the aromatic hydrocarbons connection
The hydrogen-containing gas for attaching together the hydrogen-containing gas outlet, light-hydrocarbon aromatized device set exports respectively by pipeline via pressure-swing absorption apparatus
It is connected with the hydrogen inlet of the H-G hydrocracking device.
6. system according to claim 3, which is characterized in that the Aromatic Hydrocarbon United Plant is additionally provided with the second BTX aromatics
Entrance, the second BTX aromatics entrance are connected by pipeline with the outlet of the BTX aromatics of light-hydrocarbon aromatized device.
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| US7271303B1 (en) * | 2004-09-22 | 2007-09-18 | Uop Llc | Multi-zone process for the production of diesel and aromatic compounds |
| CN1955259A (en) * | 2005-10-24 | 2007-05-02 | 中国石油化工股份有限公司 | Parallel hydrocracking method |
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