CN107267187B - A method of clean gasoline is produced by oxygenatedchemicals - Google Patents
A method of clean gasoline is produced by oxygenatedchemicals Download PDFInfo
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- CN107267187B CN107267187B CN201610210706.XA CN201610210706A CN107267187B CN 107267187 B CN107267187 B CN 107267187B CN 201610210706 A CN201610210706 A CN 201610210706A CN 107267187 B CN107267187 B CN 107267187B
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Abstract
The invention discloses a kind of methods for producing clean gasoline by oxygenatedchemicals, this method comprises: the oxygenatedchemicals after preheating continuously to be contacted with molecular sieve catalyst in a fluidized bed reactor and carried out hydrocarbon reaction processed, the reclaimable catalyst of oil gas and carbon distribution rich in gasoline component is generated；After the reclaimable catalyst drawn from reactor is delivered to reclaimable catalyst receiver, reclaimable catalyst head tank is delivered to by locking hopper again, then fluid bed regenerator is delivered to from reclaimable catalyst head tank, and carry out coke burning regeneration under an oxygen-containing atmosphere in a regenerator, obtain regenerated catalyst；After regenerated catalyst is continuously drawn out to regenerated catalyst receiver from regenerator, then regenerated catalyst head tank is delivered to by locking hopper, and continuously returned in the reactor from regenerated catalyst head tank.Method of the invention is not only safe, but also can increase the pressure of reactor, improves unit capacity.
Description
Technical field
The present invention relates to a kind of methods for producing clean gasoline by oxygenatedchemicals.
Background technique
Oil and natural gas is widely used as fuel and chemical raw material.However, their reserves are limited and consumption
Increase year by year.World's coal reserves are much more more than oil and natural gas, and the exploitation of shale gas is in the ascendant, therefore, by coal
It sets out preparing synthetic gas with shale gas and natural gas, then methanol processed, finally producing clean gasoline is a feasible outlet.
Methanol is a kind of widely applied basic organic.The oil company Mobil in 1976 has carried out methanol in ZSM-5
It is converted into the reaction of hydrocarbon on molecular sieve catalyst, becomes minerals fuel such as natural gas and coal other than petroleum etc.
Gasoline uses.The oil company Mobil successively develops the methanol system of the different reactors type such as fixed bed, fluidized bed, multitube
Process of gasoline.Wherein fixed-bed process is industrialized in New Zealand.
Since the entire reaction process of methanol dewatered gasoline is all exothermic reaction, reaction generates heat and must remove, otherwise
Adiabatic heating will be thermally decomposed into CO and H more than methanol up to 580 DEG C or more2Temperature.United States Patent (USP) USP3928483 and
USP3931349 is that the patent of hydrocarbon compound is produced in the methanol conversion of the oil company Mobil alerting bulletin, which adopts
With fixed bed two-stage method conversion process, wherein first segment is to convert methanol dehydration to dimethyl ether, then by two in second segment
Methyl ether and the complete carbinol mixture of water and unreacted generate gasoline under the action of ZSM-5 molecular sieve catalyst.Fixed bed reaction
The advantages of device technique, is that conversion ratio is relatively high, technical maturity, the disadvantage is that technical process and the device is complicated, energy consumption is high, investment is high.
United States Patent (USP) USP4579999 discloses the technology that a kind of methanol is converted into gasoline component after two reactor,
Methanol is converted to C2-C4 alkene and C5+ hydrocarbon component in the fluidized-bed reactor equipped with ZSM-5 molecular sieve catalyst first.
After refrigerated separation, C2-C4 olefin component, which enters in the second segment reactor equipped with olefinic polymerization ZSM-5 catalyst, to be carried out instead
It answers, is further converted into gasoline component.United States Patent (USP) USP4689205 discloses the skill that hydro carbons is produced in a kind of conversion of methanol multi-stage
Art, the technology and the USP4579999 technology announced of the patent disclosure are substantially similar, the difference is that first in the patented technology
Duan Caiyong fluidized-bed reactor.
United States Patent (USP) USP4788369 discloses fixed bed preparing gasoline by methanol technique, and proposes the C3-C4 hydrocarbon that will be isolated
Class first exchanges heat with unstripped gas, then squeezes into gasoline synthesis reactor through pump pressurization, plays circulating air cooling effect.
Chinese patent CN1923770A discloses the technique that a kind of methanol by one-step method produces hydrocarbon products, and this method is using solid
Fixed bed reactor, methanol on acid Si-Al zeolite molecular sieve catalyst through intermolecular or intramolecular dehydration, generate methylene or
The intermediate products such as dimethyl ether, these intermediate products acidic molecular sieve effect under, further occurrence carbochain increase, polymerization, cyclisation,
The reaction such as hydrogen migration, ultimately generates C1-C12 hydrocarbon products.
Chinese patent CN101775310A discloses a kind of method of producing gasoline by fluidized bed process methanol, this method
Using fluidized-bed reactor, methanol obtains hydro carbons mixed component under containing zirconium or iron-containing ZSM-5 molecular sieve catalyst action,
Product after gas-liquid separation, fluidized-bed reactor is sent into after overcompression and carries out lighter hydrocarbons circulation, lighter hydrocarbons circulation pair by light hydrocarbon gas
It improves reaction speed and yield of gasoline is advantageous.Using fluidized bed preparing gasoline by methanol technique, the removal of reaction heat is convenient, gasoline quality
It improves, but compared with fixed bed, yield of gasoline is relatively low.
In the technology of existing preparing gasoline by methanol, the catalyst of preparing gasoline by methanol mainly uses various modifications, unmodified
ZSM-5 molecular sieve.The patents such as United States Patent (USP) USP3911041, USP4049573, USP4100219 disclose using phosphorus, magnesium,
The modified ZSM-5 molecular sieve catalyst of silicon or alkali metal element by preparing low carbon olefinic hydrocarbon with methanol reaction.United States Patent (USP)
The molecular sieve that the catalyst for the preparing gasoline by methanol mentioned in USP4402867 and USP4480145 uses is deposit amorphous silicon
ZSM-5, the stability of catalyst can be improved in such modification.
The preparing gasoline by methanol catalyst that United States Patent (USP) US4402867 is announced is that the modified ZSM-5 molecular sieve of amorphous silicon is urged
Agent, the sial the mass ratio of the material of ZSM-5 molecular sieve are 12, and the load capacity of amorphous silicon is at least 0.3%.Methanol is in Si modification
ZSM-5 on convert after the obtained composition of gasoline products it is as follows: the alkene of 50-75%, the aromatic hydrocarbons of 15-30%, 20% or so
Alkane.ZSM-5 molecular sieve is modified through amorphous silicon, and the coking deactivation rate of catalyst significantly reduces, and urges to extend
The service life of agent.Although this catalyst has preferable stability, the olefin(e) centent in gasoline products is higher.
Preparing gasoline by methanol catalyst disclosed in the patent EP0127959A2 of Mobil Corporation includes two kinds of catalyst, is existed first
The intermediate products rich in alkene are converted by methanol on the catalyst of active component of ZSM-48, then intermediate products are with ZSM-
5 for active component catalyst on be superimposed as gasoline.
Chinese patent CN102049293A discloses a kind of modified ZSM-5/AlPO4- 5 binary structure zeolites and change containing this
Property ZSM-5/AlPO4The method of the catalyst of -5 binary structure zeolites and the preparing gasoline by methanol using the catalyst.The modification
ZSM-5/AlPO4- 5 binary structure zeolites contain ZSM-5/AlPO4- 5 binary structure zeolites and it is supported on the ZSM-5/AlPO4-5
Phosphorus on binary structure zeolite and at least one transition metal, when catalyst made of modified molecular screen is used for preparing gasoline by methanol,
Can in high yield, obtain gasoline with high selectivity.But the patent relates generally to the improvement to catalyst in preparing gasoline by methanol technique,
The concrete operations and condition of preparing gasoline by methanol are not particularly limited.
Chinese patent CN102049292A discloses a kind of preparing gasoline by methanol catalyst and the methanol system using the catalyst
The method of gasoline, the catalyst contain molecular sieve, binder and clay with MFI structure, and using the weight of catalyst as base
Standard, the content of the molecular sieve with MFI structure are 5-50 weight %, and the content of binder is 5-50 weight % in terms of oxide,
The content of clay is 5-90 weight %, and laser particle size method measures the average particle diameter of the molecular sieve with MFI structure
D50No more than 5 microns, the catalyst be used for preparing gasoline by methanol when, can in high yield, obtain gasoline with high selectivity.But the patent
The improvement to catalyst in preparing gasoline by methanol technique is related generally to, the concrete operations and condition to preparing gasoline by methanol do not limit especially
It is fixed.
Summarize existing patent and non-patent literature it can be concluded that, fixed-bed process is multiple fixed bed reactors circulation behaviour
Make, relatively frequently in reaction and regenerative process conversion；Each reactor of the process is intermittently operated, therefore, continuous to reach
Feed operation, multiple reactor are used simultaneously；The major defect of the process is reactor operating condition in oxidation and reducing environment intermediate frequency
Numerous variation, and the temperature change of reactor is very complicated.Since preparing gasoline by methanol belongs to strong exothermal reaction, and fluidized-bed reaction utensil
Have Chuan Re ﹑ mass transfer effect good, Temperature Distribution is stablized when heating and cooling, and gasoline quality is high, and catalyst property is constant, good effect of heat exchange with
And the low advantage of investment, so, it is more advantageous using fluidized-bed reactor in preparing gasoline by methanol reaction process.
To reduce investment, improving the continuity of technique and the stability of catalyst activity, a kind of possible solution
It is that the reaction that oxygenatedchemicals produces clean gasoline is carried out using the technique similar to fluid catalytic cracking (FCC), that is, uses
One reactor and a regenerator simultaneously realize successive reaction-regenerative operation.But if there can be two weights using this method
Big problem needs to solve: first, due to being hydro carbons atmosphere in reactor, and in regenerator it is oxygen-containing atmosphere, reactor and regeneration
The air-flow of device must be well isolated to ensure process safety；Second, when using a reactor, to reach and fixed bed
The identical treating capacity of technique, it is necessary to increase the size of reactor, this equally will increase investment and cost.
Summary of the invention
The object of the present invention is to provide a kind of method for producing clean gasoline by oxygenatedchemicals, this method can overcome existing
On the one hand the problem of with the presence of technology, can ensure the safety of technique, even further aspect is can be in same reactor
The treating capacity of device is improved in the case where size.
To achieve the goals above, the present invention provides a kind of method for producing clean gasoline by oxygenatedchemicals, this method
It include: continuously to contact the oxygenatedchemicals after preheating with molecular sieve catalyst in a fluidized bed reactor and to carry out hydrocarbon processed anti-
It answers, generates the reclaimable catalyst of oil gas and carbon distribution rich in gasoline component；Make oil gas and reclaimable catalyst rich in gasoline component
Oil gas after separation is sent into product separation and recovery system, reclaimable catalyst is continuously drawn from reactor by separation；It will be from anti-
Answer device draw reclaimable catalyst be delivered to reclaimable catalyst receiver after, then by locking hopper be delivered to reclaimable catalyst into
Then batch can is delivered to fluid bed regenerator from reclaimable catalyst head tank, and burnt under an oxygen-containing atmosphere in a regenerator
Coke regeneration, obtains regenerated catalyst；After regenerated catalyst is continuously drawn out to regenerated catalyst receiver from regenerator, then lead to
It crosses locking hopper and is delivered to regenerated catalyst head tank, and continuously return to the reactor from regenerated catalyst head tank
In.
Preferably, this method further include: by the C isolated through the product separation and recovery system1-C4Lighter hydrocarbons are continuously
Back to carrying out the hydrocarbon reaction processed in the fluidized-bed reactor.
Preferably, this method comprises: drawing one from the fluidized-bed reactor or the reclaimable catalyst receiver
Divide reclaimable catalyst；The part reclaimable catalyst of extraction is returned into the fluidisation directly or after external warmer reduces temperature
Bed reactor in, or be transported to mix in the regenerated catalyst head tank with regenerated catalyst after return to the fluidized bed
In reactor.
Preferably, the oxygenatedchemicals is selected from least one of alcohols, ethers and esters.
Preferably, the oxygenatedchemicals is methanol and/or dimethyl ether.
Preferably, the fluidized-bed reactor is bubbling fluidized bed reactor or turbulent fluidized bed reactor.
Preferably, the fluidized-bed reactor has the internal baffle of layered arrangement, and the internal baffle is board-like grid,
The board-like every 20~150cm of grid installs one layer, from the bottom surface of bottom board-like grid between the top surface of board-like grid topmost
Distance be reactor inner space total height 20%~70%.
Preferably, separate oil gas and reclaimable catalyst rich in gasoline component by filter, the filter is gold
Belong to sintered porous material and/or ceramic porous material, 2 μm of particle filtering precision of filter are 99.9%.
Preferably, the molecular sieve catalyst includes MFI-type molecular sieve, metal component, carrier and binder.
Preferably, the condition of the hydrocarbon reaction processed are as follows: reaction temperature be 250~530 DEG C, reaction pressure be 0.1~
4.0MPa, volume space velocity are 0.5~10 hour-1。
Preferably, the condition of described point of hydrocarbon reaction processed are as follows: reaction temperature be 340~460 DEG C, reaction pressure be 0.5~
2.5MPa, volume space velocity are 1~5 hour-1。
Preferably, the condition of the coke burning regeneration are as follows: temperature is 500~650 DEG C, and pressure is 0.1~3.0MPa, catalyst
Residence time is 5~60 minutes；The oxygen-containing atmosphere is using air, the diluted air of nitrogen or oxygen rich gas as stream
Change medium.
Preferably, this method further include: the reaction pressure in control reactor is at least higher than the regeneration pressure in regenerator
0.3MPa。
Preferably, the fluidized-bed reactor, regenerator, regenerated catalyst head tank and regenerated catalyst receiver are optional
Ground is equipped with interior heat collector and/or external warmer.
It preferably, is 0.05~20 heavy % into total phosphorus content of the catalyst of the feed zone of the fluidized-bed reactor.
Oxygenatedchemicals of the invention produces the method for clean gasoline compared with the conventional method, and major advantage is as follows:
1, the reclaimable catalyst of carbon distribution continuously can be transferred to regenerator from reactor and be regenerated, fluidized-bed reactor
Middle catalyst activity kept stable, this is different from existing method；
2, hydrocarbon reaction institute's calorific requirement processed is directly transmitted to reactant by the regenerated catalyst of heat, and the strong mixing of gas-solid avoids
Such as the appearance of hot spot in fixed-bed operation；
3, importantly, reactor hydro carbons atmosphere can be with the coke burning regeneration of regenerator by the use of locking hopper
Oxygen-containing atmosphere be well isolated from, it can be ensured that the safe operation of technique；
4, moreover, by the use of locking hopper, the operation of reactor and regenerator can neatly be adjusted
Pressure, that is to say, that the operating pressure of reactor can be improved in the case where keeping regenerator normal pressure or low pressure operates, from
And the treating capacity of device can be improved in the case where not increasing reactor size, improve the yield of gasoline, and operating pressure
The raising for being also beneficial to gasoline yield is improved in a certain range.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 includes a kind of flow diagram of specific embodiment of the method for the present invention, also includes the one of the method for the present invention
The structural schematic diagram of kind the used device of specific embodiment；
Fig. 2 includes the flow diagram of another specific embodiment of the method for the present invention, also including the method for the present invention
Another structural schematic diagram of the used device of specific embodiment；
Fig. 3 is the top view and main view of a kind of specific embodiment of the internal baffle (i.e. board-like grid) in Fig. 2.
Description of symbols
1 fluidized-bed reactor, 2 fluid bed regenerator, 3 reclaimable catalyst receiver
4 locking hopper, 5 reclaimable catalyst head tank, 6 regenerated catalyst receiver
7 pipeline, 8 pipeline, 9 pipeline, 10 pipeline, 11 pipeline, 12 pipeline
13 pipeline, 14 pipeline, 15 control valve, 16 control valve, 17 control valve
18 control valve, 19 control valve, 20 control valve, 21 pipeline, 22 pipeline
23 pipeline, 24 pipeline, 25 pipeline, 26 pipeline, 27 pipeline
28 pipeline, 29 pipeline, 30 pipeline, 31 pipeline
The board-like grid of 40 regenerated catalyst head tank, 41 pipeline, 42 pipeline 50
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of method for producing clean gasoline by oxygenatedchemicals, this method comprises: continuously will preheating
Oxygenatedchemicals afterwards contacts with molecular sieve catalyst in a fluidized bed reactor and carries out hydrocarbon reaction processed, generates and is rich in gasoline group
The reclaimable catalyst of the oil gas and carbon distribution that divide；Make oil gas and reclaimable catalyst separation rich in gasoline component, by the oil after separation
Pneumatic transmission enters product separation and recovery system, and reclaimable catalyst is continuously drawn from reactor；It to be generated is urged what is drawn from reactor
After agent is delivered to reclaimable catalyst receiver, then reclaimable catalyst head tank is delivered to by locking hopper, then to be generated
Catalyst feed tank is delivered to fluid bed regenerator, and carries out coke burning regeneration under an oxygen-containing atmosphere in a regenerator, is regenerated
Catalyst；After regenerated catalyst is continuously drawn out to regenerated catalyst receiver from regenerator, then pass through locking hopper conveying
To regenerated catalyst head tank, and continuously returned in the reactor from regenerated catalyst head tank.
According to the present invention, clean gasoline generally refers to the lower gasoline of sulfur content, and the present invention takes oxygenatedchemicals to produce
The sulfur content of gasoline, gained gasoline is very low, therefore is properly termed as clean gasoline, and the composition of gasoline mainly includes C5-C12Hydrocarbon
Class.
According to the present invention, in order to make full use of raw material, this method can also include: will be through the product separation and recovery system
Isolated C1-C4Lighter hydrocarbons, which continuously return in the fluidized-bed reactor, carries out the hydrocarbon reaction processed.
A kind of specific embodiment according to the present invention can be from the fluidisation in order to control the temperature of regenerated catalyst
A part of reclaimable catalyst is drawn in bed reactor or the reclaimable catalyst receiver；By the part reclaimable catalyst of extraction
Back in the fluidized-bed reactor directly or after external warmer reduces temperature, or be transported to the regenerated catalyst into
It is returned in the fluidized-bed reactor after being mixed in batch can with regenerated catalyst.The external warmer is those skilled in the art
Known, inside can be set coil pipe, bend pipe etc. and take thermal, for reducing the temperature for flowing through reclaimable catalyst therein.
According to the present invention, the oxygenatedchemicals can be that can be selected from least one of alcohols, ethers and esters
Single low molecular weight alcohols or alcohol-based mixtures can also be the mixture of alcohols and dimethyl ether and/or water, wherein low molecule
Alcohols can be C1-C4Monohydroxy alcohols or C2-C4Dihydroxy alcohols, preferably monohydroxy alcohols, more preferably methanol and/or
Dimethyl ether.
According to the present invention, the fluidized-bed reactor is known to those skilled in the art, can be bubbling
Fluidized-bed reactor or turbulent fluidized bed reactor, or other industrial common streams such as fluidizing fluid-bed reactor
Fluidized bed reactor.The fluidized-bed reactor is preferably bubbling fluidized bed reactor or turbulent fluidized bed reactor, more
Preferably bubbling fluidized bed reactor.
A kind of specific embodiment according to the present invention, the fluidized-bed reactor can have the built-in gear of layered arrangement
Plate makes oil gas and/or catalyst with a kind of shape of flat-pushing streaming for preventing the non-uniform mixed flow of oil gas and/or catalyst
State is reacted by reactor, to improve the conversion ratio of oxygenatedchemicals and the selectivity of required clean gasoline；It is described built-in
Baffle can be board-like grid, and board-like grid can be one layer of 20~150cm installing every, and preferably every 50~100cm installs one layer, from most
The bottom surface of board-like grid to the distance between top surface of board-like grid topmost can be reactor inner space total height below
5%~80%, preferably 20%~70%, further preferably 30%~50%；The material of the board-like grid can be selected from
Catalytic cracking regenerator gas distributor or the used material of wide bore distribution plate, grille-like can be the shapes such as waveform, lattice
The aperture or macropore passed through for catalyst and gas rule can be evenly arranged on grid.
In order to separate the oil gas and reclaimable catalyst that generate after reacting in reactor, traditional whirlwind can be used
Separator, this be it is well-known to those skilled in the art, the present invention to this without detailed description.
A kind of preferred embodiment according to the present invention can also make the oil rich in gasoline component by filter
Gas and reclaimable catalyst separation, wherein the filter can be prepared using porous material, for example, can be more for metal sintering
Porous materials and/or ceramic porous material；2 μm of particle filtering precision of the filter can reach 99.9%, it is preferable that the mistake
1.2 μm of particle filtering precision of filter can reach 99.9%；Further, it is possible to use blowback air is clear to filter progress blowback
Manage filter cake；Blowback air can be for selected from one or more of gas containing hydrocarbon, dry gas, nitrogen and vapor.
According to the present invention, routine known to those skilled in the art can be used in the molecular sieve catalyst
Catalyst, the present invention are not particularly limited it.In order to meet the operation requirement of fluidized-bed reactor and regenerator, described point
The shape of sub- sieve catalyst is generally microspheroidal.The molecular sieve catalyst typically contains active component and carrier.According to this hair
Bright a kind of specific embodiment, for example, wherein the molecular sieve catalyst may include MFI-type molecular sieve, metal component, load
Body and binder.Wherein the skeleton component of MFI-type molecular sieve can be silicon, aluminium and/or phosphorus, and molecular sieve content can account for catalyst
The 10%-50% of total weight；Metal component can for selected from zinc, iron, zirconium, gallium, silver, molybdenum, copper, nickel, manganese, chromium, platinum, ruthenium, tungsten and
At least one of metal components such as vanadium can exist with metallic forms, can also exist with metal oxide form, metal group
The total load amount (based on metallic state) divided can be the 0.5%-5% of total catalyst weight；Carrier can be kaolin and intend thin
One or both of diaspore, content can account for the 30%-70% of total catalyst weight；Binder can be molten selected from aluminium
One or more of glue, silica solution and phosphorus Aluminum sol, content can account for the 8%-25% of total catalyst weight.Preferably, institute
The catalyst stated is modified ZSM-5 molecular sieve catalyst.
According to the present invention, hydrocarbon reaction processed refers to that oxygenatedchemicals, which is carried out catalysis, produces the anti-of the hydro carbons including gasoline component
It answers, the process conditions of hydrocarbon reaction processed can be process conditions known to those skilled in the art, can also be specifically:
Reaction temperature is 250~530 DEG C, and reaction pressure is 0.1~4.0MPa, and volume space velocity is 0.5~10 hour-1.Preferably, described
The condition of hydrocarbon reaction processed are as follows: reaction temperature is 340~460 DEG C, and reaction pressure is 0.5~2.5MPa, and volume space velocity is 1~5 small
When-1。
According to the present invention, the condition of the coke burning regeneration is well-known to those skilled in the art, and the present invention does not have it
Special limitation.For example, the condition of the coke burning regeneration can be with are as follows: temperature is 500~650 DEG C, and pressure is 0.1~3.0MPa,
Catalyst residence times are 5~60 minutes；The oxygen-containing atmosphere can be for air, the diluted air of nitrogen or oxygen-enriched
For gas as fluidizing agent, preferred regenerator fluidizing agent is air or the diluted air of nitrogen, it may be necessary to be supplemented
Fuel gas such as oil refinery dry gas is to improve the temperature of catalyst bed in regenerator.
It according to the present invention, can be 0.05% into total phosphorus content of the catalyst of the feed zone of the fluidized-bed reactor
~20 heavy %, preferably 0.05%~8 heavy %.The catalyst of the feed zone into the fluidized-bed reactor can come from
Regenerated catalyst head tank can be from reclaimable catalyst receiver, wherein in the regenerated catalyst head tank
Catalyst can be regenerated catalyst, be also possible to the mixed catalyst of regenerated catalyst and reclaimable catalyst.
In the fluidized-bed process method for producing clean gasoline by oxygenatedchemicals, when only using a reactor, and
When reactor operates at atmospheric or low pressure as regenerator, to reach processing identical with fixed bed or moving bed process
Amount, it is necessary to increase the size of reactor, this equally will increase investment and cost.To solve this problem, the solution that the present invention uses
Certainly method is: improving the operating pressure of the reactor to improve the treating capacity of device.Due to the present invention in reactor and again
It is provided with locking hopper in catalyst stream channel between raw device, so that the operating pressure of control reactor is higher than regenerator
Operating pressure becomes possibility.
Therefore, according to a preferred embodiment of the present invention, provided according to the present invention by oxygenatedchemicals system
It takes in the method for clean gasoline, the reaction pressure controlled in reactor is 0.3MPa at least higher than the regeneration pressure in regenerator.
According to the present invention, the locking hopper can make low pressure of the catalyst from the high pressure hydrocarbon environment of reactor to regenerator
Oxygen environment, and safely and effectively shifted from the low pressure oxygen environment of regenerator to the high pressure hydrocarbon environment of reactor.That is,
By using locking hopper, the oxygen-containing atmosphere of the hydro carbons atmosphere of reactor and the coke burning regeneration of regenerator on the one hand can be made fine
Ground isolation, it is ensured that the on the other hand safety of present invention process method can neatly regulate and control the operation of reactor and regenerator
Pressure can be improved the operating pressure of reactor in the case where not improving regenerator operation pressure especially to improve device
Treating capacity.
Locking hopper of the present invention is a kind of same material stream can be made in different atmosphere (such as oxidizing atmosphere and also
Primordial Qi atmosphere) between and/or different pressure environments (such as from high pressure to low pressure, or otherwise) between the device that switches over,
Its structure is known to correlative technology field those of skill in the art.Catalyst granules is completed from high pressure hydrocarbon ring by locking hopper
Transfer from border to low pressure oxygen environment the step of may include: 1, oxygen remaining in the locking hopper emptied is blown using hot nitrogen
It sweeps in regenerator；2, nitrogen is purged away from locking hopper using hydrogen；3, using hydrogen to the locking hopper emptied
Pressurization；4, the reclaimable catalyst from reclaimable catalyst receiver is filled into the locking hopper emptied；5, pass through discharge
The hydrogen to pressurize in locking hopper depressurizes the locking hopper of filling；6, hydrogen is blown from the locking hopper of filling with hot nitrogen
It scans out；7, by reclaimable catalyst from the lockhopper of filling to reclaimable catalyst head tank.It is completed by locking hopper
The step of transfer of the catalyst granules from low pressure oxygen environment to high pressure hydrocarbon environment may include: 1, using hot nitrogen by oxygen from filling
The locking hopper of regenerated catalyst is purged in regenerator；2, nitrogen is purged away from locking hopper using hydrogen；3, it uses
Hydrogen pressurizes to the locking hopper of filling；4, regenerated catalyst is fed from the lockhopper of filling to regenerated catalyst
Tank；5, by the hydrogen in discharge pressurization locking hopper, the locking hopper emptied is depressurized；6, with hot nitrogen by hydrogen from
The locking hopper of emptying purges away；7, regenerated catalyst is filled into the locking hopper emptied from Regenerator receiver.
A kind of specific embodiment according to the present invention, the locking hopper can only use one, i.e. reclaimable catalyst
Conveyed with regenerated catalyst using the same locking hopper, also can according to need using different locking hoppers respectively into
The conveying of the row reclaimable catalyst and the regenerated catalyst, the grade variations all belong to the scope of protection of the present invention.
A kind of specific embodiment according to the present invention is received by setting reclaimable catalyst receiver, regenerated catalyst
Device, reclaimable catalyst head tank and regenerated catalyst head tank can continuously convey the reclaimable catalyst drawn from reactor
Reclaimable catalyst head tank is delivered to by locking hopper again after to reclaimable catalyst receiver, is then fed from reclaimable catalyst
Tank is continuously delivered to regenerator, and the regenerated catalyst that drawn from regenerator can be continuously delivered to regenerated catalyst and connect
Regenerated catalyst head tank is delivered to by locking hopper again after receiving device, is then continuously delivered to from regenerated catalyst head tank
Reactor, to realize being carried out continuously for reaction process and regenerative process.In reclaimable catalyst receiver, it can be incited somebody to action with vapor
Oil gas contained by reclaimable catalyst logistics is stripped to the loss in the reactor to avoid material；In regenerated catalyst receiver
In, it so that catalyst in receiver is kept fluidisation with nitrogen or other non-oxidising gas, on the other hand by regenerated catalyst
Oxygen contained by logistics is stripped in the regenerator；Similarly, in reclaimable catalyst head tank, air or nitrogen can be used
As the promotion gas for promoting catalyst, to keep catalyst in head tank to be in fluidized state.
Since the regeneration that oxygenatedchemicals produces clean gasoline and reclaimable catalyst is all exothermic reactions, the fluidized bed is anti-
Answer device, regenerator, regenerated catalyst head tank and regenerated catalyst receiver that interior heat collector can be optionally set and/or taken outside
Hot device, such as one or more interior heat collectors, this is well-known to those skilled in the art.The interior heat collector can be coil pipe
Or the types such as bend pipe carry out reactor to take heat by liquid such as the water of internal flow or carbon tetrachloride, it is other industrial common
Interior heat collector and external warmer, the present invention can also apply.
Below in conjunction with attached drawing, a specific embodiment of the invention is further described.
The process for the method that the oxygenatedchemicals that Fig. 1 is provided produces clean gasoline is as follows:
As shown in Figure 1, the oxygen-containing compound material after preheating enters fluidized-bed reactor by feed distributor through pipeline 7
1, the top of fluidized-bed reactor 1 is delivered to after contacting, gasify and reacting with the regenerated catalyst of the activity recovery from pipeline 28
Portion.At 1 top of fluidized-bed reactor, reaction oil gas and a small amount of catalyst granules are separated through gas-solid separation equipment, catalyst granules
Back to fluidized-bed reactor bed, the product after separation enters subsequent separation system through pipeline 8 and carries out product separation.Fluidized bed
The reclaimable catalyst of the carbon distribution on reactor top enters reclaimable catalyst receiver 3 through pipeline 21.In reclaimable catalyst receiver 3
Catalyst after the reaction oil gas of carrying is stripped off in the vapor from pipeline 11, successively flowed by pipeline 22 and control valve 15
Enter locking hopper 4, the oil gas being stripped off is sent into fluidized-bed reactor 1 through pipeline 31.
After reclaimable catalyst undergoes a series of processes such as purgings, boosting, filling and decompression in locking hopper 4, successively pass through
Pipeline 23 and control valve 18 flow into reclaimable catalyst head tank 5, then successively through pipeline 24 and control valve 19 and from pipeline 12
Air mixing after, the middle and upper part of fluid bed regenerator 2 is promoted to through pipeline 25.Reclaimable catalyst is in fluid bed regenerator 2
Concurrent raw burn coke reaction is contacted, with the oxygen-containing gas from pipeline 9 to restore catalyst activity.Regenerated flue gas is through pipeline 10 by again
It is discharged at the top of raw device 2 and is exchanged heat and be vented after catalyst powder dust recovery system.Regenerated catalyst is through control valve 20 and from pipe
After the nitrogen mixing of line 13, it is promoted to regenerated catalyst receiver 6 through pipeline 26, the catalyst in regenerated catalyst receiver 6
After the nitrogen from pipeline 14 fluidizes and the oxygen of catalyst carrying is stripped off, successively closed through pipeline 27 and the inflow of control valve 17
Lock hopper 4.
After regenerated catalyst undergoes a series of processes such as purgings, decompression, filling and boosting in locking hopper 4, successively pass through
Control valve 16 and pipeline 28 first flow into regenerated catalyst head tank 40, then are flowed into fluidized-bed reactor 1 by pipeline 42, with
From the raw material contact and reaction of pipeline 7.
Fig. 2 is a kind of further embodiment of the invention, and process raw material and is urged on the basis of Fig. 1
Agent is contacted and is reacted, the top view and main view of board-like grid 50 in the fluidized-bed reactor 1 for being disposed with board-like grid 50
As shown in Figure 3.
Not therefore embodiment below will be illustrated in conjunction with specific embodiment of the attached drawing to invention, but the present invention
And it is any way limited.
The preparation method of the used catalyst of the embodiment of the present invention includes: by 500g (NH4)2SO4It is dissolved in 10000g water,
1000g (butt) crystallization product ZSM-5 molecular sieve (production of Chang Ling catalyst plant, SiO are added into this solution2/Al2O3=30),
After 90 DEG C of exchange 1h, filter cake is filtered to obtain；By 86g (NH4)2HPO4It is dissolved in 800g water, is mixed with dipping and dries with filter cake；Again plus
Enter 76gFe (NO3)3·9H2O and 44gGa (NO3)3·9H2O is dissolved in 1000g water, is mixed with dipping drying for 24 hours with above-mentioned sample；
Gained sample 560 DEG C calcination process 2 hours, products therefrom, that is, molecular sieve catalyst provided by the invention, the catalyst trade mark is
MGA-G。
The embodiment of the present invention calculates product distribution and hydro carbons using gas chromatography measurement gas products and liquid product
Distribution counts for convenience, hydrogen is belonged in hydro carbons.
The embodiment of the present invention measures the octane number of gasoline using RIPP 85-90 test method.
RIPP test method of the invention is selected from " petrochemical egineering analysis method (RIPP test methods) ", and Yang Cui is waited surely and compiled,
Science Press, 1990.
Embodiment 1-5
Process and device carry out embodiment 1-5 as shown in Figure 2, reaction raw materials, catalyst, reaction condition and product yield
It is listed in table 1.
As it can be seen from table 1 carrying out hydrocarbon reaction processed using the method for the present invention produces gasoline, it can not only be by the hydrocarbon ring of reaction
Border and the isolation of regenerated oxygen environment, it is ensured that the safety of technique improves the place of device furthermore it is also possible to increase the pressure of reaction
Reason amount, and can be seen that the increase with reaction pressure from product distribution and distribution of hydrocarbon, due to the increase for the treatment of capacity,
Hydro carbons yield changes under little result, and the yield of gasoline increases very much, and operating pressure improves also have in a certain range
Conducive to the raising of gasoline yield.
Table 1 is reaction raw materials, catalyst, reaction condition and the product yield of embodiment 1-5
Claims (14)
1. a kind of method that clean gasoline is produced by oxygenatedchemicals, this method comprises:
The oxygenatedchemicals after preheating is contacted with molecular sieve catalyst in a fluidized bed reactor continuously and to carry out hydrocarbon processed anti-
It answers, generates the reclaimable catalyst of oil gas and carbon distribution rich in gasoline component；
Make oil gas and reclaimable catalyst separation rich in gasoline component, the oil gas after separation be sent into product separation and recovery system,
Reclaimable catalyst is continuously drawn from reactor；
After the reclaimable catalyst drawn from reactor is delivered to reclaimable catalyst receiver, then by locking hopper be delivered to
Raw catalyst feed tank, is then delivered to fluid bed regenerator from reclaimable catalyst head tank, and in a regenerator oxygenous
Coke burning regeneration is carried out under atmosphere, obtains regenerated catalyst；
After regenerated catalyst is continuously drawn out to regenerated catalyst receiver from regenerator, then it is delivered to again by locking hopper
Raw catalyst feed tank, and continuously returned in the reactor from regenerated catalyst head tank；It controls anti-in reactor
Answer at least high 0.3MPa of the regeneration pressure in pressure ratio regenerator.
2. according to the method described in claim 1, this method further include: will be isolated through the product separation and recovery system
C1-C4Lighter hydrocarbons, which continuously return in the fluidized-bed reactor, carries out the hydrocarbon reaction processed.
3. according to the method described in claim 1, this method further include: from the fluidized-bed reactor or the reclaimable catalyst
A part of reclaimable catalyst is drawn in receiver；The part reclaimable catalyst of extraction directly or through external warmer is reduced into temperature
Afterwards back in the fluidized-bed reactor, or after being transported to and being mixed in the regenerated catalyst head tank with regenerated catalyst
Back in the fluidized-bed reactor.
4. according to the method described in claim 1, wherein, the oxygenatedchemicals be in alcohols, ethers and esters extremely
Few one kind.
5. according to the method described in claim 4, wherein, the oxygenatedchemicals is methanol and/or dimethyl ether.
6. according to the method described in claim 1, wherein, the fluidized-bed reactor is bubbling fluidized bed reactor or turbulent flow
Fluidized-bed reactor.
7. according to the method described in claim 1, wherein, the fluidized-bed reactor has the internal baffle of layered arrangement, institute
Stating internal baffle is board-like grid, and the every 20~150cm of board-like grid installs one layer, from the bottom surface of bottom board-like grid to most upper
The distance between top surface of panel type grid is the 20%~70% of reactor inner space total height.
8. according to the method described in claim 1, wherein, making oil gas and reclaimable catalyst rich in gasoline component by filter
Separation, the filter are metal sintering porous material and/or ceramic porous material, and 2 μm of particle filtering precision of filter are
99.9%.
9. according to the method described in claim 1, wherein, the molecular sieve catalyst include MFI-type molecular sieve, metal component,
Carrier and binder.
10. according to the method described in claim 1, wherein, the condition of the hydrocarbon reaction processed are as follows: reaction temperature is 250~530
DEG C, reaction pressure is 0.1~4.0MPa, and volume space velocity is 0.5~10 hour-1。
11. according to the method described in claim 10, wherein, the condition of the hydrocarbon reaction processed are as follows: reaction temperature is 340~460
DEG C, reaction pressure is 0.5~2.5MPa, and volume space velocity is 1~5 hour-1。
12. according to the method described in claim 1, wherein, the condition of the coke burning regeneration are as follows: temperature is 500~650 DEG C, pressure
Power is 0.1~3.0MPa, and catalyst residence times are 5~60 minutes；The oxygen-containing atmosphere is with air, the diluted sky of nitrogen
Gas or oxygen rich gas are as fluidizing agent.
13. according to the method described in claim 1, wherein, the fluidized-bed reactor, regenerator, regenerated catalyst head tank
Interior heat collector and/or external warmer are optionally provided with regenerated catalyst receiver.
14. according to the method described in claim 1, wherein, into the feed zone of the fluidized-bed reactor catalyst it is total
Phosphorus content is 0.05~20 heavy %.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1952060A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Production process of producing cleaning gasoline |
| CN101658799A (en) * | 2009-09-14 | 2010-03-03 | 洛阳瑞泽石化工程有限公司 | Continuous catalyst regeneration method and device thereof |
| CN105018129A (en) * | 2014-04-18 | 2015-11-04 | 中石化洛阳工程有限公司 | Device and method for producing gasoline from methyl alcohol by fluidized bed |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1952060A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Production process of producing cleaning gasoline |
| CN101658799A (en) * | 2009-09-14 | 2010-03-03 | 洛阳瑞泽石化工程有限公司 | Continuous catalyst regeneration method and device thereof |
| CN105018129A (en) * | 2014-04-18 | 2015-11-04 | 中石化洛阳工程有限公司 | Device and method for producing gasoline from methyl alcohol by fluidized bed |
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