CN106190289A - 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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- CN106190289A CN106190289A CN201610825663.6A CN201610825663A CN106190289A CN 106190289 A CN106190289 A CN 106190289A CN 201610825663 A CN201610825663 A CN 201610825663A CN 106190289 A CN106190289 A CN 106190289A
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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
-
- 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
Abstract
The invention provides the method and system of a kind of diversification raw material aromatic hydrocarbons, the method comprises the following steps: H-G hydrocracking technique: by being hydrocracked, diesel oil is converted into fuel gas, liquefied gas, light naphthar and heavy naphtha；Aromatic hydrocarbons process integration: with Petroleum, BTX aromatics and H-G hydrocracking technique produce heavy naphtha as raw material, by petroleum naphtha hydrogenation, CONTINUOUS REFORMER, catalyst regeneration, Aromatics Extractive Project, disproportionation and transalkylation, adsorbing separation, isomerization and xylene fractionation technique, obtain hydrogen-containing gas, fuel gas, liquefied gas, pentane, light naphthar, raffinate oil, heavy aromatics, benzene and xylol；Light-hydrocarbon aromatized technique: one or both in light naphthar that H-G hydrocracking technique is obtained, liquefied gas, and/or light naphthar, liquefied gas, pentane and the combination of one or more in raffinating oil that aromatic hydrocarbons process integration obtains is as raw material, by light-hydrocarbon aromatized, obtain hydrogen-containing gas, propane and BTX aromatics.
Description
Technical field
The present invention relates to the method and system of a kind of diversification raw material aromatic hydrocarbons, belong to technical field of petrochemical industry.
Background technology
At present, Domestic Oil Products ' Market speedup slows down, and consumption diesel and gasoline ratio is declining year by year, higher than supply diesel and gasoline ratio, diesel oil
Using that peak period is former is expected to be 2018, in fact within 2014, come the most in advance, gasoline is former anticipated reaches peak value in 2025, and it can
Can the year two thousand twenty be advanceed to.Along with the enforcement of petrol and diesel oil state VI standard in future, alkene and arene content in gasoline will be further
Reduce, when the time comes by have part more than needed rich in aromatic hydrocarbons oil product.And the most domestic supply requirement to benzene and xylol still exists
Increase year by year, and there is also supply breach at present.Under above-mentioned market situation, reduce product oil yield, and by part price phase
To cheap middle 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 Petroleum and/or rich in aromatic naphtha (as reformation C7+ oil or reformation C8+ oil) etc. plurality of raw materials,
Thus produce aromatic hydrocarbons further, higher economic benefit can be obtained, the imbalance between supply and demand of product oil can be alleviated again.
Summary of the invention
In order to solve above-mentioned shortcoming and defect, it is an object of the invention to provide the side of a kind of diversification raw material aromatic hydrocarbons
Method.
The present invention also aims to provide the system of a kind of method for realizing above-mentioned diversification raw material aromatic hydrocarbons.
For reaching above-mentioned purpose, on the one hand, the present invention provides a kind of method of diversification raw material aromatic hydrocarbons, and it includes 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: the scheelite produced with Petroleum, BTX aromatics and step (1) H-G hydrocracking technique
Cerebrol is raw material, is divided by petroleum naphtha hydrogenation, CONTINUOUS REFORMER, catalyst regeneration, Aromatics Extractive Project, disproportionation and transalkylation, absorption
From, isomerization and xylene fractionation technique, obtain hydrogen-containing gas, fuel gas, liquefied gas, light naphthar, pentane, raffinate oil, weight
Aromatic hydrocarbons, benzene and xylol；
(3) light-hydrocarbon aromatized technique: in light naphthar that step (1) H-G hydrocracking technique is obtained, liquefied gas
One or both, and/or light naphthar, liquefied gas, pentane and the one in raffinating oil that step (2) aromatic hydrocarbons process integration obtains
Or several combinations is as raw material, by light-hydrocarbon aromatized, obtain hydrogen-containing gas, propane and BTX aromatics.
According to method of the present invention, it is preferable that the H-G hydrocracking technique described in step (1) uses fixed bed to add
Hydrogen process, the unconverted diesel oil of one way all loops back fixed bed hydrogenation cracking system to proceed to be hydrocracked, with
Maximize components such as producing liquefied gas, light naphthar and heavy naphtha.
According to method of the present invention, it is preferable that the method is further comprising the steps of:
The heavy aromatics obtained by step (2) aromatic hydrocarbons process integration returns step (1) bavin as the raw material of H-G hydrocracking
Oil hydrocracking process, to reduce product category of dispatching from the factory.
According to method of the present invention, it is preferable that the method is further comprising the steps of:
BTX aromatics step (3) light-hydrocarbon aromatized technique obtained returns step as the raw material of aromatic hydrocarbons process integration
(2) aromatic hydrocarbons process integration.
According to method of the present invention, it is preferable that the method is further comprising the steps of:
The hydrogen-containing gas of step (2) aromatic hydrocarbons process integration and step (3) light-hydrocarbon aromatized technique gained is carried out transformation suction
Attached (PSA) returns step (1) H-G hydrocracking technique, hydrogen-containing gas pressure-variable adsorption as H-G hydrocracking hydrogen after purifying
After purification, gained tail gas is used as fuel gas.Wherein, the technology of Pressure Swing Adsorption hydrogen is ordinary skill in the art means, its
Concrete operation step repeats no more in the text.
According to method of the present invention, described in step (3), " step (1) H-G hydrocracking technique obtained is light
One or both in Petroleum, liquefied gas, and/or step (2) aromatic hydrocarbons process integration obtain light naphthar, liquefied gas, penta
Alkane and the combination of one or more in raffinating oil are as raw material " include following several situation:
1, any one in the light naphthar that step (1) H-G hydrocracking technique obtained, liquefied gas and step (2) virtue
Light naphthar that hydrocarbon process integration obtains, liquefied gas, pentane and the combination of one or more in raffinating oil are as raw material；
2, two kinds and step (2) aromatic hydrocarbons in the light naphthar that step (1) H-G hydrocracking technique obtained, liquefied gas
Light naphthar that process integration obtains, liquefied gas, pentane and the combination of one or more in raffinating oil are as raw material；
3, any one in the light naphthar that step (1) H-G hydrocracking technique obtained, liquefied gas is as raw material；
4, two kinds in the light naphthar that step (1) H-G hydrocracking technique obtained, liquefied gas as raw material；
5, the light naphthar that obtained by step (2) aromatic hydrocarbons process integration, liquefied gas, pentane and any one in raffinating oil are made
For raw material；
6, the light naphthar that step (2) aromatic hydrocarbons process integration obtained, liquefied gas, pentane and several group in raffinating oil
Cooperation is raw material.
The hydrogen produced according to method of the present invention, aromatic hydrocarbons process integration and light-hydrocarbon aromatized technique and diesel oil hydrogenation
The required hydrogen of process keeps balance, so can be effectively improved the utilization rate of hydrogen product, and the present invention provides
Diversification raw material aromatic hydrocarbons method need not extra organizational system hydrogen production device, further reduces project investment.
According to method of the present invention, it is preferable that the method also 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 sulfur or sulphuric acid.
According to method of the present invention, specifically, the 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) produced obtains sulfur or sulphuric acid through sulfur recovery technology.Sulfur recovery of the present invention
Technique is ordinary skill in the art means, and sulfur recovery technology is not made specific requirement by the present invention, and those skilled in the art are permissible
Need to select suitable sulfur recovery technology according to field operation, as long as ensureing to realize the object of the invention.In the present invention
In one specific embodiment, sulfur recovery technology used is Clause recovery technology of sulfur.
According to method of the present invention, it is preferable that the method is further comprising the steps of:
Under non-hydrogen operating condition, carry out light-hydrocarbon aromatized technique, institute with outsourcing liquefied gas or light naphthar for raw material
Obtain hydrogen and be used separately as the hydrogen that goes into operation of H-G hydrocracking technique and aromatic hydrocarbons process integration.That is: lighter hydrocarbons are used during project kickoff
Aromatisation takes the lead in going into operation, and this device is to operate under conditions of non-hydrogen, and H-G hydrocracking device and aromatic hydrocarbons combine dress
Need when putting driving to operate, so light-hydrocarbon aromatized device can be former with outsourcing liquefied gas or light naphthar under facing hydrogen state
Material is preferential drives, and produces hydrogen supply hydrocracking unit and Aromatic Hydrocarbon United Plant drives to use, it is not necessary to outsourcing hydrogen is driven.
According to method of the present invention, the diesel oil used by step (1) H-G hydrocracking technique includes catalytic diesel oil, splits
Solve diesel oil, straight-run diesel oil.
According to method of the present invention, the outsourcing feed naphtha used by step (2) aromatic hydrocarbons process integration includes straight run
Petroleum, hydrocracked naphtha.
According to method of the present invention, the outsourcing BTX aromatics used by step (2) aromatic hydrocarbons process integration includes reformation C7+
Oil or reformation C8+ oil.
According to method of the present invention, the method specifically includes following steps:
H-G hydrocracking technique: its raw materials used heavy aromatics produced by diesel oil and aromatic hydrocarbons process integration.Wherein, diesel oil
Can use the diesel oil the most at a low price such as catalytic diesel oil, pyrolysis gas oil, straight-run diesel oil, hydrogen is by aromatic hydrocarbons process integration and lighter hydrocarbons aromatization
Metallization processes by-product hydrogen-containing gas provides after Pressure Swing Adsorption.Through fixed bed hydrogenation cracking reaction after raw material and hydrogen mixing
After, isolated fuel gas, liquefied gas, light naphthar, heavy naphtha and unconverted diesel oil, unconverted diesel cycle returns fixed bed
Hydrocracking reaction system further participates in cracking reaction.Light naphthar and liquefied gas deliver to light-hydrocarbon aromatized technique, scheelite brain
Aromatic hydrocarbons process integration delivered to by oil；
Aromatic hydrocarbons process integration: its raw material has Petroleum (outsourcing), BTX aromatics (outsourcing), H-G hydrocracking heavy naphtha
The BTX aromatics produced with light-hydrocarbon aromatized device.Outsourcing feed naphtha can use straight-run naphtha, hydrocracked naphtha etc.,
The BTX aromatics raw material of outsourcing can be reformation C7+ oil or reformation C8+ oil etc..Aromatic hydrocarbons process integration comprises petroleum naphtha hydrogenation, company
The techniques such as continuous reformation, catalyst regeneration, Aromatics Extractive Project, disproportionation and transalkylation, isomerization, adsorbing separation, dimethylbenzene separation, respectively
Process stream is interrelated, for conventional machining flow process, 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 content such as sulfur meets reforming process in the hydrotreated naphtha of outsourcing
Feed needs if, then outsourcing Petroleum can be carried out simple dehydration, removing light naphthar after, directly be sent to reform
Device, otherwise needs to be introduced into Naphtha hydrofining unit；
The H-G hydrocracking heavy naphtha that in this method, H-G hydrocracking technique is produced can directly enter reformer；But
Straight-run naphtha enters reformer after need to first passing through petroleum naphtha hydrogenation；And the C7+ that reforms is oily or C8+ oil needs not move through Petroleum
Hydrogenation and reformation, can be fed directly to dimethylbenzene separative element.Above-mentioned raw materials obtains hydrogen-containing gas, fuel after Aromatic Hydrocarbon United Plant
Air-liquid activating QI, light naphthar, pentane, raffinate oil, benzene and para-xylene product；Light naphthar, liquefied gas, pentane, raffinate oil all
Deliver to sell outside light-hydrocarbon aromatized device, benzene and xylol dispatch from the factory；
The hydrogen sulfide (in rich amine solution and acid water) that hydrocracking process and aromatic hydrocarbons process integration produce is sent to sulfur return
Receiving apparatus.Sulfur recovery unit combines market situation, and the sulfur brought in charging is converted into sulfur by optional different process route
Or sulphuric acid, meet environmental requirement.
Light-hydrocarbon aromatized technique: its raw material has light naphthar, liquefied gas, pentane and raffinates oil, is all from diesel oil hydrogenation and splits
Metallization processes 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 is delivered to pressure-variable adsorption in the lump and is extracted high-purity hydrogen, and BTX aromatics is used as the raw material of Aromatic Hydrocarbon United Plant, and propane goes out
Sell outside factory.
According to method of the present invention, one in light naphthar that H-G hydrocracking technique obtains, liquefied gas or
Two kinds, and aromatic hydrocarbons process integration obtain light naphthar, liquefied gas, pentane and in raffinating oil whole, one or more also may be used
As product export.
According to method of the present invention, in aromatic hydrocarbons process integration, described CONTINUOUS REFORMER, catalyst regeneration, disproportionation and
Transalkylation, adsorbing separation, isomerization can use the patented technology of UOP (UOP), and this patented technology can
With with reference at least following 5 patents:
1, catalytic reforming technology is referred to the special of invention entitled " method of the catalytic reforming with Petroleum as raw material "
Profit application, its Publication No. CN1044488A；
2, catalyst regeneration techniques is referred to invention entitled " method and apparatus for making regenerated catalyst particles "
Patent application, its Publication No. CN103517761A；
3, disproportionation and transalkylation technology be referred to invention entitled " have raising conversion ratio aromatic compounds choosing
Selecting property disproportionation process " patent application, its Publication No. CN101668723A；
4, adsorption separation technology is referred to invention entitled " method utilizing adsorbing separation and fractional distillation to reclaim product and dress
Put " patent application, its Publication No. CN104159647A；
5, isomerization technique is referred to the patent Shen of invention entitled " selective dimethyl isomerization and ethylbenzene convert "
Please, its Publication No. CN1342631A；
The regeneration of described CONTINUOUS REFORMER, catalyst, disproportionation and transalkylation, adsorbing separation, isomerization can also use France
The patented technology of Axens, this patented technology is referred at least following 5 patents:
1, catalytic reforming technology is referred to invention entitled " in several districts of the moving bed reaction side by side side of catalytic reforming
Method " patent application, its Publication No. CN1042559A；
2, catalyst regeneration techniques is referred to invention entitled " aromatic hydrocarbon preparation or the renovation process of reforming catalyst "
Patent application, its Publication No. CN1045411A；
3, disproportionation and transalkylation technology are referred to invention entitled " in the presence of two kinds of zeolite catalysts alkylaromatic hydrocarbon
Disproportionation and the method for transalkylation " patent application, its Publication No. CN1164524A；
4, adsorption separation technology is referred to the special of invention entitled " simulated mobile bed separation process of improvement and equipment "
Profit application, its Publication No. CN1714915A；
5, isomerization technique is referred to invention entitled " comprise double zeolite catalysises of group VIII metal and Group IIIA metal
Agent and the application in the isomerization of aromatic C 8 compounds thereof " patent application, its Publication No. CN101340976A.
According to method of the present invention, in aromatic hydrocarbons process integration, described Aromatics Extractive Project can use taking out of Shi Ke institute
Carrying distillation technique, this technology is referred to invention entitled " a kind of method of extractive distillation aromatics separation and use compound molten
Agent " patent application, its Publication No. CN1393507A.These above-mentioned Technologies are respectively provided with abundant achievement, and technology becomes
Ripe reliably.
According to method of the present invention, described light-hydrocarbon aromatized technique can use the lighter hydrocarbons aromatization of Dalian University of Technology
Change technology, this technology is referred to the patent application of invention entitled " process of a kind of lower carbon number hydrocarbons hydroaromatization ", its
Publication No. CN103834437A.Utilize this technique can process H-G hydrocracking and kind that Aromatic Hydrocarbon United Plant obtains relatively
Many light hydrocarbon products, such as: light naphthar, liquefied gas, pentane and raffinate oil, obtain hydrogen-containing gas, BTX aromatics and bromopropane product.
According to method of the present invention, in aromatic hydrocarbons process integration, described petroleum naphtha hydrogenation technique and xylene fractionation
Technique is also this area common process.
According to method of the present invention, light-hydrocarbon aromatized technique is with H-G hydrocracking technique and aromatic hydrocarbons process integration institute
Obtaining product is raw material, and processing BTX aromatics product, this light-hydrocarbon aromatized technique not only can improve aromatics yield, also reduce
Product category, optimizes, decreases storage and handling facility, floor space and cost of investment.
In the method for the diversification raw material aromatic hydrocarbons of present invention offer, the ratio of various external source is limited by hydrogen and puts down
Weighing apparatus, should determine the proportioning raw materials comparing optimization according to hydrogen output in factory and raw material hydrogen-consuming volume, it is to avoid building device for producing hydrogen increases
Investment, also avoids rich a large amount of hydrogen to utilize simultaneously, and burns only as fuel.That is: the various proportioning raw materials of the present invention
Being affected by raw material type and character, various proportioning raw materials are not made specific requirement by the present invention, and those skilled in the art can basis
Field operation needs rationally to select to adjust proportioning raw materials, as long as ensureing to realize the object of the invention.
On the other hand, the present invention also provides for the system of a kind of method for realizing above-mentioned diversification raw material aromatic hydrocarbons, its
Including:
H-G hydrocracking device, Aromatic Hydrocarbon United Plant and light-hydrocarbon aromatized device；
Wherein, described H-G hydrocracking device is provided with hydrogen inlet, diesel oil entrance, fuel gas exports, liquefied gas goes out
The outlet of mouth, light naphthar, heavy naphtha outlet；
Aromatic Hydrocarbon United Plant includes petroleum naphtha hydrogenation unit, CONTINUOUS REFORMER unit, catalyst regeneration units, Aromatics Extractive Project list
Unit, disproportionation and transalkylation, adsorption separation unit, isomerization unit and xylene fractionation unit；
Described Aromatic Hydrocarbon United Plant includes Petroleum entrance, the first BTX aromatics entrance, heavy naphtha entrance, hydrogen-containing gas
Outlet, fuel gas outlet, liquefied gas outlet, pentane outlet, light naphthar outlet, outlet of raffinating oil, heavy aromatics outlet, benzene outlet
Export with xylol；
Described light-hydrocarbon aromatized device is provided with liquefied gas entrance, pentane, raffinates oil and light naphthar entrance, BTX aromatics
Outlet, hydrogen-containing gas outlet, propane outlets；
The outlet of described heavy naphtha is connected with the CONTINUOUS REFORMER unit of described Aromatic Hydrocarbon United Plant by pipeline；
The light naphthar outlet of described H-G hydrocracking device, the light naphthar outlet of Aromatic Hydrocarbon United Plant are passed through respectively
Pipeline and described pentane, raffinate oil and light naphthar entrance is connected；
Pipeline is passed through in the liquefied gas outlet of described H-G hydrocracking device, the liquefied gas outlet of Aromatic Hydrocarbon United Plant respectively
It is connected with described liquefied gas entrance；
The outlet of described pentane, raffinate oil outlet respectively by pipeline and described pentane, raffinate oil and light naphthar entrance phase
Even.
According to system of the present invention, it is preferable that this system also includes sulfur recovery unit, this sulfur recovery unit is by pipe
Road is connected with described H-G hydrocracking device.
According to system of the present invention, it is preferable that described H-G hydrocracking device is additionally provided with heavy aromatics entrance, should
Heavy aromatics entrance is connected with the heavy aromatics outlet of Aromatic Hydrocarbon United Plant by pipeline.
According to system of the present invention, it is preferable that described Aromatic Hydrocarbon United Plant is additionally provided with the second BTX aromatics entrance,
This second BTX aromatics entrance is connected with the BTX aromatics outlet of light-hydrocarbon aromatized device by pipeline.
According to system of the present invention, it is preferable that this system also includes pressure-swing absorption apparatus, described 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 described
The hydrogen inlet of H-G hydrocracking device is connected.
According to system of the present invention, wherein, the first BTX aromatics entrance of Aromatic Hydrocarbon United Plant, the second BTX aromatics
Entrance is respectively used to the BTX aromatics being passed through outsourcing BTX aromatics and being produced by light-hydrocarbon aromatized device.Both BTX aromatics are equal
It is to enter xylene fractionation unit.
According to system of the present invention, petroleum naphtha hydrogenation unit included by Aromatic Hydrocarbon United Plant, CONTINUOUS REFORMER unit,
Catalyst regeneration units, Aromatics Extractive Project unit, disproportionation and transalkylation, adsorption separation unit, isomerization unit and diformazan
Between benzene fractionation unit, material has circulation, and therefore, product finally from which concrete unit is separated and do not made specifically by the present invention
Requirement, those skilled in the art can according to field operation need rationally select adjust, as those skilled in the art can
Rationally to select according to the technology disclosed in UOP and Axens, as long as ensureing to realize the purpose of the present invention.
In the method that the present invention provides, 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, mainly produce
Product include benzene, xylol and propane.First, in this work flow, between each technique, raw material and product supply mutually, reduce low value
Product category, optimizes storage and handling facility, reduces accumulating investment；Secondly, product category is concentrated, and added value is high.Additionally, this processing hands
Section flexibly, can allocate flexibly according to market demand by the distribution of each product: light naphthar, liquefied gas, pentane, raffinates oil
One or more in intermediate products can also be as product export, and the storage and handling facility under this operating mode relies on normal work as far as possible
Condition, should not additionally increase too many investment because considering various working.
In sum, 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 proportioning raw materials and product structure can be regulated neatly according to market situation, overcome and adopt merely
It is the problems such as the cost that raw material aromatic hydrocarbons exists is high, benefit is low, hydrogen is more than needed with Petroleum, and uses existing for processing of heavy oil
Investment 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.
Accompanying drawing explanation
The flow process of the method and system of the diversification raw material aromatic hydrocarbons that Fig. 1 provides for the embodiment of the present invention and structural representation
Figure.
Detailed description of the invention
In order to the technical characteristic of the present invention, purpose and beneficial effect are more clearly understood from, in conjunction with in detail below
Technical scheme is carried out described further below by embodiment and Figure of description, but it is not intended that to the present invention can
The restriction of practical range.
Embodiment 1
Present embodiments providing the system of a kind of method for realizing diversification raw material aromatic hydrocarbons, its structural representation is such as
Shown in Fig. 1, from figure 1 it appears that this system includes:
H-G hydrocracking device, Aromatic Hydrocarbon United Plant and light-hydrocarbon aromatized device；
Wherein, described H-G hydrocracking device is provided with hydrogen inlet, diesel oil entrance, fuel gas exports, liquefied gas goes out
The outlet of mouth, light naphthar, heavy naphtha outlet；
Aromatic Hydrocarbon United Plant includes petroleum naphtha hydrogenation unit, CONTINUOUS REFORMER unit, catalyst regeneration units, Aromatics Extractive Project list
Unit, disproportionation and transalkylation, adsorption separation unit, isomerization unit and xylene fractionation unit；
Described Aromatic Hydrocarbon United Plant includes Petroleum entrance, the first BTX aromatics entrance, heavy naphtha entrance, hydrogen-containing gas
Outlet, fuel gas outlet, liquefied gas outlet, pentane outlet, light naphthar outlet, outlet of raffinating oil, heavy aromatics outlet, benzene outlet
Export with xylol；
Described light-hydrocarbon aromatized device is provided with liquefied gas entrance, pentane, raffinates oil and light naphthar entrance, BTX aromatics
Outlet, hydrogen-containing gas outlet, propane outlets；
The outlet of described heavy naphtha is connected with the CONTINUOUS REFORMER unit of described Aromatic Hydrocarbon United Plant by pipeline；
The light naphthar outlet of described H-G hydrocracking device, the light naphthar outlet of Aromatic Hydrocarbon United Plant are passed through respectively
Pipeline and described pentane, raffinate oil and light naphthar entrance is connected；
Pipeline is passed through in the liquefied gas outlet of described H-G hydrocracking device, the liquefied gas outlet of Aromatic Hydrocarbon United Plant respectively
It is connected with described liquefied gas entrance；
The outlet of described pentane, raffinate oil outlet respectively by pipeline and described pentane, raffinate oil and light naphthar entrance phase
Even.
This system also includes sulfur recovery unit, and this sulfur recovery unit passes through pipeline and described H-G hydrocracking device phase
Even.
Described H-G hydrocracking device is additionally provided with heavy aromatics entrance, and this heavy aromatics entrance is combined with aromatic hydrocarbons by pipeline
The heavy aromatics outlet of device is connected.
Described Aromatic Hydrocarbon United Plant is additionally provided with the second BTX aromatics entrance, this second BTX aromatics entrance by pipeline with
The BTX aromatics outlet of light-hydrocarbon aromatized device is connected.
This system also includes pressure-swing absorption apparatus, the hydrogen-containing gas outlet of described Aromatic Hydrocarbon United Plant, light-hydrocarbon aromatized dress
The pipeline hydrogen inlet via pressure-swing absorption apparatus Yu described H-G hydrocracking device is passed through in the hydrogen-containing gas outlet put respectively
It is connected.
Embodiment 2
A kind of method present embodiments providing diversification raw material aromatic hydrocarbons, it includes 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: the scheelite produced with Petroleum, BTX aromatics and step (1) H-G hydrocracking technique
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
One or both, and/or light naphthar, liquefied gas, pentane and the one in raffinating oil that step (2) aromatic hydrocarbons process integration obtains
Or several combinations is as raw material, by light-hydrocarbon aromatized, obtain hydrogen-containing gas, propane and BTX aromatics.
Specifically, H-G hydrocracking technique is to use fixed bed hydrogenation process technology, and aromatic hydrocarbons process integration is
Using the complete set technology of Axens company, at least a part of which includes above-mentioned five patented technology, and light-hydrocarbon aromatized technique is to use greatly
The even light-hydrocarbon aromatized technology of Polytechnics, sulfur recovery uses Clause sulphur recovery+tail gas treatment process.
This example with 900,000 tons/year of catalytic diesel oils of outsourcing, 200,000 tons/year of DCC light oil, 110,000 tons/year be hydrocracked stone brain
Oil, 250,000 tons/year of reformation C7+ oil are raw material, obtain benzene, xylol, propane, sulfur product.
Using catalytic diesel oil and DCC light oil as the raw material of H-G hydrocracking technique, H-G hydrocracking device main
Product has fuel gas, liquefied gas, light naphthar and heavy naphtha.Wherein, heavy naphtha is as the raw material of Aromatic Hydrocarbon United Plant, liquid
Activating QI and light naphthar are as the raw material of light-hydrocarbon aromatized device.
The impurity contents such as this example outsourcing hydrocracked naphtha quality is higher, sulfur meet reformer charging, through simple
After dehydration, removing light naphthar component, with the CONTINUOUS REFORMER that H-G hydrocracking heavy naphtha is mixed into Aromatic Hydrocarbon United Plant
Device carries out catalytic reforming reaction, and major product is reformed oil (C6+).Major product from light-hydrocarbon aromatized device is mixed
Close aromatic hydrocarbons and enter Aromatic Hydrocarbon United Plant as raw material, converge with reformed oil (C6+), outsourcing reformation C7+ oil, join through aromatic hydrocarbons
Other devices of locking device, 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, raffinate oil, benzene, xylol and heavy aromatics product.Wherein, heavy aromatics product delivers to H-G hydrocracking device freshening；Liquid
Activating QI, light naphthar, pentane and product of raffinating oil are 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, and BTX aromatics is combined as aromatic hydrocarbons again
The raw material of device.The bromopropane product of light-hydrocarbon aromatized device dispatches from the factory sale.The hydrogen-containing gas of Aromatic Hydrocarbon United Plant and lighter hydrocarbons aromatization
The hydrogen-containing gas of gasifying device supplies H-G hydrocracking device together after Pressure Swing Adsorption and uses.
In this example, the hydrogen that Aromatic Hydrocarbon United Plant and light-hydrocarbon aromatized device produce can meet H-G hydrocracking device
Use, substantially without hydrogen more than needed, it is not necessary to additionally build device for producing hydrogen.
In this example, if when light-hydrocarbon aromatized device is stopped work or when other device product price has superiority, diesel oil hydrogenation
Light naphthar that cracking unit and Aromatic Hydrocarbon United Plant are produced, liquefied gas, pentane and in raffinating oil whole, one or more also
Can be as product export.
The final products of whole processing route are benzene, xylol and bromopropane product.If it is most to produce xylol
For principle, xylol 700,000 tons/year, benzene 310,000 tons/year, 150,000 tons/year of propane at most can be produced.
Benzaldehyde product character:
Product meets the technology requirement of petrobenzene GB/T3405-2011, and its quality index see table shown in 1.
Table 1 petrobenzene (GB/T3405-2011) quality index
Para-xylene product character:
It meets the index about high-class product in People's Republic of China's petroleum chemical industry standard SH1486.1-2008
Requirement.
Oil xylol (SH1486.1-2008) choicest quality figureofmerit is as shown in table 2 below.
Table 2 oil xylol (SH1486.1-2008) choicest quality figureofmerit
Bromopropane product character is as shown in table 3 below:
Table 3 bromopropane product quality index
In sum, the processing method that the present invention provides and system can produce the high value added product such as benzene, xylol,
And which overcoming simple employing Petroleum is the problems such as the cost existing for raw material is high, benefit is low, hydrogen is more than needed, and uses
Investment existing for processing of heavy oil is big, the problems such as difficulty of processing is big, and method provided by the present invention is that a kind of novel aromatic hydrocarbons is raw
Produce processing route.
Claims (10)
1. a method for diversification raw material aromatic hydrocarbons, it comprises the following steps:
(1) H-G hydrocracking technique: diesel oil is converted into fuel gas, liquefied gas, light naphthar and scheelite by being hydrocracked
Cerebrol；
(2) aromatic hydrocarbons process integration: the heavy naphtha produced with Petroleum, BTX aromatics and step (1) H-G hydrocracking technique
For raw material, by petroleum naphtha hydrogenation, CONTINUOUS REFORMER, catalyst regeneration, Aromatics Extractive Project, disproportionation and transalkylation, isomerization, absorption
Separate and xylene fractionation technique, obtain hydrogen-containing gas, fuel gas, liquefied gas, pentane, light naphthar, raffinate oil, heavy aromatics,
Benzene and xylol；
(3) light-hydrocarbon aromatized technique: the one in light naphthar that step (1) H-G hydrocracking technique is obtained, liquefied gas
Or two kinds, and/or light naphthar, liquefied gas, pentane and the one or several in raffinating oil that step (2) aromatic hydrocarbons process integration obtains
The combination planted, as raw material, by light-hydrocarbon aromatized, obtains hydrogen-containing gas, propane and BTX aromatics.
Method the most according to claim 1, it is characterised in that the H-G hydrocracking technique described in step (1) uses solid
Fixed bed hydrocracking process, the unconverted diesel oil of one way all loops back fixed bed hydrogenation cracking system and splits to proceed hydrogenation
Change.
Method the most according to claim 1 and 2, it is characterised in that the method is further comprising the steps of:
The heavy aromatics obtained by step (2) aromatic hydrocarbons process integration adds as raw material return step (1) diesel oil of H-G hydrocracking
Hydrogen process.
Method the most according to claim 1, it is characterised in that the method is further comprising the steps of:
BTX aromatics step (3) light-hydrocarbon aromatized technique obtained returns step (2) virtue as the raw material of aromatic hydrocarbons process integration
Hydrocarbon process integration.
Method the most according to claim 1, it is characterised in that the method is further comprising the steps of:
The hydrogen-containing gas of step (2) aromatic hydrocarbons process integration and step (3) light-hydrocarbon aromatized technique gained is carried out pressure-variable adsorption carry
Step (1) H-G hydrocracking technique is returned as H-G hydrocracking hydrogen, institute after hydrogen-containing gas Pressure Swing Adsorption after pure
Obtain tail gas and be used as fuel gas.
Method the most according to claim 1, it is characterised in that the method also 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 is returned by sulfur
Skill of knocking off obtains sulfur or sulphuric acid.
7. according to the method described in any one of claim 1-6, it is characterised in that the method is further comprising the steps of:
Under non-hydrogen operating condition, carry out light-hydrocarbon aromatized technique, gained hydrogen with outsourcing liquefied gas or light naphthar for raw material
Gas is used separately as the hydrogen that goes into operation of H-G hydrocracking technique and aromatic hydrocarbons process integration.
8. for realizing a system for the method for diversification raw material aromatic hydrocarbons described in any one of claim 1-7, comprising: bavin
Oil hydrocracking unit, Aromatic Hydrocarbon United Plant and light-hydrocarbon aromatized device；
Wherein, described H-G hydrocracking device is provided with hydrogen inlet, diesel oil entrance, fuel gas exports, liquefied gas exports, gently
Petroleum outlet, heavy naphtha outlet；
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；
Described Aromatic Hydrocarbon United Plant includes that Petroleum 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, outlet of raffinating oil, heavy aromatics outlet, benzene outlet and
Xylol exports；
Described light-hydrocarbon aromatized device is provided with liquefied gas entrance, pentane, raffinates oil and light naphthar entrance, BTX aromatics go out
The outlet of mouth, hydrogen-containing gas, propane outlets；
The outlet of described heavy naphtha is connected with the CONTINUOUS REFORMER unit of described Aromatic Hydrocarbon United Plant by pipeline；
Pipeline is passed through in the light naphthar outlet of described H-G hydrocracking device, the light naphthar outlet of Aromatic Hydrocarbon United Plant respectively
With described pentane, raffinate oil and light naphthar entrance is connected；
Pipeline and institute are passed through in the liquefied gas outlet of described H-G hydrocracking device, the liquefied gas outlet of Aromatic Hydrocarbon United Plant respectively
State liquefied gas entrance to be connected；
The outlet of described pentane, raffinate oil outlet respectively by pipeline and described pentane, raffinate oil and light naphthar entrance is connected；
Preferably, this system also includes sulfur recovery unit, and this sulfur recovery unit is by pipeline and described H-G hydrocracking device
It is connected；
It is further preferred that this system also includes pressure-swing absorption apparatus, the hydrogen-containing gas outlet of described Aromatic Hydrocarbon United Plant, lighter hydrocarbons aromatization
The pipeline hydrogen via pressure-swing absorption apparatus Yu described H-G hydrocracking device is passed through in the hydrogen-containing gas outlet of gasifying device respectively
Entrance is connected.
System the most according to claim 8, it is characterised in that described H-G hydrocracking device is additionally provided with heavy aromatics and enters
Mouthful, this heavy aromatics entrance is connected with the heavy aromatics outlet of Aromatic Hydrocarbon United Plant by pipeline.
System the most according to claim 8, it is characterised in that described Aromatic Hydrocarbon United Plant is additionally provided with the second mixing virtue
Hydrocarbon entrance, this second BTX aromatics entrance is connected with the BTX aromatics outlet of light-hydrocarbon aromatized device by pipeline.
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