CN105985793B

CN105985793B - A kind of method that oxygen containing feed is transformed into gasoline

Info

Publication number: CN105985793B
Application number: CN201510043287.0A
Authority: CN
Inventors: 郭湘波; 杨克勇; 宗保宁
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2015-01-28
Filing date: 2015-01-28
Publication date: 2018-02-23
Anticipated expiration: 2035-01-28
Also published as: CN105985793A

Abstract

The invention discloses a kind of method that oxygen containing feed is transformed into gasoline, including making oxygen containing feed and the catalyst containing molecular sieve haptoreaction in the reaction region, obtain the mixture containing gasoline, oxygen containing feed is methanol and/or dimethyl ether, wherein, reaction zone includes raw material area, product area and catalytic reaction zone, catalytic reaction zone is to be circular layout and along the axially extending of reaction zone, oxygen containing feed is located in raw material area, catalyst is located in catalytic reaction zone, raw material area and product area are abutted by catalytic reaction zone, oxygen containing feed in raw material area enters catalytic reaction zone and molecular sieve haptoreaction, the obtained mixture containing gasoline enters product area.Compared with using the technique of fixed bed reactors, the system pressure drop of this method substantially reduces, and reduces operation energy consumption；The regeneration of catalyst can be easily realized in reactor simultaneously.This method can obtain the feed stock conversion and gasoline selective of even more high suitable with the technique using fixed bed reactors.

Description

A kind of method that oxygen containing feed is transformed into gasoline

Technical field

The present invention relates to a kind of method that oxygen containing feed is transformed into gasoline.

Background technology

Methanol is structure saturated monohydroxy alcohol the simplest, is generally reacted and is made by carbon monoxide and hydrogen.By appropriate Catalytic process, methanol can transform into a variety of petrochemicals such as ethene, propylene, aromatic hydrocarbons or distillate (that is, MTH mistakes Journey).

The process (that is, MTG processes) that methanol converts gasoline processed is strongly exothermic process, and its caloric value is about 1400kg/kg, can With with its process of following three equation approximate descriptions：

Existing MTG process routes have three kinds, are fixed-bed process, fluidized-bed process and multi-tubular reactor work respectively Skill.

The MTG techniques of early stage use fixed-bed process.For example, US3931349, which discloses one kind, uses fixed bed by first Alcohol converts the technique of gasoline processed, and in the process, methanol sequentially enters two reactors, in first reactor using it is acid compared with Low non-molecular sieve type catalyst, part methanol is converted into dimethyl ether, then in second reactor, using ZSM-5 types Catalyst, it is hydrocarbon compound by unconverted methanol and dimethyl ether conversion.

It is strongly exothermic process because methanol converts gasoline process processed, and has substantial amounts of water to generate, therefore in course of reaction Catalyst inactivates comparatively fast under conditions of high temperature hydro-thermal.In general, in MTG fixed bed reactors, the general 300-500 of catalyst Hour is with regard to needing to be regenerated.It is general to use in order to ensure the continuity and security of production in the industrial production of scale Multiple fixed bed reactors are in parallel, the mode of reactor frequent switching regenerated catalyst carries out MTG reactions.It is reported that 100,000 tons/ The MTG devices in year, the regeneration period of its MTG catalyst reactor is 20 days or so, and entire life is about 1 year.On the one hand, it is fixed Bed catalyst reactor bed pressure drop is big, and total reactor pressure is dropped in more than 300kPa, causes gas circulation high energy consumption；The opposing party Face, the switching of fixed bed reactors is excessively frequent, causes labor intensity big, and running cost is high.

In order to overcome the shortcomings that catalyst inactivation is fast in fixed bed reactors, there is fluid bed and tubulation again in MTG techniques Formula fixed-bed process.

US4689205 discloses the technology that hydrocarbon is produced in a kind of methanol multi-stage conversion.In first paragraph reactor, methanol conversion For C2-C4 alkene and part C5⁺Hydro carbons, by C5⁺After hydrocarbon separation, remainder carries out reaction generation vapour into fluidized-bed reactor Oil distillate.

CN101775310A discloses a kind of fluid bed MTG techniques.Methanol steam enters from fluidized-bed reactor bottom, with Flowed out after catalyst haptoreaction from reactor head after gas solid separation, partial catalyst removes laggard from reactor top Enter regenerator regeneration, the catalyst after regeneration accomplished continuously or intermittently reacted into reactor, so as to solve catalyst inactivation compared with The problem of fast.

Although fluidized-bed reactor solves the problems, such as that MTG catalyst deactivation rates are fast, but gasoline yield is less than fixed bed Reactor, and catalyst abrasion is serious.

Lurgi companies and Mobil companies also joint development multitube fixed-bed process, reaction heat is reacted by multitube The fuse salt of device shell side circulation is taken away, so as to the purpose for reaching control reaction temperature rising, extending catalyst life.But use shell and tube Reactor and fuse salt take thermal flow process make it that equipment manufacturing costs are too high, are not suitable for large-scale production, therefore have no that industrialization should Report.

The content of the invention

It is an object of the invention to provide a kind of method that new oxygen containing feed by such as methanol transforms into gasoline, the party Method can obtain higher methanol conversion and gasoline selective, and operation energy consumption is low, while be also easy to realize the anti-of catalyst Answer ex-situ regeneration.

The invention provides a kind of method that oxygen containing feed is transformed into gasoline, this method includes making oxygen containing feed with urging Agent haptoreaction in the reaction region, obtains the mixture containing gasoline, and the oxygen containing feed is methanol and/or dimethyl ether, institute State catalyst and contain molecular sieve, wherein, the reaction zone includes raw material area, product area and catalytic reaction zone, and the catalysis is anti- It is to be circular layout and be located at along the axially extending of reaction zone, the oxygen containing feed in the raw material area, the catalyst position to answer area In the catalytic reaction zone, the raw material area and the product area are abutted by the catalytic reaction zone, the raw material area Interior oxygen containing feed enters the catalytic reaction zone and catalyst haptoreaction, described in the obtained entrance of the mixture containing gasoline Product area.

The method according to the invention has advantages below.

(1) the method according to the invention, catalyst are to be circular layout in reaction zone, pressure drop (that is, the pressure of annular both sides Difference) generally not higher than 100kPa be can be achieved driving positioned at annular side gas material by catalyst reach annular it is another Side.Compared with using the technique of fixed bed reactors, system pressure drop substantially reduces, and is used to convey material so as to significantly reduce Compressor compression ratio, reduce operation energy consumption.Specifically, compared with fixed bed reactors, the method according to the invention and Device, system pressure drop reduce 0.1-0.3MPa, and energy consumption of compressor can at least reduce about 20%.

(2) method according to the invention it is possible to easily realize being continuously added to and drawing off for catalyst in reactor, unload The catalyst gone out can be regenerated outside reactor.Compared with using the technique of fixed bed reactors, the anti-of complexity is avoided that Answer device frequent switching to regenerate flow, and multiple fixed bed reactors need not be set, reduce cost of investment and the operation of device Complexity.

(3) the method according to the invention, the methanol conversion suitable with the technique using fixed bed reactors can be obtained, with Using the feed stock conversion and gasoline selective of the suitable even more high of the technique of fixed bed reactors.

Brief description of the drawings

Accompanying drawing is for providing a further understanding of the present invention, and a part for constitution instruction, with following tool Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.

Fig. 1 is the schematic diagram of the internal structure of the reactor for illustrating to use in the method according to the invention.

Fig. 2 is used for a kind of embodiment for illustrating the method according to the invention.

Fig. 3 is used for a kind of preferred embodiment for illustrating the method according to the invention.

Fig. 4 is used for a kind of embodiment being more highly preferred to for illustrating the method according to the invention.

Description of reference numerals

1：Oxygen containing feed 2：DME reactors

3：DME reactor outlets logistics 4：MTG reactor inlet logistics

5：MTG reactors 51：First MTG reactors

52：2nd MTG reactors 6：MTG reactor outlet logistics

7：Steam generator 8：Product/circulating air heat exchanger

9：Product/raw material heat exchanger 10：Product cooler

11：Gas-liquid separator 12：Gaseous stream

13：Liquid phase stream 14：Waste water

15：Recycle gas compressor 16：Discharge gas

17：Fractionation unit 18：Intermediate product/circulating air heat exchanger

19：Toroidal container 20：The outer shroud side wall of toroidal container

21：The interior ring-side wall 22 of toroidal container：Catalyst charge pipe

23：Catalyst discharge nozzle 24：Inner annular space

25：Outer annular space 26：Product guide pipe

27：Circulating air

Embodiment

In the present invention, " optional " and " alternatively " is represented with or without including or not including.

The invention provides a kind of method that oxygen containing feed is transformed into gasoline, this method includes making oxygen containing feed with urging Agent haptoreaction in the reaction region, obtains the mixture containing gasoline.

The method according to the invention, the reaction zone include raw material area, product area and catalytic reaction zone, the raw material area For accommodating oxygen containing feed, the product area is used for the mixture containing gasoline for accommodating generation, and the catalytic reaction zone is used for Containing catalyst.The catalytic reaction zone is to be circular layout and along the axially extending of reaction zone, the raw material area and the product Area is abutted by the catalytic reaction zone.The catalytic reaction zone is preferably to be coaxially disposed with the reaction zone.It is described oxygen-containing Raw material is located in the raw material area, and the catalyst is located in the catalytic reaction zone.

In actual mechanical process, as shown in figure 1, can be by setting (the annular of toroidal container 19 in MTG reactors 5 Container 19 is preferably coaxially disposed with MTG reactors 5), and make the outer shroud side wall 20 of toroidal container 19 and the inner side of MTG reactors 5 Existential Space (that is, making the overall diameter of toroidal container 19 be less than the interior diameter of MTG reactors 5) between wall.Toroidal container 19 it is interior Ring-side wall 21 is with having the hole being enough by gas in outer shroud side wall 20.The bore dia of the hole is insufficient to allow catalyst to lead to Cross, typically can be in the range of 1-20mm.Between the outer shroud side wall 20 of toroidal container 19 and the madial wall of MTG reactors 5 By in the side wall of toroidal container 19 between outer annular space 25 and the inner annular space 24 surrounded by the interior ring-side wall 21 of toroidal container 19 Porosity communication.Toroidal container 19 is used for containing catalyst, by the outer shroud side wall 20 of toroidal container 19 and MTG reactors 5 Outer annular space 25 between side wall as the raw material area for accommodating oxygen containing feed, using the inner annular space 24 of toroidal container 19 as For accommodating the product area of the mixture containing gasoline；Vice versa, can be using the inner annular space 24 of toroidal container 19 as use In the raw material area for accommodating oxygen containing feed, by the outer shroud between the outer shroud side wall 20 of toroidal container 19 and the madial wall of MTG reactors 5 Space 25 is as the product area for accommodating the mixture containing gasoline.Guiding device can be set in product area, will generate Containing gasoline mixture export.

Preferably, as shown in figure 1, will be outer between the outer shroud side wall 20 of toroidal container 19 and the madial wall of MTG reactors 5 Annular space 25 contains the inner annular space 24 of toroidal container 19 as receiving as the raw material area for accommodating oxygen containing feed The product area of the mixture of gasoline.The mixture containing gasoline that product area obtains is defeated by product guide pipe 26 from product area Go out.

The method according to the invention, catalyst are arranged in catalytic reaction zone.

In the first embodiment, beds can be formed by Catalyst packing in catalytic reaction zone, it is oxygen-containing Raw material enters catalytic reaction zone and catalyst haptoreaction from raw material area, so as to obtain mixture (that is, the catalyst containing gasoline It is non-moving state in catalytic reaction zone).

In actual mechanical process, beds can be formed by Catalyst packing in toroidal container.Can be in ring Describe and porous plate and/or net are set in device, to avoid catalyst from leaking outside.

In second of embodiment, catalyst can also be made to enter from the top of the catalytic reaction zone, urged along described That changes reaction zone leaves the catalytic reaction zone axially through the catalytic reaction zone, and from the bottom of catalytic reaction zone, is catalyzed With oxygen containing feed haptoreaction during by catalytic reaction zone, the catalyst for leaving catalytic reaction zone is alternatively carried out for agent After regeneration, catalytic reaction zone (that is, catalyst is in mobile status in catalytic reaction zone) is recycled back to.Leave urging for reaction zone Agent can all carry out regenerating Posterior circle go back to catalytic reaction zone, can also partly be regenerated, remainder and fresh catalyst Agent and/or catalyst through regeneration are recycled back to catalytic reaction zone together.Using this embodiment, can conveniently realize to urge Agent is regenerated outside reactor, eliminates numerous and diverse operation such as reactor switching in fixed bed reactors technique.

In second of embodiment, residence time of the catalyst in catalytic reaction zone can be 150-800 hours, excellent Elect 200-700 hours, more preferably 300-500 hours as.Can be by adjusting lower terminal-velocity of the catalyst in catalytic reaction zone Spend to adjust residence time of the catalyst in catalytic reaction zone.The falling speed for adjusting catalyst is those skilled in the art institute It is known, no longer it is described in detail herein.

In actual mechanical process, as shown in figure 1, can be by catalyst from the catalyst charge pipe at the top of catalytic reaction zone 22 are sent into, in the presence of catalyst self gravitation, by catalytic reaction zone, and by the catalyst positioned at catalytic reaction zone bottom Discharge nozzle 23 leaves catalytic reaction zone.

Above two embodiment may be used alone, can also be used in combination.Combined by above two embodiment In use, former embodiment (that is, by Catalyst packing in catalytic reaction zone) can be used in initial reaction stage, it is being catalyzed Downward trend is presented, it is necessary to when being regenerated in the activity of agent, opens catalyst charge pipe and catalyst discharge nozzle, and activity is met It is required that catalyst be sent into catalytic reaction zone, while make activity reduce catalyst leave reaction zone into regeneration unit carry out again It is raw.

The method according to the invention, pressure differential (that is, pressure drop) existing for the catalytic reaction zone both sides cause the raw material Oxygen containing feed in area enters the catalytic reaction zone and catalyst haptoreaction, and the obtained mixture containing gasoline enters institute State product area.In fixed bed reactors, make oxygen containing feed and catalyst haptoreaction, so as to obtain the mixture containing gasoline When, the pressure drop of beds is higher and is gradually risen with the extension of fixed bed reactors run time；However, according to this hair Bright method, the pressure drop of catalytic reaction zone both sides are less than the pressure drop of beds in fixed bed reactors, it is often more important that, It is held essentially constant for a long time in continuous running.The method according to the invention, the pressure differential of the catalytic reaction zone both sides 100kPa is generally not higher than, so can substantially reduce the compression ratio of the compressor for conveying logistics to reaction zone, so as to Reduce operation energy consumption.On the premise of ensuring to be enough to make oxygen containing feed by catalytic reaction zone, operation energy consumption is reduced from further Angle set out, the pressure differential of the catalytic reaction zone both sides is preferably not higher than 50kPa.The pressure of the catalytic reaction zone both sides Power difference is generally more than 5kPa, preferably more than 20kPa.It can be urged by way of the thickness for adjusting catalytic reaction zone to adjust Change the pressure differential of reaction zone both sides.The method according to the invention, the thickness of catalytic reaction zone are generally no more than 1.5 meters, preferably For no more than 1 meter.The thickness of the catalytic reaction zone is generally more than 0.3 meter, preferably more than 0.4 meter.

The method according to the invention, the catalyst contain molecular sieve.Active component of the molecular sieve as catalyst, can be with There is the molecular sieve of catalytic action, preferably ZSM-5 molecular sieve for the common conversion reaction to oxygen containing feed gasoline.It is more excellent Selection of land, ZSM-5 molecular sieve contain P elements and optional rare earth element.On the basis of the total amount of the ZSM-5 molecular sieve, with Oxide (P₂O₅) count, the ZSM-5 molecular sieve preferably comprises 0.1-10 weight % phosphorus, further preferably 5-8 weight %'s Phosphorus；Counted using oxide (chemical valence of rare earth is+3), the ZSM-5 molecular sieve preferably comprises 0-10 weight % rare earth, more excellent Select the rare earth containing 3-8 weight %.

P elements and optional rare earth element can be introduced in ZSM-5 molecular sieve using various methods.A kind of real Apply in mode, P elements and optional rare earth element can be introduced in ZSM-5 molecular sieve by infusion process.Can with water The aqueous solution dipping ZSM-5 molecular sieve of dissolubility phosphorus-containing compound, is then dried and is calcined, so as to obtain phosphorus element-containing ZSM-5 molecular sieve.When ZSM-5 molecular sieve also contains rare earth element, can before introducing P elements, among or afterwards, use The aqueous solution dipping ZSM-5 molecular sieve of water dissolvable compounds containing rare earth, and be dried and be calcined, so as to obtain containing rare earth member The ZSM-5 molecular sieve of element.The instantiation of the water dissolvable phosphorus-containing compound can include but is not limited to：Phosphoric acid, aluminum phosphate, It is more than one or both of ammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate.The water dissolvable compounds containing rare earth it is specific Example can include but is not limited to：One or both of chloride of the nitrate of ceria, the sulfate of rare earth and rare earth with On.The condition of the drying and roasting can be conventional selection.Usually, the drying can enter at a temperature of 80-200 DEG C OK, the duration can be 2-10 hours；The roasting can be carried out at a temperature of 400-600 DEG C, and the duration can be 4-10 hours.

In the ZSM-5 molecular sieve, the content of the alkali metal in terms of oxide is preferably not higher than 0.2 weight %.It is described In ZSM-5 molecular sieve, the mol ratio (that is, silica alumina ratio) of silica and aluminum oxide is preferably in the range of 100-1000, more preferably In the range of 100-500.

The catalyst is in addition to containing the molecular sieve as active component, when the catalyst is preformed catalyst, also Can contain binding agent, the binding agent can be it is common can be by the material of molecular sieve molding bonded, such as inorganic oxide And/or clay.In the catalyst, the content of molecular sieve is can realize that catalysis is defined.Usually, with the total of catalyst On the basis of amount, the content of molecular sieve can be 30-95 weight %, more preferably preferably 30-88 weight %, 60-80 weight %； The content of inorganic oxide can be 5-70 weight %, more preferably preferably 10-50 weight %, 15-30 weight %；Clay Content can be 0-50 weight %, more preferably preferably 2-20 weight %, 5-10 weight %.The inorganic oxide refers to Under oxygen or oxygen-containing atmosphere, decomposition temperature not less than 300 DEG C (such as：Decomposition temperature be 300-1000 DEG C) inorganic oxygen-containing chemical combination Thing.The instantiation of the inorganic oxide can include but is not limited in aluminum oxide, silica, titanium oxide and magnesia one Kind is a variety of.Preferably, the inorganic oxide is aluminum oxide and/or silica.The clay can be it is various natural and/or Clays artificial synthesized, through or without various chemistry and/or physical method processing, such as kaolin and/or halloysite (that is, galapectite).

When the catalyst is preformed catalyst, usually, the specific surface area of the catalyst is in 300-600m²/ g's In the range of, for total pore volume in the range of 0.2-0.6mL/g, mesoporous pore volume of the bore dia more than 2nm accounts for the 30-70% of total pore volume. The specific surface area and the pore volume are determined using nitrogen adsorption methods.

When the catalyst is preformed catalyst, the volume average particle size of the catalyst is preferably 1-10mm, more excellent Elect 5-8mm as.

The method according to the invention, the oxygen containing feed can be the raw material that can transform into gasoline.Usually, it is described Oxygen containing feed is methanol and/or dimethyl ether.The oxygen containing feed can be sent into reactor by carrier gas, and the carrier gas can be Water vapour, non-active gas (such as nitrogen, group 0 element gas) and low-carbon hydro carbons (such as C₁-C₅Alkane), it is preferred to use lower carbon number hydrocarbons Class is as carrier gas.The low-carbon hydro carbons is preferably derived from the gas phase separated from the mixture containing gasoline of reaction generation Logistics (that is, circulating air described hereinafter).When oxygen containing feed is sent into reactor by carrier gas, with carrier gas and oxygen containing feed On the basis of total amount, the content of oxygen containing feed can be 1-25 weight %, preferably 5-20 weight %.

When the oxygen containing feed is methanol, methanol can be sent directly into reaction zone and be connect with the catalyst containing molecular sieve Reaction is touched, obtains the mixture containing gasoline；At least part methanol first can also be transformed into dimethyl ether, then will contain two The mixture of methyl ether is sent into reaction zone with the catalyst haptoreaction containing molecular sieve as oxygen containing feed, can so be obtained more High yield of gasoline.The method according to the invention, when oxygen containing feed is methanol, preferably also include pre-reaction step, described In pre-reaction step, at least part methanol is transformed into dimethyl ether, and the mixture that pre-reaction step is obtained is as oxygen-containing Raw material is sent into the reaction zone and the catalyst haptoreaction containing molecular sieve.In pre-reaction step, preferably methanol is turned Rate control is 50-85 weight %, is 80-85 weight % more preferably by the conversion ratio control of methanol.The conversion ratio of the methanol It is calculated using below equation：

Conversion ratio=(feed weight of weight/methanol of the methanol consumed in pre-reaction step) × 100%.

In the pre-reaction step, reaction temperature can be 240-450 DEG C, preferably 260-400 DEG C；In terms of gauge pressure, go out Mouth pressure can be 0.8-3MPa, preferably 1.5-2.5MPa, more preferably 1.6-2MPa.

Pre-reaction step can be used for catalyst of the alcohol ether reaction with catalytic action, such as aluminum oxide.Can be with The Catalyst packing with catalytic action will be reacted alcohol ether in fixed bed reactors, make methanol by beds, So as to which at least part methanol is transformed into dimethyl ether.Now, total weight (hourly) space velocity (WHSV) of gas feed can be 0.5-20h^-1, preferably For 1-10h^-1, more preferably 2-5h^-1。

The method according to the invention, oxygen containing feed in the reaction region with catalyst haptoreaction, the catalytic bar Part is enough to make oxygen containing feed transform into gasoline.Usually, the haptoreaction can be carried out at a temperature of 280-500 DEG C, It is preferred that carry out at a temperature of 300-450 DEG C, more preferably carried out at a temperature of 340-420 DEG C；In terms of gauge pressure, outlet pressure can Think 0.8-3MPa, preferably 1-2.5MPa, more preferably 1.5-2MPa；Total weight (hourly) space velocity (WHSV) of gas feed can be 0.5- 6h^-1, preferably 0.8-4h^-1, more preferably 2-4h^-1。

The method according to the invention, the quantity of the reaction zone can be one, or two or more.In reaction zone Quantity when being two or more, each reaction zone can be located in one or more reactors, such as can be located at same reactor Different zones, can also be located at multiple reactors in.Each reaction zone can contain one or more raw materials existing in groups Area, catalytic reaction zone and product area.

When the quantity of the reaction zone is one, the mixture containing gasoline that reaction zone obtains can be directly as production Thing logistics exports.Can be to be connected in parallel between reaction zone, i.e., each reaction zone obtains when the quantity of the reaction zone is multiple The mixture containing gasoline can be exported directly as product stream；Can also be to be connected in series between reaction zone, i.e., it is previous What reaction zone obtained contains raw material of the mixture of gasoline as latter reaction zone, will be located at end (with the flow direction of logistics On the basis of) the obtained mixture for containing gasoline of reaction zone exported as product stream；It can also be series connection between reaction zone With combination in parallel.

In a kind of preferred embodiment of the present invention, the reaction zone contains the first reaction zone and second reaction zone, Part oxygen containing feed in the first reaction zone with catalyst haptoreaction, and using the obtained mixture for containing gasoline as among Logistics exports；The intermediate stream and remainder oxygen containing feed in second reaction zone with molecular sieve haptoreaction, and will The mixture for containing gasoline arrived exports as product stream.Higher gasoline can be obtained according to the preferred embodiment to receive Rate.First reaction zone and second reaction zone can each contain one or more raw material areas existing in groups, catalytic reaction Area and product area.First reaction zone and second reaction zone can be located at the different zones of same reactor, can also be located at In different reactors, it is preferably placed in different reactors.

In the preferred embodiment, on the basis of the total amount of the oxygen containing feed, into the oxygen-containing of the first reaction zone The amount of raw material is preferably 20-70 weight %, more preferably 30-60 weight %, more preferably 45-55 weight %；Into The amount of the oxygen containing feed of two reaction zones is preferably 30-80 weight %, more preferably 40-70 weight %, more preferably 45-55 Weight %.

In the preferred embodiment, the intermediate stream is preferably situated between before the second reaction zone is entered with heat exchange Matter is exchanged heat, and the partial heat in the intermediate stream is taken out, can so obtain more preferable energy balance, while energy It is enough farthest to utilize the heat entrained by intermediate stream.The heat transferring medium can be it is common can be by the intermediate The medium that heat in stream takes out.Preferably, the heat transferring medium includes water, by the way that the intermediate stream is changed with water Heat, high-pressure water vapor can be produced, its pressure can reach more than 4MPa.In the preferred embodiment, the heat transferring medium The circulating air into the raw material area of the first reaction zone can also be included.The circulating air comes from from second reaction zone as product (separation process of product stream will be carried out the gaseous stream separated in the mixture containing gasoline of logistics output later Describe in detail), it lives through cooling procedure in separation process, when being recycled back to the raw material area of reaction zone, it is necessary to re-start Preheating.When the heat transferring medium includes water and circulating air, preferably the intermediate stream is changed with circulating air and water successively Heat, circulating air is preheated, while produce high-pressure water vapor, can so obtained between the first reaction zone and second reaction zone good Good energy balance, while the heat of intermediate stream carrying can also be maximally utilised.

In the preferred embodiment, catalyst is respective in the catalytic reaction zone of the first reaction zone and second reaction zone Previously described mobile status is may be at, can also be each in previously described non-moving state.Preferably, catalyst exists Previously described mobile status is in the catalytic reaction zone of first reaction zone and second reaction zone.It is highly preferred that it will leave The catalyst of first reaction zone is sent into the catalytic reaction zone of second reaction zone, can from the catalyst of second reaction zone output After selection of land is regenerated, it is recycled into the catalytic reaction zone of the first reaction zone.That is, catalysis of the catalyst from the first reaction zone The top of reaction zone enters, and leaves the first reaction zone from the bottom of catalytic reaction zone, is extending axially through catalytic reaction zone During with oxygen containing feed haptoreaction, the catalyst for leaving the first reaction zone enters into and through urging for second reaction zone from top Change reaction zone, from bottom leave the catalyst of second reaction zone alternatively carry out regenerating Posterior circle return the first reaction zone catalysis it is anti- Answer area.Total residence time of the catalyst in the catalytic reaction zone of the catalytic reaction zone of the first reaction zone and second reaction zone is preferred For 150-800 hours, more preferably 300-700 hours.It is further preferred that catalyst is in the catalytic reaction zone of the first reaction zone It is 400-600 hours with the total residence time in the catalytic reaction zone of second reaction zone, can so obtains higher gasoline production Rate, while can also make catalyst that there is longer service life.

The method according to the invention, carried largely from reaction zone as the mixture containing gasoline that product stream exports Heat, itself and at least one heat transferring medium can be exchanged heat, so as to which partial heat be taken out.Exchanged heat with product stream Heat transferring medium can be selected from water, circulating air and oxygen containing feed.In one embodiment, exchanged heat with product stream Heat transferring medium is water, circulating air and oxygen containing feed, can be now situated between respectively with various heat exchange by the way that product stream is shunted Matter is exchanged heat and realized.Specifically, product stream can be divided into three parts, Part I logistics is exchanged heat with water, with Water vapour is produced, the pressure of obtained water vapour is typically in the range of 1-2.5MPa；Part II logistics is carried out with circulating air Heat exchange, circulating air is preheated；Part III logistics is exchanged heat with oxygen containing feed, and oxygen containing feed is preheated.Described first The amount of fraction of stream, Part II logistics and Part III logistics can be according to the bar of the heat transferring medium to be exchanged heat therewith respectively Part is selected, and is not particularly limited.

The method according to the invention, separating step can also be included, in separating step, using what is exported as product stream Mixture containing gasoline carries out gas-liquid separation, obtains gaseous stream and liquid phase stream, gasoline (that is, C₅-C₁₀Hydrocarbon) it is located at institute State in liquid phase stream.Conventional method can be used to carry out gas-liquid separation, such as condensed.

The liquid phase stream contains gasoline, can be fractionated, and so as to isolate gasoline and other products, such as fires Expect gas and liquefied gas.After at least part in the gaseous stream can boost, it is re-fed into instead as circulating air (that is, carrier gas) , typically will circulation when the reaction zone contains previously described first reaction zone and second reaction zone in the raw material area for answering area Pneumatic transmission enters in the raw material area of the first reaction zone.In order to avoid oxygen, CO, CO₂Accumulate Deng incoagulable gas, preferably will in systems Arranged outside partial gas phase logistics.

Fig. 2 shows a kind of embodiment of the method according to the invention, the embodiment is carried out below in conjunction with Fig. 2 detailed Describe in detail bright.

As shown in Fig. 2 oxygen containing feed 1 enters MTG reactors 5 (its internal structure is as shown in figure 1, be no longer described in detail herein) In raw material area, (catalyst may be at previously described mobile status, can also be in described previously with catalyst haptoreaction Non-moving state), at least part oxygen containing feed is transformed into gasoline, obtain as product stream output MTG reactors Outlet streams 6.MTG reactor outlets logistics 6 is divided into three parts logistics, wherein, Part I logistics enters steam generator 7 In, exchanged heat with water, to produce water vapour (for low pressure water vapor, pressure is typically in the range of 1-2.5MPa)；Second Divide logistics to enter in product/circulating air heat exchanger 8, exchanged heat with circulating air, circulating air is preheated；Part III logistics is entered Enter in product/raw material heat exchanger 9, exchanged heat with fresh oxygen containing feed, fresh oxygen containing feed is preheated.Each portion through heat exchange After point product stream is collected, through being cooled down in product cooler 10, into gas-liquid separator 11, to be separated into gas gas-phase objects Stream 12, liquid phase stream 13 and the waste water 14 arranged outside, the condition of the cooling cause gasoline to be located in liquid phase stream 13.Gas gas-phase objects Stream 12 is sent back in the raw material area of MTG reactors 5 after the boosting of recycle gas compressor 15 as circulating air 27.Alternatively, gas gas-phase objects Fraction of stream in stream 12 is discharged into fractionation unit 17 as discharge gas 16, to avoid the accumulation of incoagulable gas in systems. Liquid phase stream 13, which enters in fractionation unit 17, to be fractionated, and obtains gasoline, fuel gas and liquefied gas.

Fig. 3 shows a kind of preferred embodiment when oxygen containing feed is methanol.Below only in conjunction with Fig. 3 to the embodiment Illustrated with the difference of Fig. 2 illustrated embodiments.As shown in figure 3, the methanol as oxygen containing feed 1 initially enters DME In reactor 2, part methanol is transformed into dimethyl ether, after obtained DME reactor outlets logistics 3 mixes with circulating air 27, Enter as MTG reactor inlets logistics 4 in MTG reactors 5, contact, obtained containing gasoline with the catalyst containing molecular sieve Mixture.

Fig. 4 shows a kind of embodiment being more highly preferred to of the method according to the invention, below in conjunction with Fig. 4 to the implementation Mode is described in detail.For purposes of brevity, below only to the embodiment shown in Fig. 4 and the embodiment shown in Fig. 2 Difference illustrate.

As shown in figure 4, being sent into as the methanol of oxygen containing feed 1 in DME reactors 2, part methanol is transformed into two Methyl ether.Part DME reactor outlets logistics 3 enters in the first MTG reactors 51 together with circulating air 27, with urging containing molecular sieve Agent haptoreaction, obtain the mixture containing gasoline.As the output of the first MTG reactors 51 outlet streams containing gasoline Mixture passes sequentially through intermediate product/circulating air heat exchanger 18 and steam generator 7, will enter the first MTG reactors respectively The circulating air preheating in 51 raw material area, make water be transformed into water vapour (for high-pressure water vapor, its pressure can reach 4MPa with On).The outlet streams of the first MTG reactors 51 through heat exchange enter second together with remainder DME reactor outlets logistics 3 In MTG reactors 52, with catalyst haptoreaction, the mixture containing gasoline is obtained, and it is anti-from the 2nd MTG as product stream Device 52 is answered to export.The product stream of 2nd MTG reactors 52 output is divided into two parts logistics, wherein, Part I logistics is being produced Exchanged heat in thing/circulating air heat exchanger 8 with circulating air, circulating air is preheated；Part II logistics is in product/raw material heat exchange Exchanged heat in device 9 with fresh oxygen containing feed, fresh oxygen containing feed is preheated.After each several part logistics after heat exchange collects, Through being cooled down in product cooler 10, separated in gas-liquid separator 11, obtain gaseous stream 12, liquid phase stream 13 with And waste water 14, the condition of the cooling cause gasoline to be located in liquid phase stream 13.The gaseous stream 12 and liquid phase stream isolated 13, using being further processed with Fig. 2 illustrated embodiment identical modes, are no longer described in detail herein.

Embodiment according to Fig. 4, catalyst in the first MTG reactors 51 and the 2nd MTG reactors 52 can be with In previously described non-moving state, previously described mobile status can also be in.Preferably, the first MTG reactors 51 Mobile status is in the catalyst in the 2nd MTG reactors 52.It is highly preferred that as shown in the dotted portion in Fig. 4, catalyst The catalytic reaction zone of the first MTG reactors 51 is entered into and through from the top of the first MTG reactors 51, from the first MTG reactors The catalyst of 51 outputs is subsequently entered and by the catalytic reaction zone of the 2nd MTG reactors 52, exported from the 2nd MTG reactors 52 Catalyst alternatively regenerated after be recycled back in the catalytic reaction zone of the first MTG reactors 51.

It should be noted that in embodiment shown in Fig. 4, the oxygen containing feed used is methanol, those skilled in the art It is understood that the embodiment shown in Fig. 4 is also applied for the occasion that oxygen containing feed contains dimethyl ether, at this point it is possible to not set DME reactors 2 are put, part oxygen containing feed 1 enters in the first MTG reactors 51, and remainder oxygen containing feed 1 enters the 2nd MTG In reactor 52.

Oxygen containing feed is transformed into by gasoline using the method according to the invention, the operation energy of system can be greatly reduced Consumption, and higher methanol conversion and gasoline selective can be obtained, while the catalyst containing molecular sieve can conveniently realize Ex-situ regeneration is reacted, catalyst also has longer service life in addition.

Describe in detail with reference to embodiments, but and be not so limited the scope of the present invention.

In following examples and comparative example, the selectivity of gasoline is calculated using below equation：

Gasoline selective=(C in product₅-C₁₀The feed weight of weight/methanol of hydrocarbon) × 100%.

Embodiment 1-9 is used for the method for illustrating the present invention.

Embodiment 1

The catalyst that the present embodiment uses is prepared by the following method.

(1) the powdered ZSM-5 molecular sieve as raw material is impregnated (with Na by the use of ammonium dihydrogen phosphate aqueous solution saturation₂O meters Na contents are 0.2 weight %, SiO₂/Al₂O₃(mol ratio)=100, purchased from sinopec Chang Ling catalyst plant), the time is 5 hours. Obtained mixture will be impregnated to dry 7 hours in 150 DEG C of baking oven；By Muffle furnace of the dried solid powder at 560 DEG C Middle roasting 5 hours.Obtained solid is calcined after pulverizing and sieving, obtains phosphorous ZSM-5 molecular sieve, wherein, with P₂O₅Meter, phosphorus Content be 5 weight %.

(2) boehmite is mixed with kaolin, and obtained mixture is configured to slurries with deionized water, then The phosphorous ZSM-5 molecular sieve that step (1) obtains is added, after stirring, is spray-dried, controls going out for spray dryer For mouth temperature within the scope of 100-110 DEG C, the dry materials time is 2 minutes.Obtained particle will be spray-dried in 450 DEG C of roastings Burn 4 hours, so as to obtain the preformed catalyst (volume average particle size 8mm) containing ZSM-5, wherein, phosphorous ZSM-5 molecular sieve Content be 80 weight %, the content of aluminum oxide is 15 weight %, and the content of clay is 5 weight %.

The internal structure for the MTG reactors that the present embodiment uses is as shown in figure 1, wherein, the annular diameters of toroidal container are 0.8m, outer annular diameter 1.3m, it is highly 4m；The interior diameter of reactor is 2.2m；Toroidal container is coaxially disposed in the reactor. Have in interior ring-side wall and the outer shroud side wall of toroidal container and be for the hole by gas material, the average pore diameter of hole 9mm.The annular space of toroidal container is internally provided with porous plate, to prevent catalyst from leaking outside.By the inner annular space of toroidal container As product area, using the outer annular space between the lateral wall of toroidal container and the madial wall of reactor as raw material area, catalyst It is seated in toroidal container, forms beds.

The present embodiment is using methanol as oxygen containing feed, and the technological process shown in reference picture 2 is carried out, and specific method is as follows.

Methanol and circulating air (on the basis of the total amount of methanol and circulating air, the content of methanol is 10 weight %) are sent into In the raw material area of MTG reactors, and enter in toroidal container with catalyst haptoreaction, obtained reactant mixture enters product Qu Zhong, exported as product stream.Wherein, it is 340 DEG C by the inlet temperature control of MTG reactors, by the outlet of MTG reactors Temperature control is 420 DEG C；Pressure differential between the outer shroud side wall of toroidal container and interior ring-side wall is 50kPa (bases in course of reaction This holding is constant), it is 1.6MPa by the outlet pressure control of MTG reactors in terms of gauge pressure；Total weight (hourly) space velocity (WHSV) of gas feed is 4h^-1。

Product stream is divided into three strands, respectively enters steam generator, product/circulating air heat exchanger and product/oxygen-containing In raw material heat exchanger, it is respectively used to produce water vapour (in terms of gauge pressure, the pressure of caused water vapour is 1.0MPa) and circulating air Exchanged heat, exchanged heat with fresh methanol.After the product stream come out from each heat exchanger is collected, enter into product cooler Row cooling (wherein, cooling medium is air).Product stream through cooling is further condensed to enter promoting the circulation of qi in gas-liquid separator Liquid separates, and is separated into gaseous stream and liquid phase stream.0.5 weight % in the gaseous stream isolated enters as discharge pneumatic transmission In fractionating system, remaining gaseous stream as circulating air is re-fed into the anti-of MTG reactors after being boosted in recycle gas compressor Answer in area.The liquid phase stream isolated, which enters in fractionating system, to be fractionated, and obtains fuel gas, liquefied gas and gasoline.

It is carried out continuously the reaction of 300 hours, in course of reaction, the conversion ratio and gasoline selective of methanol are listed in table 1.

Embodiment 2

Methanol is transformed into by gasoline using method same as Example 1, unlike, it is not that Catalyst packing exists In reactor, but catalyst is continuously introduced into toroidal container by being arranged on the catalyst charge pipe at the top of toroidal container, By the gravity of catalyst itself, toroidal container is passed to, and reaction is left from the catalyst discharge nozzle of ring-shaped container bottom Device, wherein, it is 300 hours to control residence time of the catalyst in the toroidal container of reactor.

It is carried out continuously the reaction of 300 hours, in tandem reaction sequence, the conversion ratio of methanol and the selectivity of gasoline are in table 1 In list.

Embodiment 3

Methanol is transformed into by gasoline using method same as Example 1, unlike, the catalyst used use with It is prepared by lower section method：

Boehmite is mixed with kaolin, and obtained mixture is configured to slurries, Ran Houjia with deionized water Enter with ZSM-5 molecular sieve identical ZSM-5 molecular sieve as raw material in the step of embodiment 1 (1), after stirring, sprayed Mist is dried, and controls the outlet temperature of spray dryer within the scope of 100-110 DEG C, and the dry materials time is 2 minutes.Will spray The particle that mist is dried to obtain is calcined 4 hours at 450 DEG C, and so as to obtain the preformed catalyst containing ZSM-5, (volume average particle size is 8mm), wherein, the content of ZSM-5 molecular sieve is 80 weight %, and the content of aluminum oxide is 15 weight %, and the content of clay is 5 weights Measure %.

Comparative example 1

By Catalyst packing same as Example 1 in fixed bed reactors (interior diameter and the reactor used in embodiment 1 Interior diameter it is identical) in, form beds (thickness of beds be 4 meters).By methanol and circulating air (with methanol and On the basis of the total amount of circulating air, the content of methanol is 10 weight %) it is sent into from top in fixed bed reactors and passes through catalyst Bed, with catalyst haptoreaction.Wherein, it is 340 DEG C by the inlet temperature control in reactor, by the outlet temperature of reactor Control as 420 DEG C；The initial pressure difference of beds is 0.1MPa, with the pressure differential of the extension beds in reaction time 0.3MPa is gradually increased to, is 1.6MPa by the outlet pressure control of reactor in terms of gauge pressure；Total weight (hourly) space velocity (WHSV) of gas feed For 4h^-1。

Exchanged heat and separated using method same as Example 1 from the reactant mixture of fixed bed reactors output, Obtain gasoline.

It is carried out continuously the reaction of 300 hours, in tandem reaction sequence, the conversion ratio and gasoline selective of methanol are in table 1 List.Under identical methyl alcohol process amount, the total energy consumption of the compressor for conveying circulating air is the total energy consumption of embodiment 1 120%.

Embodiment 4

Methanol is transformed into gasoline by the present embodiment using method same as Example 1, unlike, reference picture 3 is shown The flow gone out, concrete operations are as follows.

Methanol and circulating air (on the basis of the total amount of methanol and circulating air, the content of methanol is 10 weight %) are first sent into In DME reactors, part methanol is transformed into dimethyl ether (methanol conversion is controlled in the range of 80-85 weight %).Its In, the catalyst loaded in DME reactors is aluminum oxide, and the inlet temperature of DME reactors is 260 DEG C, outlet temperature 360 ℃；In terms of gauge pressure, the outlet pressure of DME reactors is 1.8MPa；Total weight (hourly) space velocity (WHSV) of gas feed is 4h^-1。

(mass ratio for the logistics that circulating air exports with DME reactors is 5 for the logistics and circulating air that DME reactors are exported： 1) it is sent into the raw material area of MTG reactors, and enters in toroidal container with catalyst haptoreaction, obtained reactant mixture enters Enter in product area, and exported as product stream.Wherein, it is 330 DEG C by the inlet temperature control of reactor, by going out for reactor Mouth temperature control is 410 DEG C；Pressure differential between the outer shroud side wall of toroidal container and interior ring-side wall is 50kPa (in course of reaction It is held essentially constant), it is 1.6MPa by the outlet pressure control of reactor in terms of gauge pressure；Total weight (hourly) space velocity (WHSV) of gas feed is 4h^-1。

Product stream is divided into three strands, respectively enters steam generator, product/circulating air heat exchanger and product/oxygen-containing In raw material heat exchanger, be respectively used to produce water vapour (in terms of gauge pressure, pressure 1.0MPa), exchanged heat with circulating air, with it is new Fresh methanol is exchanged heat.After the product stream come out from each heat exchanger is collected, cooled down (wherein, into product cooler Cooling medium is air).Further condensation to carry out gas-liquid separation, is separated into product stream through cooling in gas-liquid separator For gaseous stream and liquid phase stream.0.5 weight % in the gaseous stream isolated enters in fractionating system as discharge pneumatic transmission, remains Remaining gaseous stream is re-fed into the reaction zone of MTG reactors after being boosted in recycle gas compressor as circulating air.Isolate Liquid phase stream enter fractionating system in be fractionated, obtain fuel gas, liquefied gas and gasoline.

It is carried out continuously the reaction of 500 hours, in tandem reaction sequence, the conversion ratio of methanol and the selectivity of gasoline are in table 1 In list.

Embodiment 5

The catalyst that the present embodiment uses is prepared using following methods.

(1) powdered ZSM-5 molecular sieve is impregnated (with Na with ammonium dihydrogen phosphate aqueous solution saturation₂O meter Na contents be 0.1 weight %, SiO₂/Al₂O₃(mol ratio)=500, purchased from sinopec Chang Ling catalyst plant), the time is 6 hours.It will impregnate To mixture in 140 DEG C of baking oven dry 10 hours；By Muffle kiln roasting 5 of the dried solid powder at 560 DEG C Hour.Obtained solid is calcined after pulverizing and sieving, obtains phosphorous ZSM-5 molecular sieve, wherein, with P₂O₅Meter, the content of phosphorus are 8 weight %.

Phosphorous ZSM-5 molecular sieve is impregnated with lanthanum nitrate aqueous solution saturation, the time is 8 hours.Obtained mixing will be impregnated Thing is dried 8 hours in 130 DEG C of baking oven；By Muffle kiln roasting 6 hour of the dried solid powder at 550 DEG C.Roasting Obtained solid obtains phosphorous and lanthanum ZSM-5 molecular sieve, with La after pulverizing and sieving₂O₃Total amount on the basis of, the content of lanthanum For 5 weight %.

(2) boehmite is mixed with kaolin, and obtained mixture is configured to slurries with deionized water, then The ZSM-5 molecular sieve for the phosphorous and lanthanum that step (1) obtains is added, after stirring, is spray-dried, controls spray dryer Outlet temperature within the scope of 100-110 DEG C, the dry materials time be 2 minutes.Obtained particle will be spray-dried 450 DEG C roasting 4 hours, so as to obtain the preformed catalyst (volume average particle size 5mm) containing ZSM-5, wherein, phosphorous and lanthanum The content of ZSM-5 molecular sieve is 60 weight %, and the content of aluminum oxide is 30 weight %, and the content of clay is 10 weight %.

The first MTG reactors and the internal structure of the 2nd MTG reactors that the present embodiment uses are as shown in figure 1, wherein, ring The annular diameters for describing device are 0.6m, outer annular diameter 1.2m, are highly 4m；The interior diameter of reactor is 2.4m；Toroidal container It is coaxially disposed in the reactor.There is the hole being used for by gas material in interior ring-side wall and the outer shroud side wall of toroidal container, The average pore diameter of hole is 15mm.The annular space of toroidal container is internally provided with porous plate, to prevent catalyst from leaking outside.Will The inner annular space of toroidal container is as product area, by the outer annular space between the lateral wall of toroidal container and the madial wall of reactor As raw material area.

The present embodiment is using methanol as oxygen containing feed, and the technological process shown in reference picture 4 is carried out, and specific method is as follows.

Methanol and circulating air (on the basis of the total amount of methanol and circulating air, the content of methanol is 20 weight %) are first sent into In DME reactors, part methanol is transformed into dimethyl ether (methanol conversion is controlled in the range of 80-85 weight %).Its In, the catalyst loaded in DME reactors is aluminum oxide, is 260 DEG C by the inlet temperature control of DME reactors, DME is reacted The outlet temperature control of device is 360 DEG C；In terms of gauge pressure, the outlet pressure of DME reactors is 1.9MPa；During the gross weight of gas feed Air speed is 3h^-1。

By the outlet streams of 50 weight % DME reactors and circulating air (circulating air and the logistics of DME reactors output Mass ratio is 5：1) it is sent into together in the raw material area of the first MTG reactors, methanol is entered in toroidal container and contacted with catalyst Reaction, obtained reactant mixture enter in product area, and are exported as intermediate stream.Wherein, entering the first MTG reactors Mouth temperature control is 340 DEG C, is 420 DEG C by the outlet temperature control of the first MTG reactors；The outer shroud side wall of toroidal container with it is interior Pressure differential control between ring-side wall is 50kPa (being held essentially constant in course of reaction), and in terms of gauge pressure, the first MTG is reacted The outlet pressure control of device is 1.8MPa；Total weight (hourly) space velocity (WHSV) of gas feed is 2h^-1。

The intermediate stream of first MTG reactors output is occurred in intermediate product/circulating air heat exchanger and water vapour successively Exchanged heat respectively with the circulating air and water for entering the first MTG reactors in device, respectively obtain (the heat exchange of preheated circulating air The temperature of Posterior circle gas is 330 DEG C) and water vapour (in terms of gauge pressure, the pressure of caused water vapour is 4MPa).

Intermediate stream through heat exchange enters the original of the 2nd MTG reactors together with the outlet streams of remaining DME reactors Expect in area, the material in raw material area is entered with catalyst haptoreaction in toroidal container, obtained reactant mixture enters production In thing area, and exported as product stream.Wherein, it is 350 DEG C by the inlet temperature control of the 2nd MTG reactors, by the 2nd MTG The outlet temperature control of reactor is 420 DEG C；It is by the pressure differential control between the outer shroud side wall of toroidal container and interior ring-side wall 50kPa (is held essentially constant) in course of reaction, is 1.7MPa by the outlet pressure control of the 2nd MTG reactors in terms of gauge pressure； Total weight (hourly) space velocity (WHSV) of gas feed is 2h^-1。

In course of reaction, catalyst is passed through into the catalyst charge that is arranged at the top of the toroidal container of the first MTG reactors Pipe is continuously introduced into toroidal container, by the gravity of catalyst itself, is passed to toroidal container, and from ring-shaped container bottom Catalyst discharge nozzle leaves the first MTG reactors.As shown in the dotted portion in Fig. 4, the catalysis of the first MTG reactors will be left Agent is continuously introduced into the 2nd MTG reactors by being arranged on the catalyst charge pipe at the top of the toroidal container of the 2nd MTG reactors In toroidal container, by the gravity of catalyst itself, toroidal container is passed to, and discharge from the catalyst of ring-shaped container bottom Pipe, which leaves the 2nd MTG reactors and is sent into regeneration unit, to be regenerated.By catalyst the first MTG reactors toroidal container It is 500h with the total residence time control in the toroidal container of the 2nd MTG reactors, wherein, catalyst is in the first MTG reactors Toroidal container in residence time it is identical with the residence time in the toroidal container of the 2nd MTG reactors.

Product stream is divided into two strands, respectively enterd in product/circulating air heat exchanger and product/oxygen containing feed heat exchanger, It is respectively used to be exchanged heat (temperature of heat exchange Posterior circle gas is 300 DEG C) with circulating air and fresh methanol is exchanged heat and (obtains temperature Spend the methanol steam for 260 DEG C).After the product stream come out from each heat exchanger is collected, cooled down into product cooler (wherein, cooling medium is water).Further condensation to carry out gas-liquid separation, divides product stream through cooling in gas-liquid separator From as gaseous stream and liquid phase stream.0.5 weight % in the gaseous stream isolated enters fractionating system as discharge pneumatic transmission In, remaining gaseous stream is re-fed into the reaction zone of MTG reactors after being boosted in recycle gas compressor as circulating air.Point The liquid phase stream separated out, which enters in fractionating system, to be fractionated, and obtains fuel gas, liquefied gas and gasoline.

It is carried out continuously the reaction of 500 hours, in tandem reaction sequence, the conversion ratio of methanol and the selectivity of gasoline are in table 2 In list.

Embodiment 6

Methanol is transformed into by gasoline using method same as Example 5, unlike, by catalyst in the first MTG Total residence time control in the toroidal container of the toroidal container of reactor and the 2nd MTG reactors is 300h.

It is carried out continuously the reaction of 300 hours, in tandem reaction sequence, the conversion ratio of methanol and the selectivity of gasoline are in table 2 In list.

Embodiment 7

Methanol is transformed into by gasoline using method same as Example 5, unlike, by catalyst in the first MTG Total residence time control in the toroidal container of the toroidal container of reactor and the 2nd MTG reactors is 700h.

It is carried out continuously the reaction of 700 hours, in tandem reaction sequence, the conversion ratio of methanol and the selectivity of gasoline are in table 2 In list.

Embodiment 8

The present embodiment and the difference of embodiment 5 are that methanol is transformed into gasoline by the technological process shown in reference picture 3, have Body technology flow is as follows.

By the outlet streams of DME reactors and circulating air, (mass ratio for the logistics that circulating air exports with DME reactors is 5： 1) raw material of MTG reactors (specification is identical with the first MTG reactors in embodiment 5 and the 2nd MTG reactors) is sent into together Qu Zhong, methanol is set to enter in toroidal container with catalyst haptoreaction, obtained reactant mixture enters in product area, and conduct Product stream exports.Wherein, it is 340 DEG C by the inlet temperature control of MTG reactors, the outlet temperature of MTG reactors is controlled For 420 DEG C；Pressure differential control between the outer shroud side wall of toroidal container and interior ring-side wall (is protected substantially for 50kPa in course of reaction Hold constant), it is 1.8MPa by the outlet pressure control of MTG reactors in terms of gauge pressure；Total weight (hourly) space velocity (WHSV) of gas feed is 2h^-1。

Catalyst is continuously introduced into toroidal container by being arranged on the catalyst charge pipe at the top of toroidal container, by urging The gravity of agent itself, toroidal container is passed to, and reactor is left from the catalyst discharge nozzle of ring-shaped container bottom, its In, it is 500 hours to control residence time of the catalyst in the toroidal container of reactor.

Product stream is divided into three strands, respectively enters steam generator, product/circulating air heat exchanger and product/oxygen-containing In raw material heat exchanger, it is respectively used to produce water vapour (in terms of gauge pressure, pressure 2MPa), is exchanged heat with circulating air (after heat exchange The temperature of circulating air is 300 DEG C), exchanged heat and (obtain the methanol steam that temperature is 262 DEG C) with fresh methanol.From each heat exchanger After product stream out is collected, cooled down into product cooler (wherein, cooling medium is air).Production through cooling Further condensation to carry out gas-liquid separation, is separated into gaseous stream and liquid phase stream in gas-liquid separator for thing logistics.Separation 0.5 weight % in the gaseous stream gone out enters in fractionating system as discharge pneumatic transmission, and remaining gaseous stream is in recycle gas compressor It is re-fed into after middle boosting as circulating air in the reaction zone of MTG reactors.The liquid phase stream isolated enters in fractionating system It is fractionated, obtains fuel gas, liquefied gas and gasoline.

Embodiment 9

Methanol is transformed into by gasoline using method same as Example 5, unlike, Catalyst packing is first Beds are formed in MTG reactors and the 2nd MTG reactors (that is, in the first MTG reactors and the 2nd MTG reactors, to urge Agent is in non-moving state).

Embodiment 1-9's as a result, it was confirmed that using the present invention method the oxygen containing feed of such as methanol is transformed into gasoline, urge The pressure drop of agent bed is low, so as to be effectively reduced the compression ratio of EGR, reduces operation energy consumption；Also, the present invention Method can also obtain higher methanol conversion and gasoline selective.

Embodiment 5-9 result also demonstrates, by the way that oxygen containing feed is transformed into gasoline in the reaction zone being serially connected, On the one hand the gasoline selective further improved can be obtained, on the other hand can also more effectively reclaims reaction heat, reduce device Energy consumption, and it is more beneficial for the control of reaction temperature.

Claims

1. a kind of method that oxygen containing feed is transformed into gasoline, this method includes making oxygen containing feed and catalyst in the reaction region Haptoreaction, obtains the mixture containing gasoline, and the oxygen containing feed is methanol and/or dimethyl ether, and the catalyst contains point Son sieve, it is characterised in that the reaction zone includes raw material area, product area and catalytic reaction zone, and the catalytic reaction zone is ring Shape arranges and is located at along the axially extending of reaction zone, the oxygen containing feed in the raw material area that the catalyst is urged positioned at described Change in reaction zone, the raw material area and the product area are abutted by the catalytic reaction zone, oxygen-containing in the raw material area Raw material enters the catalytic reaction zone and molecular sieve haptoreaction, and the obtained mixture containing gasoline enters the product area, The catalyst enters from the top of the catalytic reaction zone, along the catalytic reaction zone axially through the catalytic reaction Area, and the catalytic reaction zone is left from the bottom of catalytic reaction zone, the catalyst is during by catalytic reaction zone With oxygen containing feed haptoreaction, leave catalytic reaction zone catalyst alternatively regenerated after, be recycled back to catalytic reaction zone.

2. according to the method for claim 1, wherein, the oxygen containing feed is methanol, and this method also includes pre-reaction step, In the pre-reaction step, at least part methanol is transformed into dimethyl ether, and the mixture that pre-reaction step is obtained is sent Enter in the reaction zone with molecular sieve haptoreaction.

3. wherein, it is according to the method for claim 2,50- by the conversion ratio control of methanol in the pre-reaction step 85 weight %.

4. according to the method in claim 2 or 3, wherein, in the pre-reaction step, reaction temperature is 240-450 DEG C；With Gauge pressure meter, outlet pressure 0.8-3MPa.

5. according to the method for claim 1, wherein, the pressure differential of the catalytic reaction zone both sides is not higher than 100kPa.

6. according to the method for claim 5, wherein, the scope of the pressure differentials of the catalytic reaction zone both sides in 5-100kPa It is interior.

7. according to the method for claim 1, wherein, the molecular sieve is ZSM-5 molecular sieve.

8. the method according to claim 11, wherein, on the basis of the total amount of the ZSM-5 molecular sieve, in terms of oxide, The ZSM molecular sieve contains 0.1-10 weight % phosphorus, 0-10 weight % rare earth.

9. according to the method for claim 8, wherein, the alkali metal content in the ZSM-5 molecular sieve in terms of oxide is Not higher than 0.2 weight %, the mol ratio of silica and aluminum oxide is in the range of 100-1000.

10. according to the method described in any one in claim 7-9, wherein, it is described on the basis of the total amount of the catalyst Catalyst contains 30-95 weight % ZSM-5 molecular sieve, 5-70 weight % inorganic oxide and gluing for 0-50 weight % Soil.

11. according to the method for claim 1, wherein, the oxygen containing feed and the catalytic temperature of catalyst are 280- 500℃；In terms of gauge pressure, outlet pressure 0.8-3MPa；Weight (hourly) space velocity (WHSV) is 0.5-6h^-1。

, will in the separating step 12. according to the method for claim 1, wherein, this method also includes separating step The mixture containing gasoline as product stream output carries out gas-liquid separation, obtains gaseous stream and liquid phase stream, gasoline In the liquid phase stream, sent back at least part gaseous stream as circulating air in the raw material area of reaction zone.

13. according to the method for claim 12, wherein, the mixture containing gasoline as product stream output is being carried out Before gas-liquid separation, exchanged heat with least one heat transferring medium, using as in the mixture containing gasoline that product exports Partial heat take out.

14. according to the method for claim 13, wherein, the heat transferring medium is selected from water, circulating air and oxygen containing feed.

15. according to the method described in any one in claim 1-3,7-9 and 11-14, wherein, the reaction zone contains first Reaction zone and second reaction zone, part oxygen containing feed, with catalyst haptoreaction, and contain in the first reaction zone by what is obtained The mixture of gasoline exports as intermediate stream；The intermediate stream and remainder oxygen containing feed are in second reaction zone with urging Agent haptoreaction, and exported the obtained mixture for containing gasoline as product stream.

16. according to the method for claim 15, wherein, on the basis of the total amount of the oxygen containing feed, reacted into first The amount of the oxygen containing feed in area is 20-70 weight %, and the amount into the oxygen containing feed of second reaction zone is 30-80 weight %.

17. according to the method for claim 15, wherein, the catalyst is from the top of the catalytic reaction zone of the first reaction zone Into along the catalytic reaction zone of first reaction zone axially through the catalytic reaction zone, and from the bottom of catalytic reaction zone The first reaction zone is left, the catalyst, with oxygen containing feed haptoreaction, leaves first during by catalytic reaction zone The catalyst of reaction zone enters into and through the catalytic reaction zone of second reaction zone from top, and the catalysis along the second reaction zone is anti- Answer area axially through the catalytic reaction zone, the catalyst that second reaction zone is left from bottom is alternatively carried out regenerating Posterior circle and returned The catalytic reaction zone of first reaction zone.

18. according to the method for claim 17, wherein, catalyst is anti-in the catalytic reaction zone of the first reaction zone and second The total residence time for answering the catalytic reaction zone in area is 150-800 hours.

19. according to the method for claim 18, wherein, catalyst is anti-in the catalytic reaction zone of the first reaction zone and second The total residence time for answering the catalytic reaction zone in area is 300-700 hours.

20. according to the method for claim 19, wherein, catalyst is anti-in the catalytic reaction zone of the first reaction zone and second The total residence time for answering the catalytic reaction zone in area is 400-600 hours.

21. according to the method for claim 15, wherein, the intermediate stream is situated between before second reaction zone is entered with heat exchange Matter is exchanged heat, and the partial heat in the intermediate stream is taken out.

22. according to the method for claim 21, wherein, the intermediate stream is exchanged heat with circulating air and water successively, Water is caused to be transformed into water vapour with the condition of water heat exchange.