CN104844402B - Efficient heat-integrated method for preparing hydrocarbon from methanol by adopting moving bed - Google Patents
Efficient heat-integrated method for preparing hydrocarbon from methanol by adopting moving bed Download PDFInfo
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Abstract
The invention relates to an efficient heat-integrated method for preparing hydrocarbon from methanol by adopting a moving bed. The method comprises a hydrocarbon synthesis step, a separation step and an after-treatment step, wherein in the hydrocarbon synthesis step, two reactors which are connected with each other in series are adopted; reaction products of a plurality of reactors are utilized to perform heat-exchange heating on reaction raw materials and low-carbon-hydrogen containing recycle gas produced in the separation step, so that the recycle gas is returned to different feeding positions of the hydrocarbon synthesis step as quenching gas or raw material supplementing gas of the hydrocarbon synthesis step; the raw material methanol is utilized to perform scrubbing-absorption on C1-C4 light components generated in the separation step, and returned for being fed and converted, so that the methanol is transformed into high value-added stable light hydrocarbon comprising mixed aromatic hydrocarbons. According to the method, the refining control on a reaction process is improved through inter-stage heat exchange of reaction prdocuts, so that the materials are effectively utilized and thermally integrated among processing processes, and the environmental pollution is reduced while the product yield is increased and the energy consumption is reduced.
Description
Technical field
The present invention relates to a kind of methanol process for producing hydrocarbons of employing moving bed, the heat of the technological reaction product can be obtained efficiently
Circulation and utilization.
Background technology
BTX aromatic hydrocarbons (Benzene, Toluene, Xylene) 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, extremely
2013, China's xylol external dependence degree was up to 55.3%, and insufficiency of supply-demand is further increased.Conventionally produced PX items
Mesh engineering construction difficulty is big, production technology threshold is high, investment is big, is limited more by raw material naphtha resource.Current China's oil
The increase of 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
New way substitutes traditional petroleum path production aromatic hydrocarbon product.It is domestic rich coal resources with this formation sharp contrast, it is main
Methanol production capacity that will be 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 ", using rich
Rich coal resources synthesizing methanol, research and development methanol oxidation conversion prepares aromatic hydrocarbons (MTA) technique, can be in production link just
High concentration PX is 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) 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) 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 be all
The efficiency of gas solid separation system can be affected, and then affects subsequent fractionation system；(5) 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 movement of High Efficiency Thermal integrated-type
Bed methanol hydrocarbon method, the method can realize the serialization of aromatization of methanol reaction and catalyst regeneration process, it is possible to increase
The refinement controlling extent of course of reaction, realizes that effectively material is utilized and is thermally integrated between processing technique, with catalyst activity
The advantages of stable, pressure drop is low, laminar flow reacts, back-mixing is few.
The technical scheme is that：
A kind of High Efficiency Thermal integrated-type moving bed methanol hydrocarbon method, including hydrocarbon synthesis step, adopt in the hydrocarbon synthesis step
The reactor being serially connected with least two, anti-applications catalyst is according to by most order of the top reactor to least significant end reactor
Sequentially pass through and regenerated into regenerator after each reactor, be then back to most top reactor, methanol feedstock is advanced after heating up
Enter most top reactor, its product enters its latter reactor as reaction raw materials, and the rest may be inferred, until second from the bottom
The product of individual reactor enters least significant end reactor as reaction raw materials, and the reactor is radially moving bed reactor,
Can be " π " type reactor or " Z " type reactor, can be to cardioid reactor or centrifugal type reactor.Multiple reactors
Product successively carry out heat exchange with methanol feedstock as exothermic medium, cascade raising temperature is carried out to methanol feedstock, it is the plurality of
Reactor at least includes most top reactor and least significant end reactor, and the product of least significant end reactor is divided into multiply, wherein
At least one is used to heat up methanol feedstock, anti-by changing the stock according to the temperature of the product of least significant end reactor
The flow-control for answering product enters the temperature of charge of most top reactor, and then controls the reaction temperature of most top reactor.This
Invention makes catalyst sequentially pass through the reactor of one group of series connection, realizes that the substep to catalyst activity is utilized；According to product
Temperature, by heat exchange mode flexible feeding temperature between level, so as to flexibly control the reaction temperature of substep, and then realize it is right
Corresponding substep catalyst activity makes full use of.The present invention realizes that by the way the coupling step by step of reaction, relay are effective
The control to temperature rise is realized on ground, makes feeding temperature match with reaction temperature rising.
The product of least significant end reactor preferably rises prior to the product of most top reactor to methanol feedstock
Temperature, because the product potential temperature of least significant end reactor is higher, latent heat is bigger, and using it the temperature of methanol feedstock is can significantly modify
Degree, is accurately to control methanol feedstock to reserve more free regulation space into the temperature of most top reactor.In methanol feedstock only
In the case of introducing most top reactor, the reaction temperature that can control most top reactor is not higher than the anti-of least significant end reactor
Temperature is answered, the reaction temperature of previous reactor is not higher than the reaction temperature of latter reactor in adjacent two reactor.
The High Efficiency Thermal integrated-type moving bed methanol hydrocarbon method also includes separating 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 each stock of product of end reaction device converges and sends into the gas and oil water afterwards (such as to 40～60 DEG C) according to technological requirement cooling
Three-phase separating device, isolated most of gas phase Jing recycle gas compressor compression is pressurized to 0.25～1.9MPaG and is used as to follow
Ring gas, the circulating air sub-thread enters the most top reactor Jing after heating up as reaction raw materials, or be divided into two strands it is respective
Most top reactor and least significant end reactor are respectively enterd as reaction raw materials after being heated up, according to the temperature of each stock circulating air
By the reaction depth for adjusting the online independent regulation respective reaction device of each stock circulating air flow；Circulating air enters respective reaction device
Mode is to converge to enter back into respective reaction device with the reaction feed of respective reaction device after intensification；When circulating air is divided into two strands, examine
The circulating air for entering most top reactor is considered in addition to participating in reaction and improve yield, also to play cold shock effect, therefore
It is preferred that making the circulating air flow into most top reactor be more than the circulating air flow into least significant end reactor.Isolated
Fraction gas phase can enter post-processing step as pending material.Isolated aqueous portion sends into oily waste water treatment
Device, it is also possible to direct reuse to upstream coal gasification apparatus, so as to effectively save public work；Isolated oil phase part
The fractionating device is sent into, liquid phase C6 that fractional distillation is obtained～C10 components or C8～C10 components are drawn as product, correspondingly, liquid
Phase C3～C5 components or C3～C7 components return hydrocarbon synthesis step as reaction raw materials, converge with different reactor charging respectively；
Remaining light component enters post-processing step as pending material.Isolated fraction gas phase and fractional distillation obtain remaining
Light component is introduced into post-processing step after can converging.The product of least significant end reactor is cooled to the type of cooling of room temperature
It can be the combination of dry type air cooling, wet type air cooling, water-cooled or aforesaid way.It is relative due to gas phase as circulating air can be changed
The accounting of whole gas phases that three phase separation is obtained, and when circulating air is divided into two strands enter most top reactor and least significant end it is anti-
The allocation proportion of the circulating air flow of device is answered, can further promote feeding temperature to match with reaction temperature rising, each stock can be made
The regulation of circulating air flow all has very strong independence, and this also implies that the anti-of most top reactor and least significant end reactor
Degree and depth is answered to carry out independent regulation without restricting each other by circulating air.
Before each stock of the product of least significant end reactor converges, there are one or two bursts of conducts to put in multiply product
Thermal medium is heated up respectively by heat exchange to per share circulating air, and again each stock converges the product Jing after heat exchange cooling.With
Methanol feedstock carries out the flow that the flow of the product of heat exchange preferably smaller than carries out the product of heat exchange with circulating air,
Also, when heat exchange is carried out with multiply circulating air, the reaction for carrying out heat exchange with the circulating air for entering most top reactor is produced
The flow of thing preferably greater than carries out the flow of the product of heat exchange with the circulating air into least significant end reactor, right to meet
The heating of more circulating air is needed with heat.
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, absorption tower bottom liquid most top reactor described in feeding 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～C10 fragrant
Hydrocarbon product mix is discharged into product storage tank by bottom of towe；Top gaseous phase C1～C5 Jing dry type air coolings, wet type air cooling, water-cooled or above-mentioned
The combination type of cooling cooling of mode, temperature is down under logistics current pressure between C4 and the boiling point of C5, is returned into tower top
Stream tank, C1～C4 gaseous components are 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 refluxes pump is pressurized, and part backflow returns tower top；Another part returns most end after heating up as reaction raw materials
End reactor；When using fractionating column, C8～C10 aromatic hydrocarbons product mix is set to be discharged into product storage tank by bottom of towe；Top gaseous phase
The combination type of cooling cooling of C1～C7 Jing dry type air coolings, wet type air cooling, water-cooled or aforesaid way, temperature is down to and is worked as between logistics
Under front pressure between C5 and the boiling point of C6, into return tank of top of the tower, C1～C5 gaseous components are 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, and C6～C7 liquid phase Jing overhead refluxes pump supercharging, part backflow is returned
Tower top；Another part C6～C7 liquid phases are produced as product, or least significant end reactor is returned after heating up as reaction raw materials, or
Person part returns least significant end reactor as product extraction after another part heats up as reaction raw materials.Return least significant end reaction
The C5 or C6～C7 of device mixes laggard after heating up with the product (i.e. intermediate products) of the previous reactor of least significant end reactor
Enter least significant end reactor and participate 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～C10 aromatic hydrocarbons product mix be discharged into product by depentanizer bottom of towe
Storage tank, gas phase and liquid phase, gas phase are separated into after depentanizer top gaseous phase C1～C5 is condensed into depentanizer top return tank
Discharged by the tank deck of depentanizer top return tank, liquid phase Jing depentanizer top reflux pump supercharging, part backflow returns de- pentane
Column overhead, another part enters debutanizing tower；Depentanizer top gaseous phase condense and detached method for it is following any one：
(1) depentanizer top gaseous phase temperature is reduced under logistics current pressure between C2 and the boiling point of C3, isolates C1～C2
Gas phase and C3～C5 liquid phases；(2) depentanizer top gaseous phase temperature is reduced to the boiling point of the C4 and C5 under logistics current pressure
Between, isolate C1～C4 gas phases and C5 (generally also containing a small amount of C1～C4) liquid phase；Jing debutanizing tower fractional distillation, produces C5 liquid phases
Product are discharged by debutanizing tower bottom of towe, are heated up as reaction raw materials Jing and are returned least significant end reactor, and debutanizing tower top gaseous phase C1～
Gas phase and liquid phase are separated into into debutanizing tower top return tank after C4 is 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
Most top 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
It is allocated as entering post-processing step for pending material；Debutanizing tower top gaseous phase is condensed and detached method is following any one
Kind：(1) debutanizing tower top gaseous phase temperature is reduced under logistics current pressure between C2 and the boiling point of C3, isolate C1～
C2 gas phases and C3～C4 liquid phases；(2) debutanizing tower top gaseous phase temperature is reduced to the boiling of the C3 and C4 under logistics current pressure
Between point, C1～C3 gas phases and C4 (usually containing a small amount of C3) liquid phase are isolated.Depentanizer top gaseous phase and debutanizing tower tower
Top gas 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 least significant end
The C5 of reactor is entered most after mixing with the product (i.e. intermediate products) of the previous reactor of least significant end reactor after heating up
End reaction device 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, C3～C4 liquid of debutanization overhead reflux
Phase (correspondence said method (1)) or C4 liquid phases (correspondence said method (2)) the Jing debutanization overhead refluxes pump containing part C3 increase
Pressure, part backflow returns debutanizing tower tower top, and another part enters dehydrogenation reactor dehydrogenation, obtains after dehydrogenation after heating up
C3, C4 unsaturated hydrocarbons are used as return least significant end reactor after reaction raw materials intensification.After C3～C4 liquid phases and dehydrogenation before dehydrogenation
C3, C4 unsaturated hydrocarbons are realized heating up by heat exchange, and the C3～C4 liquid phases before dehydrogenation are preferably warming up to 350～540 DEG C, dehydrogenation
C3, C4 unsaturated hydrocarbons afterwards are preferably warming up to 150～250 DEG C, with the product of the previous reactor of least significant end reactor (i.e.
Intermediate products) mixing after enter least significant end reactor participate in reaction, intensification thermal source can be each reactor product or
Outer supplying heat 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
0.25～1.75MPaG, temperature is 320～520 DEG C；The pressure of least significant end reactor is 0.20～1.73MPaG, and temperature is 370
～550 DEG C；It is not higher than the maximum pressure of previous reactor per the maximum pressure of latter reactor in adjacent two reactor, and not
Higher than the maximum pressure of most top reactor, the minimum pressure of latter reactor is not higher than the minimum pressure of previous reactor, and
It is not higher than the minimum pressure of most top 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 270～490 DEG C；Methanol feedstock is successively
It is warming up to 98～250 DEG C and 250～480 DEG C；Absorb tower bottom liquid and first mix with methanol feedstock and together rise step by step with methanol feedstock again
Temperature；It is 5-20 that methanol spray flow rises flow-rate ratio with bottom gas phase, and operation temperature is room temperature, and pressure is 0.3～1.4MPaG；
The tower top pressure of depentanizer is 0.3～1.75MPaG, and tower reactor pressure is 0.35～1.8MPaG；The tower top pressure of fractionating column is
0.06～1.6MPaG, such as 0.06,0.8,1.6MPaG, can determine according to practical situation；Tower reactor pressure be 0.07～
1.8MpaG, such as 0.07,0.85,1.8MPaG, can determine according to practical situation.The C5 or C6 of return least significant end reactor～
C7 realizes heating up by heat exchange, is warming up to 150～250 DEG C, and 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 is 0.25
～1.75MPaG, temperature is 320～520 DEG C；The pressure of least significant end reactor is 0.20～1.73MPaG, and temperature is 370～550
℃；The maximum pressure of latter reactor is not higher than the maximum pressure of previous reactor in per adjacent two reactor, and is not higher than
The most maximum pressure of top reactor, the minimum pressure of latter reactor is not higher than the minimum pressure of previous reactor, and not
Higher than the minimum pressure of most top 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 270～490 DEG C；Methanol feedstock successively heats up
To 98～250 DEG C and 250～480 DEG C；Absorb tower bottom liquid first to mix with methanol feedstock again with methanol feedstock together cascade raising temperature；First
It is 5-20 that alcohol spray flow rises flow-rate ratio with bottom gas phase, and operation temperature is room temperature, and pressure is 0.3～1.4MPaG；De- pentane
The tower top pressure of tower is 0.3～1.75MPaG, and tower reactor pressure is 0.35～1.8MPaG；The tower top pressure of debutanizing tower be 0.4～
1.6MPaG, tower reactor pressure is 0.45～1.65MPaG；The C5 liquid phases for returning least significant end reactor are realized 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；Return the C3～C4 of most top reactor
Liquid phase first mixes again with methanol feedstock together cascade raising temperature with methanol feedstock.
For aforementioned High Efficiency Thermal integrated-type moving bed methanol hydrocarbon method described in any one, can also be by methanol feedstock
Be divided into multiply after intensification, in addition to wherein one enters most top reactor, other each stocks respectively enter other reactors, and make into
Enter the methanol feedstock accounting of most top reactor more than the methanol feedstock into other each reactors.Methanol is directly added into reaction
Device, can provide CH3- groups for reaction, and the alkane such as LPG, C5 of later separation part return for returning with circulating air carries out alkane
Aromatisation, methanol alkylation etc. react, and promote the carrying out of aromatization, are conducive to improving aromatics yield.
Above-mentioned heat exchange unit can include the heat exchanger of 1 or more than 2 serial or parallel connection.Its thermal source can
Being 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 through reactor order and catalyst through reactor
Order it is identical.Fresh methanol initially enters the most top reactor of arranged in series, with the high activated catalyst from regenerator
Haptoreaction.It is heated in view of fresh methanol and easily decompose, therefore keep the most relatively low reaction temperature of top reactor, makes to react
Journey is more gentle, and reaction temperature rising is less, can be effectively prevented from methanol short time decomposes, reacts easily controllable.Most top is anti-
Answer and react in device in addition to the reactions such as aromatization of methanol, hydrocarbon restructuring generate aromatic hydrocarbons, due to relatively low reaction temperature, also there is first
The side reactions such as the intermediate products such as alcohol generation low-carbon (LC) hydro carbons, thus the intermediate products wider distribution for generating.Due to most top reactor
Catalyst activity is higher, and while reaction efficiency height, high conversion rate relatively low reaction temperature is kept, and reaction can be made to be easy to control
System.
By taking 2 reactors in series as an example, intermediate product temperature reduction after heat exchange of the 1st reactor goes successively to the 2nd
Reactor is with the activity from the 1st reactor compared with low catalyst haptoreaction.Because intermediate product has contained part aromatic hydrocarbon product,
Therefore only need relatively low catalyst activity that the alkane that the lower carbon number hydrocarbons in intermediate products and later separation part return is continued into virtue
Structure reaction, hydrocarbon recombinant conversion are aromatic product, and this outer portion methanol feedstock provides CH3- groups, also promotees when entering reactor
The degree of alkylation conversion is entered.Because catalyst activity is relatively low, reaction is more gentle, and reaction temperature rising is less, is effectively prevented
Coking, reacts easily controllable.
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 the catalyst equidirectional type of flow, using raw material reaction speed difference and its to catalyst
The characteristics of active demand is different, to catalyst activity branch's utilization has been carried out, 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, efficiently avoid methanol and cross thermal decomposition, make reactions steps equal
It is more gentle, the refinement control of course of reaction is realized, reaction temperature rising has been efficiently controlled, be conducive to product purity with yield
Lifted simultaneously.
3rd, the application utilizes the characteristics of product potential temperatures at different levels are high, latent heat is big, makes full use of its heat to reaction feed
And the circulating air that product is isolated carries out one or many preheating, efficiently utilize own heat and realize reaction raw materials temperature
It is up to standard, so as to save outer heating load.Additionally, the heat of intermediate product is removed in time so as to the reactor reaction in downstream
Temperature is reduced, and is conducive to keeping course of reaction more steady, the generation of slagging prevention.
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：Most top reactor is returned, i.e., is mixed with fresh methanol charging 1, the C1～C4 groups in circulating air
The CH3- groups that dividing can provide with methanol participate in reaction jointly, improve yield, promote alkylation conversion and alkane aromatization to convert.
Further, since most top reactor catalyst activity is high, reaction is violent, and heat release is big, and the most top reactor of circulating air 1 pair plays cold
But/cold shock effect, prevents from reacting too fast coking.
(2) circulating air 2：Least significant end reactor is returned, i.e., is mixed with the intermediate products of penultimate reactor production.By
C1～C4 components and later separation part in least significant end reactor based on aromatization of low carbon hydrocarbon, alkylation, in circulating air
The alkane of return promotes methanol alkylation reaction with the methanol in charging, 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 product yield.
5th, liquid phase component enters depentanizer after product three phase separation, and bottom of towe obtains C6～C10 target products.Tower top
The cooling of C1～C5 components Jing, gas-liquid separation, C5 components return least significant end reactor feed, i.e., with penultimate reactor product
Intermediate products mix, and participate in the hydrocarbon synthesis of least significant end reactor, are effectively utilized the value of C5 side-products, reduce whole device
Side-product quantity, improves aromatics yield.It is former for also fresh methanol is entered to each reactor in addition to most top reactor
The situation of material, because methanol charging brings CH3- groups in least significant end reactor, C5 can be rapid fragrant under catalyst action
Structureization reaction generates aromatic hydrocarbons, so as to the value of further effectively utilizes C5 side-product, reduces whole device side-product quantity.
6th, depentanizer top light component C1～C4 is entered in an absorption tower, is drawn one methanol from fresh methanol charging and is entered
2 couples of C1～C4 of material carry out spray-absorption, effectively C3, C4 component in depentanizer top gas are absorbed and are dissolved in wherein.This strand of thing
Expect to mix with the charging for entering most top reactor, i.e., mix with fresh methanol charging 1, so as to efficiently utilize C3, C4 group
Point, 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
Wash mode to be capable of achieving to be efficiently absorbed at normal temperatures, both eliminated the reboiler of conventional fractionation tower height energy consumption, work is make use of again
The raw material of skill itself 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
The boiling temperature of C2.Debutanizing tower separates C5 with C1～C4, and C5 components return least significant end reactor feed, effective land productivity
With the value of C5 side-products, whole device side-product quantity is reduced, improve aromatics yield.Tower top C1, C2 component and C3,
C4 Component seperations, C1, C2 component and depentanizer C1, C2 component wash absorption tower after converging into room temperature methanol.Debutanizing tower has
C3, C4 content into absorption tower is reduced to effect, methanol usage is reduced, the saving of raw material and the energy is realized.
Isolated C3～C4 the components of debutanizing tower are effectively converted into C3, C4 insatiable hunger by the 8th, setting of dehydrogenation reactor
And hydrocarbon, converge with debutanizing tower bottom of towe C5, and then mix with intermediate products, into least significant end reactor, its own C=for containing
C participates in reaction, directly participates in cyclisation, hydrocarbon restructuring, increased product yield.Additionally, the setting of dehydrogenation reactor is effectively improved
Methanol washes the hydrogen purity of absorption tower tower top fixed gas, and 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, C7 light 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 High Efficiency Thermal integrated-type moving bed methanol hydrocarbon method, below by way of several specific embodiments
Describe the method utilization aborning in detail.
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 1st reactor (equivalent to most top reactor) after heating up, and urges from the highly active of regenerator
Agent carries out radially moving bed haptoreaction, and liquid hourly space velocity (LHSV) is 1.0h-1, (i.e. the reaction of the 1st reactor is produced to generate intermediate products
Thing), pressure 0.46MPaG, 520 DEG C of temperature.Intermediate products leave and enter after the 1st reactor the 1st heat exchange unit, used as thermal source pair
1st reactor feed is heated, and methanol charging 1 is heated to 480 DEG C, and intermediate products are cooled to 490 DEG C.Intermediate products leave
The 2nd reactor (equivalent to least significant end reactor) is entered after 1st heat exchange unit, with the catalyst from the 1st reactor conduct is entered
To moving-bed contacting reaction, liquid hourly space velocity (LHSV) is 1.0h-1, reaction of formation product, pressure 0.44MPaG, 550 DEG C of temperature.Product
It is divided into 2 strands after being drawn by the 2nd reactor --- product 1, product 2, flow-rate ratio is 0.40.Product 1 and methanol
Charging 1 is exchanged heat in the 2nd heat exchange unit, and methanol charging 1 is heated to 250 DEG C.Product 2 with from cycle compressor
The circulating air of machine is exchanged heat in the 3rd heat exchange unit, after the product 1 after heat exchange is converged with product 2, Jing wet type air coolings
45 DEG C are cooled to, 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
650 DEG C of degree, regeneration pressure 0.60MPaG.The regenerator is conventional regeneration device.High activated catalyst Jing after regenerator regeneration is carried
The 1st reactor head is risen to, bed is moved with the 1st reactor feed and is radially contacted with reaction, enter back into the 2nd reactor, with
Bed is moved from the intermediate product of the 1st reactor radially contact 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 18.0.Gas phase 1 enters recycle gas compressor, is pressurized to 0.56MPaG, is exchanged heat in the 3rd heat exchange unit, circulation
Gas is heated to 320～480 DEG C, such as 480 DEG C, converges with the methanol charging 1 in the 1st heat exchange unit heat-absorbing medium exit, altogether
With the reaction feed as 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：0.3MPaG；Tower reactor pressure：0.35MPaG.Jing depentanizer fractional distillation, in liquid-phase reaction product
C5 following components (i.e. C1～C5) is discharged by tower top, and C6～C10 aromatic hydrocarbons product mix is discharged into product storage tank by bottom of towe.De- penta
Alkane column overhead gas phase Jing dry type air cooling, water-cooled combination type of cooling cooling, temperature is down to 45 DEG C, into depentanizer fight back stream
Tank.C1～C4 gaseous components are discharged by tank deck, and C5 liquid phase Jing depentanizers top reflux pump supercharging, part backflow returns de- pentane
Column overhead；The heat exchange units of another part C5 liquid-phase products Jing the 5th are warming up to 250 DEG C, mixed with the 1st reactor product intermediate products
Close, as the charging of the 2nd reactor reaction reaction is participated in, the 5th heat exchange unit thermal source is outer confession 1.2MPaG steam.
After the C1～C4 gaseous components gas phase 2 detached with three phase separation tank discharged by depentanizer fight back stream tank deck is converged
Into absorption tower bottom.Mode of operation is washed in absorption tower using room temperature methanol, and one fresh methanol feeds 2 (30 DEG C) and entered by tower top
Absorption tower, is sprayed from top to bottom.Absorption tower top methanol spray flow rises flow-rate ratio with bottom C1～C4 gas phases
20.0,25 DEG C of tower top operation temperature, operating pressure 0.3MPaG.Absorb tower top fixed gas (C1, C2 component) to be discharged by tower top；Tower
Bottom 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 enters
Enter 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 1.77MPaG, 30 DEG C of temperature.Fresh methanol feed 1 Jing with it is anti-
Product heat exchange is answered to initially enter the 1st reactor (equivalent to most top reactor) after heating up, and from the highly active of regenerator
Catalyst carries out radially moving bed haptoreaction, and liquid hourly space velocity (LHSV) is 5.0h-1, (i.e. the reaction of the 1st reactor is produced to generate intermediate products
Thing), pressure 1.75MPaG, 350 DEG C, or 320 DEG C of temperature.Intermediate products leave the 1st heat exchange unit after the 1st reactor,
The 1st reactor feed is heated as thermal source, methanol charging is heated to 270 DEG C or 250 DEG C, and intermediate products are cooled to
320℃.Intermediate products leave and enter after the 1st heat exchange unit the 2nd reactor (equivalent to least significant end reactor), anti-with from the 1st
Answering the catalyst of device carries out radially moving bed haptoreaction, and liquid hourly space velocity (LHSV) is 5.0h-1, reaction of formation product, pressure 1.73MPaG,
400 DEG C, or 370 DEG C of temperature.Product is divided into 2 strands after being drawn by the 2nd reactor --- and product 1, reaction are produced
Thing 2, flow-rate ratio is：0.8.Product 1 is exchanged heat with methanol charging 1 in the 2nd heat exchange unit, and methanol charging 1 is heated
To 170 DEG C.2 points of product is product 3, product 4, and flow-rate ratio is 0.73, respectively with from recycle gas compressor
Circulating air exchanged heat in the 3rd heat exchange unit, the 4th heat exchange unit.Product 1, product 3 after heat exchange,
Product 4 is converged, and Jing wet type air coolings are cooled to 50 DEG C, and 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, regeneration pressure 1.85 or 1.9MPaG.The regenerator is conventional regeneration device.Highly active catalytic Jing after regenerator regeneration
Agent is promoted to the 1st reactor head, moves bed with the 1st reactor feed and radially contacts with reaction, enters back into the 2nd reactor,
Bed is moved with the intermediate product from the 1st reactor radially contact 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 18.0.Gas phase 1 enters recycle gas compressor, is pressurized to 1.82MPaG.Send into before being heated in the 3rd heat exchange unit, follow
Ring edema caused by disorder of QI is two strands --- circulating air 1 and circulating air 2, flow-rate ratio is 0.9.Circulating air 1 is with product 3 in the 3rd heat exchange unit
In exchanged heat, circulating air 1 is heated to 270 DEG C or 250 DEG C.Circulating air 2 is carried out with product 4 in the 4th heat exchange unit
Heat exchange, circulating air 2 is heated to 320 DEG C or 270 DEG C.The fresh methanol in the heat exchange unit heat-absorbing medium exit of circulating air 1 and the 1st
Charging 1 converges, collectively as the reaction feed of the 1st reactor；The centre of the heat exchange unit exothermic medium of circulating air 2 and the 1st outlet
Product converges, 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：1.75MPaG；Tower reactor pressure：1.8MPaG.Jing depentanizer fractional distillation, in liquid-phase reaction product
C5 following components is discharged by tower top, and C6～C10 aromatic 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 42 DEG C, into depentanizer top return tank.C1～C2 gaseous components are discharged by tank deck,
C3～C5 liquid phases (generally also containing a small amount of C1, C2) Jing depentanizers top reflux pump supercharging, part backflow returns de- pentane
Column overhead；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, tower top fixed gas (C1～C4 components) is discharged by tower top；The heat exchange units of bottom of towe C5 liquid-phase product Jing the 5th are warming up to 150 DEG C,
The 2nd reactor feed is returned, i.e., is mixed with the 1st reactor product intermediate products and is participated in reacting as reaction feed, the 5th heat exchange is single
First 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 38 DEG C, enters de- fourth
Alkane return tank of top of the tower.C1～C2 gaseous components are discharged by tank deck, the supercharging of C3, C4 liquid phase Jing debutanization overhead reflux pump, a part
Backflow returns debutanizing tower tower top；Another part liquid-phase product mixes with fresh methanol charging 1 before reactor, used as reaction feed
Participate in reaction.
Depentanizer tower top C1～C2 gaseous components and debutanizing tower tower top C1～C2 gaseous components and three phase separation tank point
From 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 DEG C) enter absorption tower by tower top, are sprayed from top to bottom.Absorption tower top methanol spray flow rises with bottom gas phase
Flow-rate ratio is 5 or 6.25 DEG C of tower top operation temperature, operating pressure 1.3 or 1.4MPaG.Absorb tower top fixed gas (C1, C2 component)
Discharged by tower top；Bottom of towe liquid phase mixes with fresh methanol charging 1 before reactor, participates in reacting as reaction feed.Absorb tower top
The fixed gas of discharge enters follow-up methanol water washing device, to reclaim methanol.The methanol waste water for obtaining returns coal gas Jing after processing
Change 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～C4 dehydrogenations, methanol feedstock is divided to 2 strands to respectively enter two reactors.
Fresh methanol feeds and pumped outside 1 Jing battery limit (BL)s, boosts to 0.3MPaG, 30 DEG C of temperature.Fresh methanol feed 1 Jing with it is anti-
Product heat exchange is answered to be 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
2 reactors (equivalent to least significant end reactor) feed, and flow-rate ratio is 9:1.Raw material 1 enters the 1st reactor, and from regenerator
Highly active catalyst carries out radially moving bed haptoreaction, and liquid hourly space velocity (LHSV) is 2.5h-1, generate intermediate products (i.e. the 1st reactor
Product), pressure 0.25MPaG, 450 DEG C of temperature.Intermediate products leave and enter after the 1st reactor the 1st heat exchange unit, make
The 1st reactor feed is heated for thermal source, methanol charging 1 is heated to 400 DEG C, and intermediate products are cooled to 420 DEG C.It is middle
Product to leave and be mixed into the 2nd reactor with raw material 2 after the 1st heat exchange unit, carries out radially with the catalyst from the 1st reactor
Moving-bed contacting reacts, and liquid hourly space velocity (LHSV) is 2.5h-1, reaction of formation product, pressure 0.2MPaG, 490 DEG C of temperature.Product by
2nd reactor is divided into 2 strands after drawing --- and product 1, product 2, flow-rate ratio is：0.43.Product 1 and reaction first
Alcohol charging 1 is exchanged heat in the 2nd heat exchange unit, and methanol charging 1 is heated to 132 DEG C.2 points of product be product 3,
Product 4, flow-rate ratio is 0.76, single in the 3rd heat exchange unit, the 4th heat exchange with the circulating air from recycle gas compressor respectively
Exchanged heat in unit.Product 1, product 3 after heat exchange, product 4 are converged, and are cooled to 60 DEG C, enter
Three phase separation tank enters the three phase separation of circulation of qi promoting, oil, water.
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 0.2 or 0.3MPaG.The regenerator is conventional regeneration device.Highly active catalytic Jing after regenerator regeneration
Agent is promoted to the 1st reactor head, moves bed with the charging from the 1st reactor and radially contacts with reaction, enters back into the 2nd anti-
Device is answered, bed is moved with the intermediate products from the 1st reactor and is radially contacted 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 0.32MPaG.The circulating air for leaving recycle gas compressor is divided into 2
Stock --- circulating air 1, circulating air 2, flow-rate ratio is 0.8.Circulating air 1 is exchanged heat with product 3 in the 3rd heat exchange unit,
Circulating air 1 is heated to 400 DEG C.Circulating air 2 is exchanged heat with product 4 in the 4th heat exchange unit, and circulating air 2 is heated
To 420 DEG C.Circulating air 1 mixes with the raw material 1 after intensification, collectively as the reaction feed of the 1st reactor；Circulating air 2 is changed with the 1st
The intermediate products and raw material 1 of hot cell exothermic medium outlet mix, collectively as the reaction feed of the 2nd 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
C5 following components is discharged by tower top, and C6～C10 aromatic 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 48 DEG C, into depentanizer top return tank.C1～C4 gaseous components are discharged by tank deck,
C5 liquid phases (generally also containing 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～C4 components) is discharged by tower top；The heat exchange units of bottom of towe C5 liquid-phase product Jing the 5th heat up
To 180 DEG C, converge with the 1st reactor product intermediate products and raw material 2, participate in reacting as the charging of the 2nd reactor 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 37 DEG C, is entered
Enter debutanization return tank of top of the tower.C1～C3 gaseous components are discharged by tank deck, C4 (containing a small amount of C3) liquid phase Jing debutanization overhead reflux
Pump is pressurized, and part backflow returns debutanizing tower tower top；Another part liquid-phase product exchanges heat with product 1 and (does not show on figure
Go out), 430 DEG C are 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 2, as the charging of the 2nd reactor reaction reaction is participated in.
Depentanizer tower top C1～C4 gaseous components and debutanizing tower tower top C1～C3 gaseous components and three phase separation tank point
From 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 DEG C) enter absorption tower by tower top, are sprayed from top to bottom.Absorption tower top methanol spray flow and bottom C1～C4 gas
It is 7 mutually to rise flow-rate ratio.25 DEG C of tower top operation temperature, operating pressure 0.8MPaG.Absorb tower top fixed gas (C1, C2 component) by
Tower top is discharged；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 feeds and pumped outside 1 Jing battery limit (BL)s, boosts to 0.6MPaG, 30 DEG C of temperature.Fresh methanol feed 1 Jing with it is anti-
Product heat exchange is answered to be 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 8:2:1.It is anti-that raw material 1 enters the 1st
Device is answered, with the highly active catalyst from regenerator radially moving bed haptoreaction is carried out, liquid hourly space velocity (LHSV) is 1.6h-1, generate
Intermediate products 1 (i.e. the product of the 1st reactor)：Pressure 0.56MPaG, 440 DEG C of temperature.Intermediate products 1 leave the 1st reaction
The 1st heat exchange unit is entered after device, the 1st reactor feed is preheated as thermal source, methanol charging 1 is heated to 400 DEG C, in
Between product 1 be cooled to 420 DEG C.Intermediate products 1 to leave and be mixed into the 2nd reactor with raw material 2 after the 1st heat exchange unit, with from
The catalyst of the 1st reactor carries out radially moving bed haptoreaction, and liquid hourly space velocity (LHSV) is 1.8h-1, (the i.e. the 2nd is anti-to generate intermediate products 2
Answer the product of device), pressure 0.54MPaG, 480 DEG C of temperature.Intermediate products 2 mix after being drawn by the 2nd reactor with raw material 3
Into the 3rd reactor, radially moving bed haptoreaction is carried out with the catalyst from the 2nd reactor, liquid hourly space velocity (LHSV) is 2.0h-1,
Reaction of formation product, pressure 0.52MPaG, 520 DEG C of temperature.
Product is divided into 2 strands --- and product 1, product 2, flow-rate ratio is：1.5.Product 1 is entered with methanol
Material 1 is exchanged heat in the 2nd heat exchange unit, and methanol charging 1 is heated to 127 DEG C or 98 DEG C.2 points of product is product
3rd, product 4, flow-rate ratio is 1.5, single in the 3rd heat exchange unit, the 4th heat exchange with the circulating air from recycle gas compressor respectively
Exchanged heat in unit.Product 1, product 3 after heat exchange, product 4 are converged, and Jing wet type air coolings are 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 3rd reactor, is promoted to regenerator overhead, under drop down onto in regenerator and regenerated, regeneration temperature
570 DEG C of degree, regeneration pressure 0.7MPaG.The regenerator is conventional regeneration device.High activated catalyst Jing after regenerator regeneration is lifted
To the 1st reactor head, move bed with the 1st reactor feed and radially contact with reaction；Enter back into the 2nd reactor, with from
The intermediate products 1 of the 1st reactor move bed and radially contact with reaction；The 3rd reactor is entered back into, and from the 2nd reactor
Intermediate products 2 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 11.0.Gas phase 1 enters recycle gas compressor, is pressurized to 0.68MPaG.The circulating air for leaving recycle gas compressor is divided into 2
Stock --- circulating air 1, circulating air 2, flow-rate ratio is 0.8.Circulating air 1 is exchanged heat with product 3 in the 3rd heat exchange unit,
Circulating air 1 is heated to 400 DEG C.Circulating air 2 is exchanged heat with product 4 in the 4th heat exchange unit, and circulating air 2 is heated
To 490 DEG C.Circulating air 1 mixes with the raw material 1 after intensification, collectively as the reaction feed of the 1st reactor；Circulating air 2 is anti-with the 2nd
The intermediate products 2 and raw material 3 for answering device outlet mix, collectively as the reaction feed of the 3rd 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 0.06～1.6MPaG, such as 0.8MPaG；Tower reactor pressure is 0.07～1.8MpaG, for example
0.85MPaG；Tower fractional distillation is fractionated into, C7 following components is discharged by tower top, and C8～C10 aromatic hydrocarbons product mix is discharged into by bottom of towe
Product storage tank；The mode of top gaseous phase C1～C7 Jing wet type air coolings is cooled down, and temperature is down to 120 DEG C, into fractional distillation return tank of top of the tower.
C1～C5 gaseous components are discharged by tank deck, and gas phase 2 detached with three phase separation tank enters absorption tower bottom after converging.C6～C7 liquid
The supercharging of overhead reflux pump is mutually fractionated into, part backflow returns fractionator overhead；Another part produce, as light aromatic hydrocarbons product from
Opening apparatus enter auxiliary product storage tank.Certainly, another part C6～C7 liquid phases can also be with the product of certain reactor
Heat exchange returns the 3rd reactor feed after heating up.
After fractionator overhead C1～C5 gaseous components 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, and one fresh methanol feeds 2 (30 DEG C) and enters absorption tower 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, C2 component) to be discharged by tower top；It is new before bottom of towe liquid phase C3～C5 and reactor
Fresh methanol charging 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 | 0.72 | 0.68 | 0.67 | 0.07 |
| C6A | 11.9 | 12.1 | 12.18 | 4.4 |
| C7A | 29.61 | 29.23 | 28.32 | 15.78 |
| C8A | 44.25 | 44.82 | 44.86 | 54.03 |
| C9A | 11.16 | 10.96 | 11.5 | 19.49 |
| C10A | 2.26 | 2.11 | 2.37 | 6.22 |
The fixed gas of table 3 is constituted
| Composition | Embodiment 1 (Mol%) | Embodiment 2 (Mol%) | Embodiment 3 (Mol%) | Embodiment 4 (Mol%) |
| CO | 2.06 | 1.97 | 0.67 | 2.02 |
| Hydrogen | 17.02 | 16.88 | 73.09 | 17.11 |
| H2O | 0 | 0 | 0 | 0 |
| Methanol | 2.41 | 2.32 | 0.72 | 2.2 |
| C1 | 57.14 | 56.96 | 18.61 | 57.08 |
| C2 | 21.04 | 21.43 | 6.81 | 21.22 |
| C3 | 0.21 | 0.29 | 0.07 | 0.26 |
| C4 | 0.12 | 0.15 | 0.03 | 0.11 |
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.
Isolated C3～C5 the liquid-phase products of separating step return to reaction member and participate in reaction.Circulating air is returned and carried
Substantial amounts of CH3- groups, can rapidly react generation aromatic hydrocarbons, so as to efficiently utilize C5 side-products in C5 Returning reactors
Value, reduce whole device side-product quantity.In C3～C4 component Returning reactors, C3, C4 component is efficiently utilized,
Consumption of raw materials is effectively reduced, the consumption of side-product is reduced.
Claims (10)
1. one kind is thermally integrated type moving bed methanol hydrocarbon method, including hydrocarbon synthesis step, using at least in the hydrocarbon synthesis step
Two reactors being serially connected, anti-applications catalyst is according to the order by most top reactor to least significant end reactor successively Jing
Cross and regenerated into regenerator after each reactor, be then back to most top reactor, methanol feedstock is introduced into after heating up and most begins
End reactor, its product enters its latter reactor as reaction raw materials, and the rest may be inferred, until penultimate reaction
The product of device enters least significant end reactor as reaction raw materials, and the reactor is radially moving bed reactor；It is multiple anti-
Answer the product of device successively carries out heat exchange as exothermic medium with methanol feedstock, and to methanol feedstock cascade raising temperature is carried out, should
Multiple reactors at least include most top reactor and least significant end reactor, and the product of least significant end reactor is divided into multiply,
One is used to heat up methanol feedstock wherein at least, should by changing according to the temperature of the product of least significant end reactor
The flow-control of stock product enters the temperature of charge of most top reactor, and then controls the reaction temperature of most top reactor
Degree, it is characterised in that also including separating step, the separating step is successively using gas-oil-water three-phase separating device and single-stage or many
The fractionating device of level carries out separation and Extraction to the product of the hydrocarbon synthesis step, and each stock of product of least significant end reactor converges
And the gas-oil-water three-phase separating device is sent into after cooling down, isolated most of gas phase Jing recycle gas compressor compression is used as
Circulating air, the circulating air sub-thread enters the most top reactor Jing after heating up as reaction raw materials, or is divided into two strands respectively
Most top reactor and least significant end reactor are respectively enterd as reaction raw materials from after being heated up, by adjusting each stock circulating air
The reaction depth of the online independent regulation respective reaction device of flow；Isolated aqueous portion sends into oil-contained waste water treatment device；
Isolated oil phase part is distributed into the fractionating device, liquid phase C6 that fractional distillation is obtained～C10 components or C8～C10 component conducts
Product is drawn, and correspondingly, liquid phase C3～C5 components or C3～C7 components return hydrocarbon synthesis step as reaction raw materials, remaining light group
It is allocated as entering post-processing step for pending material.
2. type moving bed methanol hydrocarbon method is thermally integrated as claimed in claim 1, it is characterised in that in least significant end reactor
Before each stock of product converges, there are one or two strands to follow to per share by heat exchange as exothermic medium in multiply product
Ring edema caused by disorder of QI is not heated up.
3. type moving bed methanol hydrocarbon method is thermally integrated as claimed in claim 2, it is characterised in that the post-processing step is used
Methanol treats treated substance and carries out reverse room temperature washing, and equipment adopts absorption tower, methanol feedstock self-absorption tower top to enter and absorb
Tower, from top to down to being entered by absorption tower bottom and the pending material that rises is sprayed, absorbs tower bottom liquid as reaction
Raw material most top reactor described in feeding Jing after heating up；Absorb tower top fixed gas to be discharged by tower top, into bleed-off system as combustion
Material gas is used, or into methanol water washing device to reclaim methanol.
4. type moving bed methanol hydrocarbon method is thermally integrated as claimed in claim 3, it is characterised in that the fractional distillation dress of the single-stage
Depentanizer or fractionating column are set to, when using depentanizer, make C6～C10 aromatic hydrocarbons product mix be discharged into product by bottom of towe
Storage tank；The combination type of cooling cooling of top gaseous phase Jing dry type air coolings, wet type air cooling, water-cooled or aforesaid way, temperature is down to Jie
Under logistics current pressure between C4 and the boiling point of C5, into return tank of top of the tower, C1～C4 gaseous components are by return tank of top of the tower
Tank deck is discharged, and the light component obtained as fractional distillation is entered and absorbs tower bottom, the supercharging of C5 liquid phase Jing overhead refluxes pump, part backflow
Return tower top；Another part is used as return least significant end reactor after reaction raw materials intensification；When using fractionating column, C8～C10 is made
Aromatic hydrocarbons product mix is discharged into product storage tank by bottom of towe；Top gaseous phase Jing dry type air coolings, wet type air cooling, water-cooled or aforesaid way
The combination type of cooling cooling, temperature is down under logistics current pressure between C5 and the boiling point of C6, into return tank of top of the tower,
C1～C5 gaseous components are 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, and C6～
C7 liquid phase Jing overhead refluxes pump is pressurized, and part backflow returns tower top；Another part C6～C7 liquid phases are produced as product, or
As reaction raw materials heat up after return least significant end reactor, or part as product extraction and another part as reaction raw materials
Least significant end reactor is returned after intensification.
5. type moving bed methanol hydrocarbon method is thermally integrated as claimed in claim 3, it is characterised in that the multistage fractional distillation dress
Put including depentanizer and debutanizing tower, the isolated oil phase part of gas-oil-water three-phase separating device is distributed into the de- pentane
Tower, makes C6～C10 aromatic hydrocarbons product mix be discharged into product storage tank by depentanizer bottom of towe, and depentanizer top gaseous phase is condensed
Afterwards gas phase and liquid phase are separated into into depentanizer top return tank, gas phase is discharged by the tank deck of depentanizer top return tank, liquid phase
Jing depentanizers top reflux pump supercharging, part backflow returns depentanizer tower top, and another part enters debutanizing tower；De- pentane
Column overhead vapor condensation and detached method for it is following any one：（1）Depentanizer top gaseous phase temperature is reduced between thing
Under stream current pressure between C2 and the boiling point of C3, C1～C2 gas phases and C3～C5 liquid phases are isolated；（2）Depentanizer top gaseous phase
Temperature is reduced under logistics current pressure between C4 and the boiling point of C5, isolates C1～C4 gas phases and C5 liquid phases；Jing takes off fourth
Alkane tower fractional distillation, makes C5 liquid-phase products be discharged by debutanizing tower bottom of towe, heats up as reaction raw materials Jing and returns least significant end reactor, takes off
Gas phase and liquid phase are separated into into debutanizing tower top return tank after butane column overhead gas phase is condensed, gas phase is by debutanizing tower fight back
The tank deck of stream tank is discharged, and liquid phase Jing debutanization overhead reflux pump supercharging, part backflow returns debutanizing tower tower top, another part
Most top reactor is returned after heating up as reaction raw materials, from depentanizer fight back stream tank and the tank deck of debutanization return tank of top of the tower
The gaseous component of discharge enters post-processing step；Debutanizing tower top gaseous phase condense and detached method for it is following any one：
（1）Debutanizing tower top gaseous phase temperature is reduced under logistics current pressure between C2 and the boiling point of C3, isolates C1～C2
Gas phase and C3～C4 liquid phases；（2）Debutanizing tower top gaseous phase temperature is reduced to the boiling point of the C3 and C4 under logistics current pressure
Between, isolate C1～C3 gas phases and C4 liquid phases.
6. type moving bed methanol hydrocarbon method is thermally integrated as claimed in claim 5, it is characterised in that the separating step is also adopted
With dehydrogenation reactor, in this case, the liquid phase Jing debutanization overhead reflux pump supercharging of debutanization overhead reflux a, part flows back
Debutanizing tower tower top is returned, another part enters dehydrogenation reactor dehydrogenation after heating up, and the unsaturated hydrocarbons obtained after dehydrogenation are used as anti-
Raw material is answered to return least significant end reactor after heating up.
7. type moving bed methanol hydrocarbon method is thermally integrated as claimed in claim 4, it is characterised in that during liquid in each reactor
Air speed is 1～5h-1, the regeneration temperature of regenerator is 500～650 DEG C, and regeneration pressure is 0.2～1.9MPaG, most top reactor
Pressure be 0.25～1.75MPaG, temperature is 320～520 DEG C, and the pressure of least significant end reactor is 0.20～1.73MPaG, temperature
Spend for 370～550 DEG C, the maximum pressure of latter reactor is not higher than the maximal pressure of previous reactor in every adjacent two reactor
Power, and the maximum pressure of most top reactor is not higher than, the minimum pressure of latter reactor is not higher than previous reactor most
Low-pressure, and the minimum pressure of most top reactor is not higher than, sub-thread circulating air is warming up to 320～480 DEG C, enters most top
The circulating air of reactor is warming up to 250～480 DEG C, and the circulating air into least significant end reactor is warming up to 270～490 DEG C, methanol
Raw material is successively warming up to 98～250 DEG C and 250～480 DEG C, absorbs tower bottom liquid and first mixes with methanol feedstock again with methanol feedstock one
Same cascade raising temperature, it is 5-20 that methanol spray flow rises flow-rate ratio with bottom gas phase, and pressure is 0.3～1.4 MPaG, takes off pentane
The tower top pressure of tower is 0.3～1.75MPaG, and tower reactor pressure is 0.35～1.8MPaG, the tower top pressure of fractionating column is 0.06～
1.6MPaG, tower reactor pressure is 0.07～1.8MpaG, and the C5 or C6～C7 for returning least significant end reactor realizes rising by heat exchange
Temperature, is warming up to 150～250 DEG C, and thermal source is the product or outer supplying heat source of reactor described in hydrocarbon synthesis step.
8. type moving bed methanol hydrocarbon method is thermally integrated as described in claim 5 or 6, it is characterised in that the liquid in each reactor
When air speed be 1～5h-1, the regeneration temperature of regenerator is 500～650 DEG C, and regeneration pressure is 0.2～1.9MPaG, and most top reacts
The pressure of device is 0.25～1.75MPaG, and temperature is 320～520 DEG C, and the pressure of least significant end reactor is 0.20～1.73MPaG,
Temperature is 370～550 DEG C, and the maximum pressure of latter reactor is not higher than the maximal pressure of previous reactor in every adjacent two reactor
Power, and the maximum pressure of most top reactor is not higher than, the minimum pressure of latter reactor is not higher than previous reactor most
Low-pressure, and the minimum pressure of most top reactor is not higher than, sub-thread circulating air is warming up to 320～480 DEG C, enters most top
The circulating air of reactor is warming up to 250～480 DEG C, and the circulating air into least significant end reactor is warming up to 270～490 DEG C, methanol
Raw material is successively warming up to 98～250 DEG C and 250～480 DEG C, absorbs tower bottom liquid and first mixes with methanol feedstock again with methanol feedstock one
Same cascade raising temperature, it is 5-20 that methanol spray flow rises flow-rate ratio with bottom gas phase, and pressure is 0.3～1.4 MPaG, takes off pentane
The tower top pressure of tower is 0.3～1.75MPaG, and tower reactor pressure is 0.35～1.8MPaG, the tower top pressure of debutanizing tower is 0.4～
1.6MPaG, tower reactor pressure is 0.45～1.65MPaG, and the C5 liquid phases for returning least significant end reactor are realized 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, returns the C3～C4 of most top reactor
Liquid phase first mixes again with methanol feedstock together cascade raising temperature with methanol feedstock.
9. type moving bed methanol hydrocarbon method is thermally integrated as described in any one in claim 1-7, it is characterised in that methanol
Raw material is divided into multiply after heating up, and in addition to wherein one enters most top reactor, other each stocks respectively enter other reactors, enter
Enter the methanol feedstock accounting of most top reactor more than the methanol feedstock into other each reactors.
10. type moving bed methanol hydrocarbon method is thermally integrated as claimed in claim 8, it is characterised in that methanol feedstock divides after heating up
For multiply, in addition to wherein one enters most top reactor, other each stocks respectively enter other reactors, enter the reaction of most top
The methanol feedstock accounting of device is more than the methanol feedstock into other each reactors.
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