CN104818042B - Moving bed methanol-to-hydrocarbon method - Google Patents
Moving bed methanol-to-hydrocarbon method Download PDFInfo
- Publication number
- CN104818042B CN104818042B CN201510142484.8A CN201510142484A CN104818042B CN 104818042 B CN104818042 B CN 104818042B CN 201510142484 A CN201510142484 A CN 201510142484A CN 104818042 B CN104818042 B CN 104818042B
- Authority
- CN
- China
- Prior art keywords
- reactor
- tower
- pressure
- methanol
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention relates to a moving bed methanol-to-hydrocarbon method. The method comprises the steps of hydrocarbon synthesis, separation and post-treatment, at least two serially connected reactors are adopted in the hydrocarbon synthesis step, a reaction raw material and a catalyst sequentially flow through the reactors in a countercurrent direction, low carbon olefin-containing circulation gas generated in the separation step returns to different feeding positions in the hydrogen synthesis step as quenching gas or raw material supplement gas in the hydrocarbon synthesis step, and a raw material methanol is used to wash and absorb C1-C4 light components generated in the separation step, returns, is fed and is converted in order to convert methanol into mixed aromatic hydrocarbon-containing stable light hydrocarbon with high added values. The method allows step complete utilization of the activity of the catalyst to be carried out, so the method improves the fine control of the reaction process, realizes effective material utilization and heat integration between processing processes, improves the product yield, reduces energy consumption and reduces environmental pollution.
Description
Technical field
The present invention relates to a kind of methanol process for producing hydrocarbons of employing moving bed.
Background technology
BTX aromatic hydrocarbons（Benzene, Toluene, Xylene）It is the important base stock of petrochemical industry, wherein xylol
（PX）Demand is maximum.With domestic PX downstreams PTA, the rapid expansion of production of polyester ability, PX supplies wretched insufficiency on market,
To 2013, China's xylol external dependence degree was up to 55.3%, and insufficiency of supply-demand is further increased.Conventionally produced PX
Projects build big difficulty, production technology threshold height, investment greatly, are limited more by raw material naphtha resource.Current China stone
The increase of oily resource anxiety and consumption demand causes the shortages of resources such as raw material Petroleum, the light diesel fuel of production aromatic hydrocarbons, it is necessary to seek
Approach of looking for novelty substitutes traditional petroleum path production aromatic hydrocarbon product.It is domestic rich coal resources with this formation sharp contrast,
The main methanol production capacity with coal as raw material production is seriously superfluous.With reference to the fundamental realities of the country of China's " oil starvation, few gas, rich coal ", utilize
Abundant coal resources synthesizing methanol, research and development methanol oxidation conversion prepares aromatic hydrocarbons（MTA）Technique, can be in production link
High concentration PX is just obtained, the added value of Downstream Products of Methanol is improved, so as to effectively reduce dependency of the aromatic hydrocarbon product to oil.
At present both at home and abroad the aromatization of methanol technology of research and development is just stepping into the industrialization stage, and portion of techniques has been carried out work
Industry.MOBILE fixed bed methanol aromatic hydrocarbons（Gasoline processed）Technology in 20th century the seventies realize industrialization, and exist
The country has obtained commercial Application；Chinese Academy of Sciences's Shanxi coalification institute's bed technology obtained at home commercial Application in 2010；Clearly
Hua Da fluid bed aromatization of methanol technology realized the operation of ton industrial demonstration unit in 2013.At present, fixed bed life
Product technology range of application is wider, but is constrained to the switching between reaction regeneration, and production capacity is restricted；Although fluid bed relies on it
Successive reaction regeneration process, in production capacity have very big development space, but for methanol this special material fluidised form
Change operation there is still a need for further exploring technique and mode of operation.At present fixed bed exists certain with fluidized bed process mode
Shortcoming, governs to some extent the extensive development in methanol aromatic hydrocarbons field, specific as follows：
1）The shortcoming of fixed-bed operation mode：
（1）Reaction regeneration frequent switching, decaying catalyst needs interruption regeneration, the time that reactor is used to react to be subject to big
Amplitude compression, production capacity critical constraints；（2）Reaction regeneration frequent switching is not only cumbersome, and there is maloperation hidden danger, is unfavorable for
Long-term operation；（3）By needing a period of time to can be only achieved even running state after regeneration incision reaction, material loss is larger；
（4）Public work consumes big, and particularly reaction regeneration handoff procedure needs to consume substantial amounts of nitrogen；（5）Fixed bed was being produced
There is situations such as channel, bias current in Cheng Yi, easy coking in reactor, catalyst duct easily blocks, and affect product quality with production peace
Entirely；（6）Fixed bed reaction heat removes difficulty, catalyst change high cost.
2）The shortcoming of fluidized bed process mode：
（1）Catalyst back-mixing degree is heavier in fluidized-bed layer, and local response is excessively easily caused coking；（2）In fluidized-bed layer
Acutely, serious wear, expensive catalyst cracky and then generation runs and damages, and causes loss economically for turbulence；（3）Fluidized-bed layer
Interior residence time destribution is wider, is easily caused that product slates are wider, and the yield of target product is reduced；（4）Temperature and pressure oscillation are all
The efficiency of gas solid separation system can be affected, and then affects subsequent fractionation system；（5）The response system low for coking yield, fluidisation
The reaction-regeneration system thermal balance of bed is difficult to maintain.
The content of the invention
Drawbacks described above under in order to overcome prior art, it is an object of the invention to provide a kind of moving bed methanol hydrocarbon side
Method, the method can realize aromatization of methanol reaction and the serialization of catalyst regeneration process, it is possible to increase course of reaction it is thin
Change controlling extent, realize between processing technique that effectively material is utilized and is thermally integrated, with catalyst activity it is stable, pressure drop is low,
The advantages of laminar flow reacts, back-mixing is few.
The technical scheme is that：
A kind of moving bed methanol hydrocarbon method, including hydrocarbon synthesis step, adopt at least two phases in the hydrocarbon synthesis step
The reactor mutually connected, anti-applications catalyst is each anti-according to being sequentially passed through by most top reactor to the order of least significant end reactor
Answer and regenerated into regenerator after device, be then back to most top reactor, methanol feedstock is introduced into least significant end reaction after heating up
Device, its product enters its previous reactor as reaction raw materials, and the rest may be inferred, until the product of second reactor is made
Most top reactor is entered for reaction raw materials.The reactor be radially moving bed reactor, can be " π " type reactor or
" Z " type reactor, can be to cardioid reactor or centrifugal type reactor.
The moving bed methanol hydrocarbon method also includes separating step and post-processing step, and the separating step is successively adopted
Gas-oil-water three-phase separating device and single-stage or multistage fractionating device carry out separation and Extraction to the product of the hydrocarbon synthesis step, most
The product of top reactor is cooled down according to technological requirement（For example to 40～60 DEG C）After send into gas and oil water three phase separation dress
Put, isolated most of gas phase Jing recycle gas compressor compression is pressurized to 0.25～1.9MPaG as circulating air, described to follow
Ring gas sub-thread Jing heat up after as reaction raw materials enter the least significant end reactor, or be divided into two strands each heated up after make
Most top reactor and least significant end reactor are respectively enterd for reaction raw materials, it is accordingly anti-by adjusting each stock circulating air Flow-rate adjustment
Answer the reaction depth of device, it is contemplated that enter the circulating air of most top reactor in addition to participating in reaction and improve yield, also
Cold shock effect is played, therefore preferably makes the circulating air flow into most top reactor be more than the circulation into least significant end reactor
Throughput, circulating air into the mode of respective reaction device be heat up after converge to the reaction feed of respective reaction device enter back into it is corresponding
Reactor；Isolated fraction gas phase enters post-processing step as pending material；Isolated aqueous portion send
Enter oil-contained waste water treatment device, it is also possible to direct reuse to upstream coal gasification apparatus, so as to effectively save public work；Separate
The oil phase part for obtaining is distributed into the fractionating device, liquid phase C that fractional distillation is obtained6～C10Component or C8～C10Component is drawn as product
Go out, correspondingly, liquid phase C3～C5Component or C3～C7Component returns hydrocarbon synthesis step as reaction raw materials, respectively with differential responses
Device charging converges；Remaining light component enters post-processing step as pending material.Isolated fraction gas phase and point
Evaporate after remaining light component for obtaining can be converged and be introduced into post-processing step.The most cooling side of the product of top reactor
Formula can be the combination of dry type air cooling, wet type air cooling, water-cooled or aforesaid way.
The most product of top reactor is preferably divided into multiply before the gas-oil-water three-phase separating device is sent into, and makees
For exothermic medium the methanol feedstock and per share circulating air that will enter hydrocarbon synthesis step are heated up respectively by heat exchange, instead
Answer multiply after product cooling to converge to cool down again.It is preferably smaller than and circulation with the flow of the product that methanol feedstock carries out heat exchange
Gas carries out the flow of the product of heat exchange, also, when heat exchange is carried out with multiply circulating air, and reacts into least significant end
The circulating air of device carries out the flow of the product of heat exchange and preferably smaller than carries out heat with the circulating air for entering most top reactor
The flow of the product of exchange, to meet the heating needs to more circulating air.
Post-processing step methanol treats treated substance and carries out reverse room temperature and washs, and equipment adopts absorption tower, methanol
Raw material self-absorption tower top enters absorption tower, from top to down to being entered by absorption tower bottom and the pending material that rises is carried out
Spray, absorbs tower bottom liquid and sends into the least significant end reactor Jing after heating up as reaction raw materials；Tower top fixed gas is absorbed by tower top
Discharge, use as fuel gas into bleed-off system, or into methanol water washing device to reclaim methanol.Methanol absorption tower top
Fixed gas contains part methanol, and in direction downstream methanol recovery device is equipped with.The methanol of recovery can reuse to upstream coal gasification
Device, it is also possible to make combustion gas.
The fractionating device of the single-stage is preferably depentanizer or fractionating column, when using depentanizer, makes C6～C10Virtue
Hydrocarbon product mix is discharged into product storage tank by bottom of towe；Top gaseous phase C1～C5Jing dry type air coolings, wet type air cooling, water-cooled or above-mentioned
The combination type of cooling cooling of mode, temperature is down to the C under logistics current pressure4With C5Boiling point between, into overhead reflux
Tank, C1～C4Gaseous component is discharged by the tank deck of return tank of top of the tower, and the light component obtained as fractional distillation is entered and absorbs tower bottom, C5
Liquid phase Jing overhead reflux pump is pressurized, and part backflow returns tower top；Another part returns to most top after heating up as reaction raw materials
Reactor；When using fractionating column, C is made8～C10Aromatic hydrocarbons product mix is discharged into product storage tank by bottom of towe；Top gaseous phase C1~
C7The combination type of cooling cooling of Jing dry type air coolings, wet type air cooling, water-cooled or aforesaid way, temperature is down to and is currently pressed between logistics
C under power5With C6Boiling point between, into return tank of top of the tower, C1～C5Gaseous component is discharged by the tank deck of return tank of top of the tower, as
The light component that fractional distillation is obtained is entered and absorbs tower bottom, C6～C7Liquid phase Jing overhead reflux pump is pressurized, and part backflow returns tower top；
Another part C6～C7Liquid phase is produced as product, or returns to most top reactor, or part after heating up as reaction raw materials
As product extraction, another part returns most top reactor after heating up as reaction raw materials.Return the C of most top reactor5
Or C6～C7With the product of next reactor of most top reactor after intensification（That is intermediate products）Most top is entered after mixing
Reactor participates in reaction.
The multistage fractionating device preferably includes depentanizer and debutanizing tower, and gas-oil-water three-phase separating device is separated
To oil phase part be distributed into the depentanizer, make C6～C10Aromatic hydrocarbons product mix is discharged into product storage by depentanizer bottom of towe
Tank, depentanizer top gaseous phase C1～C5Gas phase and liquid phase are separated into after condensed into depentanizer top return tank, gas phase is by taking off
The tank deck of pentane return tank of top of the tower is discharged, and liquid phase Jing depentanizer top reflux pump supercharging, part backflow returns depentanizer tower
Top, another part enters debutanizing tower；Depentanizer top gaseous phase condense and detached method for it is following any one：（1）It is de-
Pentanizer top gaseous phase temperature is reduced to the C under logistics current pressure2With C3Boiling point between, isolate C1～C2Gas phase and C3
～C5Liquid phase；（2）Depentanizer top gaseous phase temperature is reduced to the C under logistics current pressure4With C5Boiling point between, separate
Go out C1～C4Gas phase and C5（Generally also contain a small amount of C1～C4）Liquid phase；Jing debutanizing tower fractional distillation, makes C5Liquid-phase product is by debutanization
Tower bottom of towe is discharged, and is heated up as reaction raw materials Jing and is returned most top reactor, debutanizing tower top gaseous phase C1～C4It is condensed laggard
Enter debutanization return tank of top of the tower and be separated into gas phase and liquid phase, gas phase is discharged by the tank deck of debutanization return tank of top of the tower, and liquid phase Jing takes off
Butane overhead reflux pump is pressurized, and part backflow returns debutanizing tower tower top, and another part is returned after heating up as reaction raw materials
Least significant end reactor, the gaseous component discharged from the tank deck of depentanizer fight back stream tank and debutanization return tank of top of the tower is used as waiting to locate
Reason material enters post-processing step, that is, enter and absorb tower bottom；Debutanizing tower top gaseous phase is condensed and detached method is following
Any one：（1）Debutanizing tower top gaseous phase temperature is reduced to the C under logistics current pressure2With C3Boiling point between, separate
Go out C1～C2Gas phase and C3～C4Liquid phase；（2）Debutanizing tower top gaseous phase temperature is reduced to the C under logistics current pressure3With C4
Boiling point between, isolate C1～C3Gas phase and C4（Usually contain a small amount of C3）Liquid phase.Depentanizer top gaseous phase and debutanizing tower
Top gaseous phase condensing mode is cooled down for the combination type of cooling of dry type air cooling, wet type air cooling, water-cooled or aforesaid way.Return is most begun
The C of end reactor5With the product of next reactor of most top reactor after intensification（That is intermediate products）Enter after mixing
Most top reactor participates in reaction.
Above-mentioned suitable top gaseous phase cooling and detached method should be selected according to practical operation pressure in practice, for example,
When depentanizer/debutanizing tower operating pressure is higher, such as 1.5MPaG preferably selects corresponding method（1）, when depentanizer/de-
When butane tower operating pressure is relatively low, such as 0.4MPaG preferably selects corresponding method（2）, to avoid the boiling point mistake due to different component
Separating effect is affected in being close to, it is ensured that preferable separating effect.
The separating step can also adopt dehydrogenation reactor, in this case, the C of debutanization overhead reflux3～C4Liquid phase
（Correspondence said method（1））Or containing part C3C4Liquid phase（Correspondence said method（2））Jing debutanization overhead refluxes pump is pressurized,
Part backflow returns debutanizing tower tower top, and another part enters dehydrogenation reactor dehydrogenation, the C obtained after dehydrogenation after heating up3、C4
Unsaturated hydrocarbons return most top reactor after heating up as reaction raw materials.C before dehydrogenation3～C4C after liquid phase and dehydrogenation3、C4No
Saturated hydrocarbons are realized heating up by heat exchange, the C before dehydrogenation3～C4Liquid phase is preferably warming up to 350～540 DEG C, the C after dehydrogenation3、
C4Unsaturated hydrocarbons are preferably warming up to 150～250 DEG C, the product with next reactor of most top reactor（Produce in the middle of i.e.
Product）Most top reactor is entered after mixing and participates in reaction, intensification thermal source can be the product of each reactor or outer heat supply
Source.
When the fractionating device using single-stage, it is preferred to use following technological parameter：Fresh methanol charging 1 in hydrocarbon synthesis step
Pump outside Jing battery limit (BL)s, boost to 0.2～1.8MPaG, temperature is 25～40 DEG C.Liquid hourly space velocity (LHSV) in each reactor is 1～5h-1；The regeneration temperature of regenerator is 500～650 DEG C, and regeneration pressure is 0.2～1.9MPaG；The pressure of most top reactor is
0.12～1.73MPaG, temperature is 370～550 DEG C；The pressure of least significant end reactor is 0.15～1.75MPaG, and temperature is 320
～520 DEG C；It is not higher than the maximum pressure of latter reactor per the maximum pressure of previous reactor in adjacent two reactor, and not
Higher than the maximum pressure of least significant end reactor, the minimum pressure of previous reactor is not higher than the minimum pressure of latter reactor, and
It is not higher than the minimum pressure of least significant end reactor；Sub-thread circulating air is warming up to 320～480 DEG C；Into most top reactor
Circulating air is warming up to 250～480 DEG C, and the circulating air into least significant end reactor is warming up to 320～480 DEG C；Methanol feedstock heats up
To 250～480 DEG C, absorption tower bottom liquid elder generation mixes with methanol feedstock together heats up again with methanol feedstock.Methanol spray flow and bottom
It is 5～20 that portion's gas phase rises flow-rate ratio, and operation temperature is room temperature, and pressure is 0.3～1.4 MPaG；The tower top pressure of depentanizer
For 0.3～1.75MPaG, tower reactor pressure is 0.35～1.8MPaG；The tower top pressure of fractionating column is 0.06～1.6MPaG, for example
0.06th, 0.8,1.4MPaG, can determine according to practical situation, and tower reactor pressure is 0.07～1.8MPaG, such as 0.07,0.85,
1.5 MPaG, can determine according to practical situation；Return the C of most top reactor5Or C6～C7Realize heating up by heat exchange,
150～250 DEG C are warming up to, thermal source is the product of each reactor or outer supplying heat source.
When using multistage fractionating device, it is preferred to use following technological parameter：Fresh methanol charging 1 in hydrocarbon synthesis step
Pump outside Jing battery limit (BL)s, boost to 0.2～1.8MPaG, temperature is 25～40 DEG C.Liquid hourly space velocity (LHSV) in each reactor is 1～5h-1,
The regeneration temperature of regenerator is 500～650 DEG C, and regeneration pressure is 0.2～1.9MPaG；The most pressure of top reactor be 0.2～
1.73MPaG, temperature is 370～550 DEG C；The pressure of least significant end reactor is 0.25～1.75MPaG, and temperature is 320～520
℃；The maximum pressure of previous reactor is not higher than the maximum pressure of latter reactor in per adjacent two reactor, and is not higher than
The maximum pressure of least significant end reactor, the minimum pressure of previous reactor is not higher than the minimum pressure of latter reactor, and not
Higher than the minimum pressure of least significant end reactor；Sub-thread circulating air is warming up to 320～480 DEG C；Into the circulation of most top reactor
Gas is warming up to 250～480 DEG C, and the circulating air into least significant end reactor is warming up to 320～480 DEG C；Methanol feedstock is warming up to 250
～480 DEG C, absorption tower bottom liquid elder generation mixes with methanol feedstock together heats up again with methanol feedstock.Methanol spray flow and bottom gas phase
It is 5～20 to rise flow-rate ratio, and operation temperature is room temperature, and pressure is 0.3～1.4 MPaG；The tower top pressure of depentanizer is 0.3
～1.75MPaG, tower reactor pressure is 0.35～1.8MPaG；The tower top pressure of debutanizing tower be 0.4～1.6MPaG, tower reactor pressure
For 0.45～1.65MPaG；Return the C of most top reactor5Liquid phase is realized heating up by heat exchange, is warming up to 150～250 DEG C,
Thermal source is the product of each reactor or outer supplying heat source, returns the C of least significant end reactor3～C4Liquid phase is first mixed with methanol feedstock
Conjunction together heats up again with methanol feedstock.
For aforementioned moving bed methanol hydrocarbon method described in any one, it is divided into after can also methanol feedstock be heated up many
Stock, in addition to wherein one enters least significant end reactor, other each stocks respectively enter other reactors, and make into least significant end to react
The methanol feedstock accounting of device is more than the methanol feedstock into other each reactors.Methanol is directly added into reactor, can carry for reaction
For CH3- groups, the C that the LPG returned with circulating air, later separation part return5Alkane aromatization, methanol alkane are carried out Deng alkane
Base etc. reacts, and promotes the carrying out of aromatization, is conducive to improving aromatics yield.
Above-mentioned heat exchange can be realized by the heat exchanger of 1 or more than 2 serial or parallel connection.Its thermal source can be with
It is the product, or outer supplying heat source of certain reactor.
Beneficial effects of the present invention are：
1st, aromatization of methanol is carried out using moving bed, overcomes that fixed bed production capacity is low, pressure drop is big, catalyst life is short, bed
Layer easily coking and blocking the shortcomings of；The shortcomings of fluid bed back-mixing degree is big, catalyst is easy to wear, race is damaged is overcome again.Using movement
Bed successive reaction regeneration, it is ensured that production capacity is increased substantially；Be heated for methanol easily decompose, easily coking completely in the short time
Feature, is moved using movable bed catalyst laminar flow, and raw material radially contacts with reaction, is effectively guaranteed methanol conversion with reaction
Uniformity coefficient；Using radially moving bed pressure drop it is low the characteristics of, effectively saved energy loss, catalyst laminar flow in bed
Move down, two-phase transportation, flow velocity is low, it is to avoid the abrasion of catalyst, efficiently controlled the distribution of product, improve target
The selectivity of product.While methanol high conversion is ensured, product yield is improve.
2nd, in the form of multiple reactors in series, reaction raw materials flow direction is in inverse order stream with catalyst motion direction
It is dynamic.Fresh methanol is heated and easily decompose, and initially enters the least significant end reactor of arranged in series, and through its penultimate reactor
The catalyst haptoreaction of pre-passivating, relatively low catalyst activity efficiently avoid methanol short time decomposes.Least significant end
React in reactor based on the intermediate products such as methanol generation low-carbon (LC) hydro carbons, in addition methanol feedstock provides CH3- group, necessarily
The alkylating generation of aromatization of methanol, hydro carbons is also promoted in degree.Under relatively low catalytic type activity, reaction is gentle, reaction
Temperature rise is less, reacts easily controllable.Reaction intermediate enters most top reactor, with the high activated catalyst from regenerator
Haptoreaction.Because catalyst activity is higher, the more difficult reaction for carrying out based on aromatization of low carbon hydrocarbon, hydrocarbon restructuring etc. can be obtained
To effectively promoting, this outer portion methanol feedstock provides CH when entering most top reactor3- group, also promotes alkylation
The degree of conversion.Therefore reaction rate is very fast, and reaction efficiency is high, is conducive to the generation of aromatic hydrocarbons target product.
There are problems that temperature rise is larger, operational control difficulty relative to single reactor operation, the technique is using multiple
Reactors in series, reaction raw materials and catalyst are different and its to catalysis using raw material reaction speed against the order direction type of flow
The characteristics of agent activity demand is different, efficiently avoid methanol and cross thermal decomposition, and the high low activity of catalyst had both been carried out completely
Utilize, and it is utilized step by step according to reaction depth, realize the refinement control of course of reaction, efficiently control
Reaction temperature rising, improve the complexity of differential responses process and catalyst activity height matches adaptability, is conducive to product
Purity is lifted with while yield.
3rd, the application makes full use of the characteristics of product potential temperature of each reactor is high, latent heat is big, with its heat to reaction
The circulating air that charging and product are isolated carries out one or many preheating, efficiently utilizes own heat and realizes reaction raw materials
Temperature it is up to standard, so as to save outer heating load.
Using product being divided into by the way of multiply and respectively pre- hot feed and circulating air, can be by adjusting multiply thing
The flow-rate ratio of stream, flexible feeding temperature makes feeding temperature match with reaction temperature rising.So that whole reaction is with very strong
Regulating power and anti-fluctuation ability.It is this to realize that Energy Efficient is recycled, being thermally integrated for flexible can be realized again
Mode has effectively saved energy.
4th, the gas phase portion Jing compressors that product is obtained Jing after vapour, oil, water three phase separation pressurize as circulating air, point
2 reactor feeds are not returned for two stocks, and has played different effects respectively：
（1）Circulating air 1：Least significant end reactor is returned, i.e., is mixed with fresh methanol charging 1, due in least significant end reactor
Based on generation lower carbon number hydrocarbons intermediate product, aromatization of methanol, the C in circulating air1～C4The CH that component can be provided with methanol3- group
It is common to participate in reaction, yield is improved, promote alkylation conversion.
（2）Circulating air 2：Most top reactor is returned, i.e., is mixed with the product of second reactor.Due to most top
In reactor based on alkane aromatization, restructuring, catalyst activity is high, and reaction is violent, and heat release is big, therefore circulating air is to most top
Reactor plays cooling/cold shock effect, prevents from reacting too fast coking.C in circulating air1～C4Component and later separation part are returned
The alkane for returning promotes methanol alkylation reaction with the methanol in raw material 2, may advantageously facilitate the generation of aromatic hydrocarbons, improves PX and selects
Property.
By adjusting two strands of circulating air flows, the reaction depth of scalable most top reactor and least significant end reactor makes
Two reactor reactions can effectively relay, coupling, improve aromatics yield.
5th, liquid phase component enters depentanizer after product three phase separation, and bottom of towe obtains C6～C10Target product.Tower top
C1～C5The cooling of component Jing, gas-liquid separation, C5Component returns most top reactor feed, i.e., produce with the reaction of second reactor
Thing mixes.Because most top catalyst reactor activity is high, it is swift in response, there is CH again3- group, C5Component and circulating air
The lighter hydrocarbons of return can generate aromatic hydrocarbons by aromatization rapidly in most top reactor, so as to efficiently utilize C5Side-product
Value, reduce whole device side-product quantity, improve aromatics yield.
6th, depentanizer top light component C1～C4Into in an absorption tower, draw one methanol from fresh methanol charging and enter
2 couples of C of material1～C4Spray-absorption is carried out, effectively by C in depentanizer top gas3、C4Component absorbs and is dissolved in wherein.This strand of material
Mix with the charging into least significant end reactor, i.e., mix with fresh methanol charging 1, so as to efficiently utilize C3、C4Component,
Using the dissolubility of raw material itself, the quantity and multiformity of raw material is increased, reduce consumption of raw materials.This room temperature methanol side of washing
Formula is capable of achieving to be efficiently absorbed at normal temperatures, has both eliminated the reboiler of conventional fractionation tower height energy consumption, and technique is make use of again certainly
The raw material of body all has big advantage with creativeness as absorbing medium from energy-conservation and in terms of saving raw material.
Additionally, room temperature methanol washes mode by the fixed gas wash-off in depentanizer top gas, the particularly hydrogen in system
Body, effectively prevent fixed gas aggregation in systems.
7th, the setting of debutanizing tower significantly reduces the load on depentanizer top, and depentanizer top condensation temperature need to be higher than only
C2Boiling temperature.Debutanizing tower is by C5With C1～C4Separate, C5Component returns most top reactor feed, due to most top
Catalyst reactor activity is high, is swift in response, and there is CH again3- group, C5The lighter hydrocarbons that component and circulating air are returned are at most top
Aromatic hydrocarbons can be generated in reactor by aromatization rapidly, so as to efficiently utilize C5The value of side-product, reduces whole
Device side-product quantity, improves aromatics yield.Tower top C1、C2Component and C3、C4Component seperation, C1、C2Component and depentanizer
C1、C2Component washes absorption tower after converging into room temperature methanol.Debutanizing tower effectively reduces the C into absorption tower3、C4Content,
Methanol usage is reduced, the saving of raw material and the energy is realized.
8th, the setting of dehydrogenation reactor is effectively by C that debutanizing tower is isolated3～C4Component is converted into C3、C4Insatiable hunger
And hydrocarbon, with debutanizing tower bottom of towe C5Converge, and then mix with intermediate products, into reactor 1, the C=C that its own contains is participated in
Reaction, directly participates in cyclisation, restructuring, increased product yield.Additionally, the setting of dehydrogenation reactor is effectively improved methanol washing
The hydrogen purity of absorption tower tower top fixed gas, high hydrogen purity is conducive to the separation of subsequent gases.
9th, the isolated gas phase of three phase separation tank produces one charging that absorption tower is washed as room temperature methanol, will be in time
Hydrogen extraction in system, effectively reduces the hydrogen aggregation in system.
10th, the process products only include the stable light hydrocarbon containing BTX aromatics and small part fixed gas, do not produce liquefied gas, secondary
Product is all recycled, and farthest realizes the effectively utilizes of material.By the setting to fractionating column operating parameter, can
By-product part C6、C7Light aromatic hydrocarbons, according to the market quotation flexible adjusting device product category of aromatic hydrocarbon product species.
Description of the drawings
Fig. 1 is the general flow chart of one embodiment of the present invention；
Fig. 2 is the general flow chart of second embodiment of the present invention；
Fig. 3 is the general flow chart of the 3rd embodiment of the present invention；
Fig. 4 is the general flow chart of the 4th embodiment of the present invention.
Specific embodiment
The invention provides a kind of moving bed methanol hydrocarbon method, below by way of several specific embodiments the party is described in detail
Method utilization aborning.
Embodiment one（Referring to Fig. 1）：Containing the 1st, the 2nd two reactor, separating step adopts depentanizer fractional distillation.
Fresh methanol charging Jing is pumped outside battery limit (BL), boosts to 0.5MPaG, 25 DEG C of temperature.Fresh methanol feeds 1 Jing with reaction
Product heat exchange initially enters the 2nd reactor after heating up（Equivalent to least significant end reactor）, and from the 1st reactor（Equivalent to most
Top reactor）Radially moving bed haptoreaction is carried out through the catalyst of pre-passivating, liquid hourly space velocity (LHSV) is 1.0h-1, generate middle
Product（That is the product of the 2nd reactor）, pressure 0.45MPaG, 520 DEG C of temperature.2nd reactor product intermediate products leave
The 1st reactor being entered afterwards, with the high activated catalyst from regenerator radially moving bed haptoreaction being carried out, liquid hourly space velocity (LHSV) is
1.0h-1, reaction of formation product, pressure 0.42MPaG, 550 DEG C of temperature.Product is divided into 2 after being drawn by the 1st reactor
Stock --- product 1, product 2, flow-rate ratio is 0.52.Product 1 is entered with methanol charging 1 in the 1st heat exchange unit
Row heat exchange, methanol charging 1 is heated to 480 DEG C.Product 2 is single in the 2nd heat exchange with the circulating air from recycle gas compressor
Exchanged heat in unit, after the product 1 after heat exchange is converged with product 2, the mode of Jing dry types air cooling and water-cooled is cooled to 40
DEG C, enter the three phase separation of circulation of qi promoting, oil, water into three phase separation tank.
Catalyst is left after the 2nd reactor, is promoted to regenerator overhead, under drop down onto in regenerator and regenerated, regeneration temperature
650 DEG C of degree, regeneration pressure 0.6MPaG.The regenerator is conventional regeneration device.High activated catalyst Jing after regenerator regeneration is lifted
To the 1st reactor head, move bed with the product from the 2nd reactor and radially contact with reaction, enter back into the 2nd reaction
Device, moves bed and radially contacts with reaction with the 2nd reactor feed.
Gaseous component Jing after the three phase separation that three phase separation tank enters circulation of qi promoting, oil, water is divided into two strands：Gas phase 1, gas phase 2, stream
Amount is than being 18.0.Gas phase 1 enters recycle gas compressor, is pressurized to 0.52 MPaG.Leave the circulating air of recycle gas compressor with it is anti-
Product 2 is answered to be exchanged heat in the 2nd heat exchange unit, circulating air is heated to 320～480 DEG C, such as 480 DEG C, after intensification
Methanol charging 1 mixes, collectively as the reaction feed of the 2nd reactor.
Oil phase component Jing after the three phase separation that three phase separation tank enters circulation of qi promoting, oil, water enters depentanizer.Depentanizer is grasped
It is as follows to make parameter：Tower top pressure：0.5MPaG；Tower reactor pressure：0.55MPaG.Jing depentanizer fractional distillation, in liquid-phase reaction product
C5Following components（That is C1～C5）Discharged by tower top, C6～C10Aromatic hydrocarbons product mix is discharged into product storage tank by bottom of towe.De- pentane
Column overhead gas phase Jing dry type air cooling, water-cooled combination type of cooling cooling, temperature is down to 50 DEG C, into depentanizer top return tank.
C1～C4Gaseous component is discharged by tank deck, C5Liquid phase Jing depentanizer top reflux pump supercharging, part backflow returns depentanizer tower
Top；Another part C5The heat exchange units of liquid-phase product Jing the 5th are warming up to 250 DEG C, return the 1st reactor feed, i.e., with the 2nd reactor
The mixing of product intermediate products participates in reacting as reaction feed, and the 5th heat exchange unit thermal source is outer confession 1.2MPaG steam.
The C discharged by depentanizer fight back stream tank deck1～C4After gaseous component gas phase 2 detached with three phase separation tank is converged
Into absorption tower bottom.Mode of operation is washed in absorption tower using room temperature methanol, one fresh methanol charging 2（25℃）Entered by tower top
Absorption tower, is sprayed from top to bottom.Absorption tower top methanol spray flow and bottom C1～C4Gas phase rises flow-rate ratio
20.0,25 DEG C of tower top operation temperature, operating pressure 0.3MPaG.Absorb tower top fixed gas（C1、C2Component）Discharged by tower top；Bottom of towe
Liquid phase mixes with fresh methanol charging 1 before reactor, participates in reacting as reaction feed.The fixed gas that absorption tower top row goes out is entered
Follow-up methanol water washing device, to reclaim methanol.The methanol waste water for obtaining returns coal gasification unit Jing after processing.
Embodiment two（Referring to Fig. 2）：Containing the 1st, the 2nd two reactor, separating step adopts depentanizer, debutanizing tower two
Level fractional distillation.
Fresh methanol charging Jing is pumped outside battery limit (BL), boosts to 1.76MPaG, 30 DEG C of temperature.Fresh methanol feed 1 Jing with it is anti-
Product heat exchange is answered to initially enter the 2nd reactor after heating up（Equivalent to least significant end reactor）, and from the 1st reactor（Equivalent to
Most top reactor）Radially moving bed haptoreaction is carried out through the catalyst of pre-passivating, liquid hourly space velocity (LHSV) is 4.8h-1, it is also possible to
It is 5.0h-1, generate intermediate products（That is the product of the 2nd reactor）, pressure is 1.74 MPaG or 1.75MPaG, and temperature is
350 DEG C or 320 DEG C.2nd reactor product enters the 1st reactor after leaving, and carries out with the high activated catalyst from regenerator
Radially moving bed haptoreaction, air speed is 2.0h-1, reaction of formation product, pressure 1.72MPaG or 1.73MPaG, temperature 380
DEG C, or 370 DEG C.Product is divided into 2 strands after being drawn by the 1st reactor --- product 1, product 2, flow
Than for：1.3.Product 1 and methanol charging 1 is exchanged heat in the 1st heat exchange unit, methanol charging 1 be heated to 250 or
270℃.2 points of product is product 3, product 4, and flow-rate ratio is 0.92, respectively with from recycle gas compressor
Circulating air is exchanged heat in the 2nd heat exchange unit, the 3rd heat exchange unit.It is product 1, product 3 after heat exchange, anti-
Answer product 4 to converge, be cooled to 50 DEG C, into three phase separation tank the three phase separation of circulation of qi promoting, oil, water is entered.
Catalyst is left after the 2nd reactor, is promoted to regenerator overhead, under drop down onto in regenerator and regenerated, regeneration temperature
500 DEG C of degree, the MPaG of regeneration pressure 1.85, or 1.9 MPaG.The regenerator is conventional regeneration device.Jing regeneratoies regenerate
High activated catalyst afterwards is promoted to the 1st reactor head, moves bed with the intermediate products from the 2nd reactor and radially connects
Reaction is touched, the 2nd reactor is entered back into, bed is moved with the 2nd reactor feed and is radially contacted with reaction.
Gaseous component Jing after the three phase separation that three phase separation tank enters circulation of qi promoting, oil, water is divided into two strands：Gas phase 1, gas phase 2, stream
Amount is than being 15.0.Gas phase 1 enters recycle gas compressor, is pressurized to 1.84MPaG.The circulating air for leaving recycle gas compressor is divided into 2
Stock --- circulating air 1, circulating air 2, flow-rate ratio is：1.2.Circulating air 1 is exchanged heat with product 3 in the 2nd heat exchange unit,
Circulating air is heated to 320 DEG C.Circulating air 2 is exchanged heat with product 4 in the 3rd heat exchange unit, and circulating air is heated to
350℃.Circulating air 1 mixes with the methanol charging 1 after intensification, collectively as the reaction feed of the 2nd reactor；Circulating air 2 and the 2nd
The intermediate products logistics mixing of reactor outlet, collectively as the reaction feed of the 1st reactor.
Oil phase component Jing after the three phase separation that three phase separation tank enters circulation of qi promoting, oil, water enters depentanizer.Depentanizer is grasped
It is as follows to make parameter：Tower top pressure：1.75MPaG；Tower reactor pressure：1.80MPaG.Jing depentanizer fractional distillation, liquid-phase reaction product
Middle C5Following components is discharged by tower top, C6～C10Aromatic hydrocarbons product mix is discharged into product storage tank by bottom of towe.Depentanizer tower top
Gas phase Jing wet type air cooling is cooled down, and temperature is down to 40 DEG C, into depentanizer top return tank.C1～C2Gaseous component is discharged by tank deck,
C3～C5Liquid phase（Generally also contain a small amount of C1、C2）Jing depentanizers top reflux pump supercharging, part backflow returns depentanizer
Tower top；Another part enters debutanizing tower.
Debutanizing tower operating parameter is as follows：Tower top pressure：1.6MPaG；Tower reactor pressure：1.65MPaG.Jing debutanizing towers
Fractional distillation, top gaseous phase（C1～C4Component）Discharged by tower top；Bottom of towe C5The heat exchange units of liquid-phase product Jing the 5th are warming up to 160 DEG C, return
The 1st reactor feed is returned, i.e., is mixed with the 2nd reactor product intermediate products and is participated in reacting as reaction feed, the 5th heat exchange unit
Thermal source is outer confession 1.2MPaG steam.Debutanizing tower top gaseous phase Jing wet types air cooling is cooled down, and temperature is down to 40 DEG C, into debutanization
Return tank of top of the tower.C1～C2Gaseous component is discharged by tank deck, C3、C4Liquid phase Jing debutanization overhead reflux pump is pressurized, part backflow
Return debutanizing tower tower top；Another part liquid-phase product mixes with fresh methanol charging 1 before reactor, participates in as reaction feed
Reaction.
Depentanizer tower top C1～C2Gaseous component and debutanizing tower tower top C1～C2Gaseous component and three phase separation tank are separated
Gas phase 2 converge after, into absorb tower bottom.Mode of operation is washed in absorption tower using room temperature methanol, one fresh methanol charging 2
（30℃）Absorption tower is entered by tower top, is sprayed from top to bottom.Absorption tower top methanol spray flow and bottom C1～C4Gas phase
It is 5 or 6 to rise flow-rate ratio.25 DEG C of tower top operation temperature, operating pressure 1.3 or 1.4MPaG.Absorb tower top fixed gas（C1、C2Group
Point）Discharged by tower top；Bottom of towe liquid phase mixes with fresh methanol charging 1 before reactor, participates in reacting as reaction feed.Absorption tower
The fixed gas that top row goes out enters follow-up methanol water washing device, to reclaim methanol.The methanol waste water for obtaining returns coal Jing after processing
Gasification unit.
Embodiment three（Referring to Fig. 3）：Containing the 1st, the 2nd two reactor, separating step adopts depentanizer, debutanizing tower two
Level fractional distillation, and using dehydrogenation reactor to C3～C4Dehydrogenation, methanol feedstock is divided to 2 strands to respectively enter two reactors.
Fresh methanol charging Jing is pumped outside battery limit (BL), boosts to 0.3MPaG, 30 DEG C of temperature.Fresh methanol feeds 1 Jing with reaction
Product heat exchange is divided into 2 strands after heating up：Raw material 1 and raw material 2, respectively as the 1st reactor（Equivalent to most top reactor）, the 2nd
Reactor（Equivalent to least significant end reactor）Charging, flow-rate ratio is 1:9.Raw material 2 enters the 2nd reactor, and from the 1st reactor
Radially moving bed haptoreaction is carried out through the catalyst of pre-passivating, liquid hourly space velocity (LHSV) is 2.5h-1, generate intermediate products（I.e. the 2nd is anti-
Answer the product of device）, pressure 0.25MPaG, 420 DEG C of temperature.2nd reactor product intermediate products mix after leaving with raw material 1
Into the 1st reactor, radially moving bed haptoreaction is carried out with the high activated catalyst from regenerator, liquid hourly space velocity (LHSV) is
2.5h-1, reaction of formation product, pressure 0.2MPaG, 460 DEG C of temperature.Product is divided into 2 strands after being drawn by the 1st reactor ---
Product 1, product 2, flow-rate ratio is：0.75.Product 1 is carried out with methanol of reaction charging 1 in the 1st heat exchange unit
Heat exchange, methanol charging 1 is heated to 365 DEG C.2 points of product is product 3, product 4, and flow-rate ratio is 0.76, point
Do not exchanged heat in the 2nd heat exchange unit, the 3rd heat exchange unit with the circulating air from recycle gas compressor., after heat exchange
Product 1, product 3, product 4 are converged, and are cooled to 60 DEG C, into three phase separation tank enter circulation of qi promoting, oil, water three
It is separated.
Catalyst is left after the 2nd reactor, is promoted to regenerator overhead, under drop down onto in regenerator and regenerated, regeneration temperature
570 DEG C of degree, regeneration pressure 0.3MPaG, or 0.2MPaG.The regenerator is conventional regeneration device.Jing after regenerator regeneration
High activated catalyst is promoted to the 1st reactor head, moves bed with the intermediate products from the 2nd reactor and radially contacts with instead
Should, the 2nd reactor is entered back into, move bed with the 2nd reactor feed and radially contact with reaction.
Gaseous component Jing after the three phase separation that three phase separation tank carries out vapour, oil, water is divided into two strands：Gas phase 1, gas phase 2, stream
Amount is than being 12.0.Gas phase 1 enters recycle gas compressor, is pressurized to 0.3MPaG.The circulating air for leaving recycle gas compressor is divided into 2
Stock --- circulating air 1, circulating air 2, flow-rate ratio is 0.9.Circulating air 1 is exchanged heat with product 3 in the 2nd heat exchange unit,
Circulating air is heated to 365 DEG C.Circulating air 2 is exchanged heat with product 4 in the 3rd heat exchange unit, and circulating air is heated to
420℃.Circulating air 1 mixes with the raw material 2 after intensification, collectively as the reaction feed of the 2nd reactor；Circulating air 2 and the 2nd reacts
The intermediate products and raw material 1 of device outlet mix, collectively as the reaction feed of the 1st reactor.
Oil phase component Jing after the three phase separation that three phase separation tank carries out vapour, oil, water enters depentanizer.Depentanizer is grasped
It is as follows to make parameter：Tower top pressure：0.3MPaG；Tower reactor pressure：0.35MPaG.Jing depentanizer fractional distillation, in liquid-phase reaction product
C5Following components is discharged by tower top, C6～C10Aromatic hydrocarbons product mix is discharged into product storage tank by bottom of towe.Depentanizer tower overhead gas
Phase Jing wet type air cooling is cooled down, and temperature is down to 45 DEG C, into depentanizer top return tank.C1～C4Gaseous component is discharged by tank deck, C5
Liquid phase（Generally also contain a small amount of C1～C4）Jing depentanizers top reflux pump supercharging, part backflow returns depentanizer tower top；
Another part liquid-phase product enters debutanizing tower.
Debutanizing tower operating parameter is as follows：Tower top pressure：0.4 or 0.5MPaG；Tower reactor pressure：0.45 or 0.55MPaG.Jing
Debutanizing tower fractional distillation, top gaseous phase（C1～C4Component）Discharged by tower top；Bottom of towe C5The heat exchange units of liquid-phase product Jing the 5th are warming up to
180 DEG C, the 1st reactor feed is returned, i.e., mix with the 2nd reactor product intermediate products and raw material 1 and participated in as reaction feed
Reaction, the 5th heat exchange unit thermal source is outer confession 1.2MPaG steam.Debutanizing tower top gaseous phase Jing wet types air cooling is cooled down, and temperature is down to
40 DEG C, into debutanization return tank of top of the tower.C1～C3Gaseous component is discharged by tank deck, C4（Containing a small amount of C3）Liquid phase Jing debutanizing tower
Top reflux pump supercharging, part backflow returns debutanizing tower tower top；The heat exchange units of another part liquid-phase product Jing the 4th are produced with reaction
Thing 1 exchanges heat, and 430 DEG C is heated to, into dehydrogenation reactor.Dehydrogenation reactor outlet streams and debutanizing tower bottom liquid-phase mixing,
And then mix with intermediate products and raw material 1, participate in reaction as the charging of the 1st reactor reaction.
Depentanizer tower top C1～C4Gaseous component and debutanizing tower tower top C1～C3Gaseous component and three phase separation tank are separated
Gas phase 2 converge after, into absorb tower bottom.Mode of operation is washed in absorption tower using room temperature methanol, one fresh methanol charging 2
（30℃）Absorption tower is entered by tower top, is sprayed from top to bottom.Absorption tower top methanol spray flow and bottom C1～C4Gas phase
It is 7.1 to rise flow-rate ratio.25 DEG C of tower top operation temperature, operating pressure 0.8MPaG.Absorb tower top fixed gas（C1、C2Component）By tower
Top row goes out；Bottom of towe liquid phase mixes with fresh methanol charging 1 before reactor, participates in reacting as reaction feed.
Example IV（Referring to Fig. 4）：Containing the 1st, the 2nd, the 3rd three reactor, separating step adopts fractionating column single-stage fractional distillation,
3 strands of methanol feedstock point respectively enters three reactors.
Fresh methanol charging Jing is pumped outside battery limit (BL), boosts to 0.6MPaG, 30 DEG C of temperature.Fresh methanol feeds Jing with reaction
Product heat exchange is divided into 3 strands after heating up：Raw material 1, raw material 2, raw material 3, respectively as the 1st reactor（Equivalent to the reaction of most top
Device）, the 2nd reactor, the 3rd reactor（Equivalent to least significant end reactor）Charging, flow-rate ratio is 1:2:8.It is anti-that raw material 3 enters the 3rd
Device is answered, radially moving bed haptoreaction is carried out through the catalyst of pre-passivating with from the 2nd reactor, liquid hourly space velocity (LHSV) is 1.6h-1,
Generate intermediate products 1（That is the product of the 3rd reactor）, the MPaG of pressure 0.55,470 DEG C of temperature.In 3rd reactor product
Between product 1 leave after with raw material 2 be mixed into the 2nd reactor, with the greater activity catalyst from the 1st reactor carry out radial direction
Moving-bed contacting reacts, and liquid hourly space velocity (LHSV) is 1.3h-1, generate intermediate products 2（That is the product of the 2nd reactor）, pressure
0.53MPaG, 500 DEG C of temperature.2nd reactor product intermediate products 2 are mixed into the 1st reactor after drawing with raw material 1, with
Radially moving bed haptoreaction is carried out from the high activated catalyst of regenerator, liquid hourly space velocity (LHSV) is 1.1h-1, reaction of formation product, pressure
Power 0.51MPaG, 510 DEG C of temperature.
Product after the extraction of the 1st reactor by being divided into 2 strands --- and product 1, product 2, flow-rate ratio is：1.8.
Product 1 is exchanged heat with methanol of reaction charging 1 in the 1st heat exchange unit, and methanol charging 1 is heated to 420 DEG C.Reaction is produced
2 points of thing is product 3, product 4, product 5, and flow-rate ratio is 6：4：2, respectively with following from recycle gas compressor
Ring gas and Fractionator Bottom product are exchanged heat in the 2nd heat exchange unit, the 3rd heat exchange unit, the 5th heat exchange unit.After heat exchange
Product 1, product 3, product 4, product 5 converge, be cooled to 40 DEG C, carry out into three phase separation tank
Gas, oil, the three phase separation of water.
Catalyst is left after the 3rd reactor, is promoted to regenerator overhead, under drop down onto in regenerator and regenerated, regeneration temperature
590 DEG C of degree, regeneration pressure 0.6MPaG.The regenerator is conventional regeneration device.High activated catalyst Jing after regenerator regeneration is lifted
To the 1st reactor head, move bed with the intermediate products 2 from the 2nd reactor and radially contact with reaction；Enter back into the 2nd anti-
Device is answered, bed is moved with the intermediate products 1 from the 3rd reactor and is radially contacted with reaction；The 3rd reactor is entered back into, it is anti-with the 3rd
Answer device to move bed and radially contact with reaction.
Gaseous component Jing after the three phase separation that three phase separation tank carries out vapour, oil, water is divided into two strands：Gas phase 1, gas phase 2, stream
Amount is than being 10.0.Gas phase 1 enters recycle gas compressor, is pressurized to 0.64MPaG.The circulating air for leaving recycle gas compressor is divided into 2
Stock --- circulating air 1, circulating air 2, flow-rate ratio is 1.1.Circulating air 1 is exchanged heat with product 3 in the 2nd heat exchange unit,
Circulating air is heated to 420 or 480 DEG C.Circulating air 2 is exchanged heat with product 4 in the 3rd heat exchange unit, and circulating air is added
Heat is to 470 or 480 DEG C.Circulating air 1 mixes with the raw material 3 after intensification, collectively as the reaction feed of the 3rd reactor；Circulating air 2
Mix with the intermediate products 2 and raw material 1 of the 2nd reactor outlet, collectively as the reaction feed of the 1st reactor.
Oil phase component Jing after the three phase separation that three phase separation tank enters circulation of qi promoting, oil, water enters fractionating column, fractionating column operation ginseng
Number is as follows：Tower top pressure is 0.06～1.6 MPaG, such as 0.8MPaG；Tower reactor pressure is 0.07～1.8MpaG, for example
0.85MPaG；It is fractionated into tower fractional distillation, C7Following components is discharged by tower top, C8～C10Aromatic hydrocarbons product mix is discharged into producing by bottom of towe
Product storage tank；Top gaseous phase C1～C7The mode of Jing wet type air coolings is cooled down, and temperature is down to 130 DEG C, into fractional distillation return tank of top of the tower.C1
～C5Gaseous component is discharged by tank deck, and gas phase 2 detached with three phase separation tank enters absorption tower bottom after converging.C6～C7Liquid phase
The supercharging of overhead reflux pump is fractionated into, part backflow returns fractionator overhead；The heat exchange units of another part Jing the 5th and product
190 DEG C are warming up to after 5 heat exchange, the 1st reactor feed is returned, i.e., mix work with the 2nd reactor product intermediate products 2 and raw material 1
Participate in reacting for reaction feed.
Fractionator overhead C1～C5After gaseous component gas phase 2 detached with three phase separation tank is converged, into absorption tower bottom.
Mode of operation is washed in absorption tower using room temperature methanol, one fresh methanol charging 2（30℃）Absorption tower is entered by tower top, from top to bottom
Sprayed.It is 9.2 that absorption tower top methanol spray flow rises flow-rate ratio with bottom gas phase.25 DEG C of tower top operation temperature, behaviour
Make pressure 0.8MPaG.Absorb tower top fixed gas（C1、C2Component）Discharged by tower top；Fresh methanol is entered before bottom of towe liquid phase and reactor
Material 1 mixes, and participates in reacting as reaction feed.
The present invention is verified that the result for obtaining is as follows according to embodiment 1,2,3,4：
The reaction raw materials of table 1 are constituted
| Composition | Mol% |
| Methanol | 99.9 |
| Water | 0.1 |
The product form of table 2
| Composition | Embodiment 1（Mol%） | Embodiment 2（Mol%） | Embodiment 3（Mol%） | Embodiment 4（Mol%） |
| C4 | 0.1 | 0.1 | 0.1 | 0.01 |
| C5 | 0.56 | 0.55 | 0.61 | 0.06 |
| C6A | 12.23 | 12.01 | 11.52 | 4.6 |
| C7A | 30.16 | 30.02 | 29.08 | 15.83 |
| C8A | 43.04 | 42.76 | 43.4 | 53.69 |
| C9A | 11.46 | 12.19 | 12.53 | 19.74 |
| C10A | 2.45 | 2.37 | 2.76 | 6.07 |
The fixed gas of table 3 is constituted
| Composition | Embodiment 1（Mol%） | Embodiment 2（Mol%） | Embodiment 3（Mol%） | Embodiment 4（Mol%） |
| CO | 2.23 | 2.19 | 0.74 | 2.21 |
| Hydrogen | 16.22 | 16.4 | 72.07 | 16.33 |
| H2O | 0 | 0 | 0 | 0 |
| Methanol | 2.39 | 2.01 | 0.80 | 2.28 |
| C1 | 58.13 | 57.96 | 19.38 | 58.01 |
| C2 | 20.62 | 21.06 | 6.87 | 20.78 |
| C3 | 0.28 | 0.26 | 0.1 | 0.27 |
| C4 | 0.13 | 0.12 | 0.04 | 0.12 |
Traditional single-reactor is changed to the present invention form of more than 2 reactors in series, using raw material reaction speed
Different and its different to catalyst activity demand the characteristics of, efficiently avoid methanol and cross thermal decomposition, by violent course of reaction
Be divided into it is several more leniently react, successively couple relay carry out.The high low activity of catalyst was both utilized completely,
Again it is utilized step by step according to reaction depth, realized the refinement control of course of reaction, efficiently controlled reaction
Temperature rise, is conducive to product purity to be lifted with while yield.Efficiently solve temperature rise that the operation of traditional single-reactor is present compared with
Greatly, the problems such as operational control difficulty is larger.
The isolated C of separating step3～C5Liquid-phase product returns to reaction member and participates in reaction.Circulating air is returned and carried
Substantial amounts of CH3- group, C5Generation aromatic hydrocarbons can be rapidly reacted in Returning reactor, so as to efficiently utilize C5Side-product
Value, reduces whole device side-product quantity.C3～C4In component Returning reactor, C is efficiently utilized3、C4Component, has
Effect consumption of raw materials is reduced, reduce the consumption of side-product.
Claims (11)
1. a kind of moving bed methanol hydrocarbon method, including hydrocarbon synthesis step, it is characterised in that using extremely in the hydrocarbon synthesis step
Few two reactors being serially connected, anti-applications catalyst according to the order by most top reactor to least significant end reactor successively
Regenerated into regenerator after each reactor, be then back to most top reactor, methanol feedstock is advanced after heating up
Enter least significant end reactor, its product enters its previous reactor as reaction raw materials, and the rest may be inferred, until second reactor
Product as reaction raw materials enter most top reactor, the reactor be radially moving bed reactor.
2. moving bed methanol hydrocarbon method as claimed in claim 1, it is characterised in that also walk including separating step and post processing
Suddenly, the separating step is successively walked using gas-oil-water three-phase separating device and single-stage or multistage fractionating device to hydrocarbon synthesis
Rapid product carries out separation and Extraction, and after the product cooling of most top reactor the gas-oil-water three-phase separating device is sent into,
Isolated most of gas phase Jing recycle gas compressor compression is used as circulating air, and the circulating air sub-thread is Jing after heating up as anti-
Answer raw material to enter the least significant end reactor, or be divided into two strands each heated up after respectively enter as reaction raw materials and most begin
End reactor and least significant end reactor, by the reaction depth for adjusting each stock circulating air Flow-rate adjustment respective reaction device；Separate
To fraction gas phase enter post-processing step as pending material, isolated aqueous portion sends into oily waste water treatment
Device, isolated oil phase part is distributed into the fractionating device；Liquid phase C that fractional distillation is obtained6～C10Component or C8～C10Component
Draw as product, correspondingly, liquid phase C3～C5Component or C3～C7Component returns hydrocarbon synthesis step as reaction raw materials, remaining
Light component enters post-processing step as pending material.
3. moving bed methanol hydrocarbon method as claimed in claim 2, it is characterised in that the product of most top reactor exists
Send into and be divided into before the gas-oil-water three-phase separating device multiply, and pass through heat exchange to synthesizing into hydrocarbon as exothermic medium
The methanol feedstock of step and per share circulating air are heated up respectively, and multiply is converged after product cooling.
4. moving bed methanol hydrocarbon method as claimed in claim 3, it is characterised in that the post-processing step is treated with methanol
Treated substance carries out reverse room temperature washing, and equipment adopts absorption tower, methanol feedstock self-absorption tower top to enter absorption tower, from upper and
Lowerly to being entered by absorption tower bottom and the pending material that rises is sprayed, absorb tower bottom liquid and heat up as reaction raw materials Jing
After send into the least significant end reactor；Absorb tower top fixed gas to be discharged by tower top, use as fuel gas into bleed-off system, or
Person enters methanol water washing device to reclaim methanol.
5. moving bed methanol hydrocarbon method as claimed in claim 4, it is characterised in that the fractionating device of the single-stage is de- penta
Alkane tower or fractionating column, when using depentanizer, make C6～C10Aromatic hydrocarbons product mix is discharged into product storage tank by bottom of towe；Tower top
The combination type of cooling cooling of gas phase Jing dry type air cooling, wet type air cooling, water-cooled or aforesaid way, temperature is down to current between logistics
C under pressure4With C5Boiling point between, into return tank of top of the tower, C1～C4Gaseous component is discharged by the tank deck of return tank of top of the tower, is made
The light component obtained for fractional distillation is entered and absorbs tower bottom, C5Liquid phase Jing overhead reflux pump is pressurized, and part backflow returns tower top；Separately
A part returns most top reactor after heating up as reaction raw materials；When using fractionating column, C is made8～C10Aromatic hydrocarbons product mix
Product storage tank is discharged into by bottom of towe；The combination cooling side of top gaseous phase Jing dry type air coolings, wet type air cooling, water-cooled or aforesaid way
Formula is cooled down, and temperature is down to the C under logistics current pressure5With C6Boiling point between, into return tank of top of the tower, C1～C5Gas phase group
Divide and discharged by the tank deck of return tank of top of the tower, the light component obtained as fractional distillation is entered and absorbs tower bottom, C6～C7Liquid phase Jing tower top is returned
Stream pump supercharging, part backflow returns tower top；Another part C6～C7Liquid phase is produced as product, or as reaction raw materials liter
Most top reactor is returned after temperature, or part returns after another part heats up as reaction raw materials as product extraction and most begins
End reactor.
6. moving bed methanol hydrocarbon method as claimed in claim 4, it is characterised in that the multistage fractionating device includes de-
Pentanizer and debutanizing tower, the isolated oil phase part of gas-oil-water three-phase separating device is distributed into the depentanizer, makes C6~
C10Aromatic hydrocarbons product mix is discharged into product storage tank by depentanizer bottom of towe, and de- penta is entered after depentanizer top gaseous phase is condensed
Alkane return tank of top of the tower is separated into gas phase and liquid phase, and gas phase is discharged by the tank deck of depentanizer top return tank, liquid phase Jing depentanizer
Top reflux pump supercharging, part backflow returns depentanizer tower top, and another part enters debutanizing tower；Depentanizer top gaseous phase
Condensation and detached method for it is following any one：（1）Depentanizer top gaseous phase temperature is reduced between logistics current pressure
Lower C2With C3Boiling point between, isolate C1～C2Gas phase and C3～C5Liquid phase；（2）Depentanizer top gaseous phase temperature is reduced to Jie
The C under logistics current pressure4With C5Boiling point between, isolate C1～C4Gas phase and C5Liquid phase；Jing debutanizing tower fractional distillation, makes C5Liquid
Phase product is discharged by debutanizing tower bottom of towe, is heated up as reaction raw materials Jing and is returned most top reactor, debutanizing tower top gaseous phase
Gas phase and liquid phase are separated into into debutanizing tower top return tank after condensed, gas phase is arranged by the tank deck of debutanization return tank of top of the tower
Go out, liquid phase Jing debutanization overhead reflux pump supercharging, part backflow returns debutanizing tower tower top, and another part is used as reaction raw materials
Least significant end reactor is returned after intensification, from the gas phase group that the tank deck of depentanizer fight back stream tank and debutanization return tank of top of the tower is discharged
Divide and enter post-processing step；Debutanizing tower top gaseous phase condense and detached method for it is following any one：（1）Debutanizing tower tower
Top gas phase temperature is reduced to the C under logistics current pressure2With C3Boiling point between, isolate C1～C2Gas phase and C3～C4Liquid
Phase；（2）Debutanizing tower top gaseous phase temperature is reduced to the C under logistics current pressure3With C4Boiling point between, isolate C1~
C3Gas phase and C4Liquid phase.
7. moving bed methanol hydrocarbon method as claimed in claim 6, it is characterised in that the separating step is also anti-using dehydrogenation
Device is answered, in this case, the liquid phase Jing debutanization overhead reflux pump supercharging of debutanization overhead reflux, part backflow returns de- fourth
Alkane column overhead, another part enters dehydrogenation reactor dehydrogenation after heating up, and the unsaturated hydrocarbons obtained after dehydrogenation are used as reaction raw materials liter
Most top reactor is returned after temperature.
8. moving bed methanol hydrocarbon method as claimed in claim 5, it is characterised in that the liquid hourly space velocity (LHSV) in each reactor
For 1～5h-1, the regeneration temperature of regenerator is 500～650 DEG C, and regeneration pressure is 0.2～1.9MPaG, the most pressure of top reactor
Power is 0.20～1.73MPaG, and temperature is 370～550 DEG C, and the pressure of least significant end reactor is 0.25～1.75MPaG, and temperature is
320～520 DEG C, the maximum pressure of previous reactor is not higher than the maximum pressure of latter reactor in every adjacent two reactor, and
The maximum pressure of least significant end reactor is not higher than, the minimum pressure of previous reactor is not higher than the minimal pressure of latter reactor
Power, and the minimum pressure of least significant end reactor is not higher than, sub-thread circulating air is warming up to 320～480 DEG C, enters the reaction of most top
The circulating air of device is warming up to 250～480 DEG C, and the circulating air into least significant end reactor is warming up to 320～480 DEG C, methanol feedstock
250～480 DEG C are warming up to, absorption tower bottom liquid elder generation mixes with methanol feedstock together heats up again with methanol feedstock, methanol spray flow
It is 5-20 to rise flow-rate ratio with bottom gas phase, and pressure is 0.3～1.4 MPaG, the tower top pressure of depentanizer is 0.3～
1.75MPaG, tower reactor pressure is 0.35～1.8MPaG, and the tower top pressure of fractionating column is 0.06～1.6MPaG, and tower reactor pressure is
0.07～1.8MpaG, returns the C of most top reactor5Or C6～C7Realize heating up by heat exchange, be warming up to 150～250 DEG C,
Thermal source is the product or outer supplying heat source of each reactor.
9. moving bed methanol hydrocarbon method as claimed in claim 6, it is characterised in that the liquid hourly space velocity (LHSV) in each reactor
For 1～5h-1, the regeneration temperature of regenerator is 500～650 DEG C, and regeneration pressure is 0.2～1.9MPaG, the most pressure of top reactor
Power is 0.20～1.73MPaG, and temperature is 370～550 DEG C, and the pressure of least significant end reactor is 0.25～1.75MPaG, and temperature is
320～520 DEG C, the maximum pressure of previous reactor is not higher than the maximum pressure of latter reactor in every adjacent two reactor, and
The maximum pressure of least significant end reactor is not higher than, the minimum pressure of previous reactor is not higher than the minimal pressure of latter reactor
Power, and the minimum pressure of least significant end reactor is not higher than, sub-thread circulating air is warming up to 320～480 DEG C, enters the reaction of most top
The circulating air of device is warming up to 250～480 DEG C, and the circulating air into least significant end reactor is warming up to 320～480 DEG C, methanol feedstock
250～480 DEG C are warming up to, absorption tower bottom liquid elder generation mixes with methanol feedstock together heats up again with methanol feedstock, methanol spray flow
It is 5～20 to rise flow-rate ratio with bottom gas phase, and pressure is 0.3～1.4 MPaG, the tower top pressure of depentanizer is 0.3～
1.75MPaG, tower reactor pressure is 0.35～1.8MPaG, and the tower top pressure of debutanizing tower is 0.4～1.6MPaG, and tower reactor pressure is：
0.45～1.65MPaG, returns the C of most top reactor5Liquid phase is realized heating up by heat exchange, is warming up to 150～250 DEG C, heat
Source is the product or outer supplying heat source of each reactor, returns the C of least significant end reactor3～C4Liquid phase elder generation and methanol feedstock
Mixing together heats up again with methanol feedstock.
10. moving bed methanol hydrocarbon method as claimed in claim 7, it is characterised in that the liquid hourly space velocity (LHSV) in each reactor
For 1～5h-1, the regeneration temperature of regenerator is 500～650 DEG C, and regeneration pressure is 0.2～1.9MPaG, the most pressure of top reactor
Power is 0.20～1.73MPaG, and temperature is 370～550 DEG C, and the pressure of least significant end reactor is 0.25～1.75MPaG, and temperature is
320～520 DEG C, the maximum pressure of previous reactor is not higher than the maximum pressure of latter reactor in every adjacent two reactor, and
The maximum pressure of least significant end reactor is not higher than, the minimum pressure of previous reactor is not higher than the minimal pressure of latter reactor
Power, and the minimum pressure of least significant end reactor is not higher than, sub-thread circulating air is warming up to 320～480 DEG C, enters the reaction of most top
The circulating air of device is warming up to 250～480 DEG C, and the circulating air into least significant end reactor is warming up to 320～480 DEG C, methanol feedstock
250～480 DEG C are warming up to, absorption tower bottom liquid elder generation mixes with methanol feedstock together heats up again with methanol feedstock, methanol spray flow
It is 5～20 to rise flow-rate ratio with bottom gas phase, and pressure is 0.3～1.4 MPaG, the tower top pressure of depentanizer is 0.3～
1.75MPaG, tower reactor pressure is 0.35～1.8MPaG, and the tower top pressure of debutanizing tower is 0.4～1.6MPaG, and tower reactor pressure is：
0.45～1.65MPaG, returns the C of most top reactor5Liquid phase is realized heating up by heat exchange, is warming up to 150～250 DEG C, heat
Source is the product or outer supplying heat source of each reactor, returns the C of least significant end reactor3～C4Liquid phase elder generation and methanol feedstock
Mixing together heats up again with methanol feedstock.
The 11. moving bed methanol hydrocarbon methods as described in any one in claim 1-10, it is characterised in that methanol feedstock liter
It is divided into multiply after temperature, in addition to wherein one enters least significant end reactor, other each stocks respectively enter other reactors, into most end
The methanol feedstock accounting of end reactor is more than the methanol feedstock into other reactors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510142484.8A CN104818042B (en) | 2015-03-27 | 2015-03-27 | Moving bed methanol-to-hydrocarbon method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510142484.8A CN104818042B (en) | 2015-03-27 | 2015-03-27 | Moving bed methanol-to-hydrocarbon method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104818042A CN104818042A (en) | 2015-08-05 |
| CN104818042B true CN104818042B (en) | 2017-05-03 |
Family
ID=53728530
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510142484.8A Active CN104818042B (en) | 2015-03-27 | 2015-03-27 | Moving bed methanol-to-hydrocarbon method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104818042B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818042B (en) * | 2015-03-27 | 2017-05-03 | 中国昆仑工程有限公司 | Moving bed methanol-to-hydrocarbon method |
| CN105130730A (en) * | 2015-09-02 | 2015-12-09 | 中国昆仑工程公司 | Technological method for preparing light hydrocarbons through methanol by means of continuous regeneration moving beds and production system |
| CN105331389B (en) * | 2015-12-10 | 2017-08-11 | 上海优华系统集成技术股份有限公司 | One kind reforms heat recovery and utilization technique and device |
| CN106008126B (en) * | 2016-05-20 | 2018-08-10 | 四川金象赛瑞化工股份有限公司 | A kind of method and system of methanol hydrocarbon |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818042A (en) * | 2015-03-27 | 2015-08-05 | 中国昆仑工程公司 | Moving bed methanol-to-hydrocarbon method |
-
2015
- 2015-03-27 CN CN201510142484.8A patent/CN104818042B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104818042A (en) * | 2015-03-27 | 2015-08-05 | 中国昆仑工程公司 | Moving bed methanol-to-hydrocarbon method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104818042A (en) | 2015-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101559320B (en) | Separation method of Fischer-Tropsch synthesis gas by combining rectification and solvent absorption | |
| CN102040445B (en) | Technology device and method for preparing propylene by dehydrogenating propane or propane-enriched low carbon hydrocarbon | |
| CN104818042B (en) | Moving bed methanol-to-hydrocarbon method | |
| US20130116348A1 (en) | Fischer-tropsch synthesis process and system | |
| CN101830769B (en) | Method for converting methanol into propylene | |
| CN104140847B (en) | A kind of F-T synthesis petroleum naphtha upgrading produces the method for stop bracket gasoline | |
| WO2016054879A1 (en) | Regeneration method for catalytic cracking reaction | |
| CN103571530B (en) | Wax catalysis cracking is for the method for low-carbon alkene | |
| CN104818043B (en) | Heat integrated moving bed methanol aromatization method for coproducing liquefied gas | |
| CN105349172A (en) | Naphtha raw material catalysis cracking method | |
| CN102942435B (en) | Reaction technology using moving bed technique to convert methanol into propylene | |
| CN106854135A (en) | The method of benzene and methanol alkylation paraxylene | |
| CN104844402B (en) | Efficient heat-integrated method for preparing hydrocarbon from methanol by adopting moving bed | |
| CN102267859B (en) | Method for producing ethylbenzene by using ethylene | |
| CN104818044B (en) | Moving bed methanol aromatization method for coproducing liquefied gas | |
| CN104926584B (en) | A kind of system and method preparing iso-butane | |
| CN204503035U (en) | High Efficiency Thermal integrated-type moving bed Methanol hydrocarbon system | |
| CN204848758U (en) | Remove bed methyl alcohol system hydrocarbon system all | |
| CN111871343A (en) | Device for producing low-carbon olefin by using oxygen-containing compound | |
| CN104193570B (en) | The method of MTO technique and the coupling of naphtha pyrolysis order separating technology | |
| CN109651038A (en) | The method that MTO technique is coupled with dehydrogenating propane technique | |
| CN109761736A (en) | Naphtha and ethane cracking sequentially separate the method coupled with PDH | |
| CN109851461A (en) | The method that naphtha and Deposition During Propane Pyrolysis front-end deethanization are coupled with PDH | |
| CN104478642A (en) | Device and method for producing olefin from methanol | |
| CN110041157B (en) | Method for improving yield of propylene prepared from methanol and prolonging service life of catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| CB02 | Change of applicant information |
Address after: 100037 Beijing city Haidian District Zengguang Road No. 21 Applicant after: CHINA KUNLUN CONTRACTING & ENGINEERING Corp. Applicant after: China Textile Industry Design Institute Address before: 100037 Beijing city Haidian District Zengguang Road No. 21 Applicant before: CHINA KUNLUN CONTRACTING & ENGINEERING Corp. Applicant before: China Textile Industry Design Institute |
|
| COR | Change of bibliographic data | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20170227 Address after: 100037 Beijing city Haidian District Zengguang Road No. 21 Applicant after: CHINA KUNLUN CONTRACTING & ENGINEERING Corp. Address before: 100037 Beijing city Haidian District Zengguang Road No. 21 Applicant before: CHINA KUNLUN CONTRACTING & ENGINEERING Corp. Applicant before: China Textile Industry Design Institute |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201221 Address after: 100007 No. 9 North Main Street, Dongcheng District, Beijing, Dongzhimen Patentee after: CHINA NATIONAL PETROLEUM Corp. Patentee after: CHINA KUNLUN CONTRACTING & ENGINEERING Corp. Address before: 100037 No. 21, shining road, Beijing, Haidian District Patentee before: CHINA KUNLUN CONTRACTING & ENGINEERING Corp. |