CN105130729A - Durene-poly-generation technological method and production system for preparing light hydrocarbon through methyl alcohol - Google Patents
Durene-poly-generation technological method and production system for preparing light hydrocarbon through methyl alcohol Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The invention relates to a durene-poly-generation technological method and production system for preparing light hydrocarbon through methyl alcohol. The technological method is adopted for the production system. The technological method includes the steps that multiple moving bed synthesis reactors connected in series form a synthesis reaction system; the methyl alcohol or the water-contained methyl alcohol serves as raw materials and is mixed with circulating gas, then the mixture is introduced into the synthesis reaction system to be subjected to a catalysis reaction, and a reaction product containing the C1-C11 light hydrocarbon is generated; an oil phase in the reaction product is further separated to prepare gasoline blending components and the high-purity durene; the circulating gas serves as heat carriers of heat generated by the reaction, and the synthesis reaction temperature is controlled to control the component distribution of the synthesis reaction product and the yield of the target product to enable the mass ratio of the durene to the hydrocarbon in the reaction product to be larger than or equal to 10%. The system comprises the corresponding synthesis reaction system and the light hydrocarbon separating system. By means of the technological method and production system, continuous production of light hydrocarbon produced through the methyl alcohol and poly-production of the durene and the like is achieved, technological conditions are stable and easy to control, and product quality is good.
Description
Technical field
The present invention relates to a kind of Methanol lighter hydrocarbons processing method of Poly-generation durol, also relate to a kind of Methanol lighter hydrocarbons production system adopting the Poly-generation durol of the method, belong to chemical technology field.
Background technology
Crude oil is a kind of important Nonrenewable resources, is a kind of strategic resource being related to national economy.China is an oil consumption big country, a large amount of import of current crude oil, and the crude oil external dependence degree of China continues can not increase any more.Coal resources in China relative abundance, the rapid rising of Coal Chemical Industry, particularly prepares fuel gasoline by coal in recent years, provides a practicable approach for alleviating oil shortage situation.By coal, through intermediates methyl alcohol, resynthesis gasoline, and the Chemicals of by-product liquefied petroleum gas (LPG), high performance fuel gas and high added value.Compared to DCL/Direct coal liquefaction gasoline and synthesis gas from coal gasification through F-T synthesis gasoline, the made benzene content in gasoline of Methanol lighter hydrocarbons is low, product quality is high, is paid attention to more and more widely.
Existing is using methyl alcohol as raw material with Methanol for the method for lighter hydrocarbons, and adopt fixed-bed reactor, under the catalysis of catalyzer, methanol dehydration is formed and generates dme, and dme dewaters generation hydro carbons further.This Methanol is that fixed-bed reactor can not operate continuously for the defect one of lighter hydrocarbons method, and catalyzer coking is fast, needs frequent regeneration; Two is that reaction heat can not remove very well, only controls temperature of reaction, poor controllability by cold methanol charging, can not ensure stable processing condition, is difficult to control reaction process and product composition, causes unstable product quality.
On the other hand, durol is the one that in current many toluene, industrial use is wider, mainly for the production of pyromellitic acid anhydride or equal acid anhydride, because its methyl is very active, has higher selectivity and high speed of response, is industrially more and more paid attention to.The raw material preparing durol is at present mainly derived from naphtha cracking or catalytic reforming aromatic hydrocarbons.But due to petroleum resources shortage, the many dependence on import of domestic crude oil, so the raw material preparing durol is limited.Compared to the shortage of petroleum resources, China's methyl alcohol production capacity compares demand in recent years is but present serious superfluous situation.Therefore, develop Poly-generation durol Methanol lighter hydrocarbons tool to be of great significance.
Summary of the invention
In order to overcome the above-mentioned defect of prior art, the invention provides a kind of Methanol lighter hydrocarbons processing method of Poly-generation durol, also relate to a kind of Methanol lighter hydrocarbons production system adopting the Poly-generation durol of the method, to realize the continuous seepage of Methanol lighter hydrocarbons, and stable process conditions and be easy to control, good product quality.
Technical scheme of the present invention is:
A kind of Methanol lighter hydrocarbons processing method of Poly-generation durol, to be equipped with the continuous generating moving-bed reactor of catalyzer for synthesis reactor, with the multistage synthesis reactor composition synthesis reaction system of mutually connecting, it is characterized in that mixing with circulation gas for raw material with methyl alcohol or aqueous methanol, pass into synthesis reaction system and carry out catalyzed reaction, temperature of reaction is 250-450 DEG C, pressure is 1.0-6.0MPaG, generate the reaction product comprising C1-C11 lighter hydrocarbons, reaction product is carried out liquid-liquid three phase separation, isolate noncondensable gas, water and oily three-phase, using after three phase separation most of noncondensable gas pressurization out as described circulation gas Returning reacting system, oil phase produces gasoline blending component and high purity durol through being separated further, methyl alcohol and circulation gas heated separately and/or together heat after mixing before entering reactive system, reactor is entered after making it reach the temperature of reaction of the first synthesis reactor, between each synthesis reactor, adopt inter-stage heat-obtaining mode to remove the part or all of reaction Heat of Formation of prime synthesis reactor, thermophore using circulation gas as reaction Heat of Formation, by controlling building-up reactions pressure and temperature with the yield of the component distribution and target product that control building-up reactions product, the mass ratio making durol in reaction product account for hydro carbons is not less than 10%.
Described catalyzer can adopt ZSM-5 molecular sieve catalyzer, the silica alumina ratio of described ZSM-5 molecular sieve catalyzer is 40-60, and molecular sieve bore diameter is 0.4-0.5nm, and particle diameter is about 1.6-2.0mm, load or not loaded metal component on molecular sieve, the weight hourly space velocity of described synthesis reaction system is 0.5-8hr
-1, in described synthesis reaction system, synthesis reactor quantity is 2-4, and the temperature of reaction of each reactor is identical or different.
Synthesis reaction system is provided with moving bed reaction regeneration system rapidly, described moving bed reaction regeneration system rapidly is can quantity-produced reaction-regeneration system, regeneration system rapidly regeneration is entered continuously from synthesis reactor catalyzer to be regenerated out, regenerate and entered synthesis reactor continuously afterwards, described moving bed reaction regeneration system rapidly has universality to catalyzer, in described reaction-regeneration system, synthesis reactor quantity is 2-4, regeneration reactor 1-2.
Methanol feedstock is except passing into the first moving-burden bed reactor, can also pass into and also can not pass into other moving-burden bed reactors, when needs pass into multiple moving-burden bed reactor, by relevant methyl alcohol transport pipe some roads respectively, corresponding moving-burden bed reactor can be accessed respectively.
Regeneration temperature is 350-600 DEG C, pressure 0.1-1.0MPaG, and the rare gas element of resurgent gases to be oxygen level be 0.1-21%, when catalyst cupport metal component, revivifier burns CO, CO in gas
2content <3%.
The methyl alcohol entering the first synthesis reactor first enters the first synthesis reactor again or directly enters the first synthesis reactor without methanol etherification reactor after methanol etherification reactor reaction, and described methanol etherification reactor is fixed-bed reactor.
Controlled the temperature of reactor by the inter-stage heat-obtaining between synthesis reactor, described inter-stage heat-obtaining mode comprises the modes such as heating process material, byproduct steam.
Separation of oil after adopting following manner to carry out three phase separation, to produce gasoline blending component and high purity durol: the oil phase that three phase separation goes out is sent into deethanizing column and carried out being separated of C2-with C3+, deethanizer overhead extraction C2-gas phase, extraction C3+ liquid phase at the bottom of tower, the C3+ liquid phase of extraction at the bottom of deethanizing column tower is sent into debutanizing tower and carries out being separated of C4-with C5+, debutanizing tower overhead extraction liquefied gas, extraction C5+ liquid phase at the bottom of tower, the C5+ liquid phase of extraction at the bottom of debutanizing tower tower is sent into stable light hydrocarbon tower and removes heavy aromatics, the extraction of stable light hydrocarbon column overhead removes the C5+ mixture after heavy aromatics, extraction C10+ heavy aromatics at the bottom of tower, C10+ heavy aromatics is sent into heavy aromatics tower and carry out being separated of C10 heavy aromatics and C11 heavy aromatics, the mixture of extraction C11+ heavy aromatics at the bottom of heavy aromatics tower tower, overhead extraction is containing C10 heavy aromatics, the Crystallization Separation that crystal system carries out C10 heavy aromatics is sent in the extraction of C10 heavy aromatics, isolate durol product and crystalline mother solution, described durol product is highly purified durol.
Preferably, durol accounts for total hydrocarbon is 10-30%(mass ratio).
A kind of Methanol lighter hydrocarbons production system of Poly-generation durol, comprise and generate the synthesis reaction system of lighter hydrocarbons and the lighter hydrocarbons separation system for producing gasoline blending component and high purity durol for methyl alcohol reaction, described synthesis reaction system is provided with the synthesis reactor of connecting successively, also be provided with catalyst regeneration system, described catalyst regeneration system mainly comprises revivifier and catalyst delivery system, described synthesis reactor is the continuous generating moving-bed reactor that catalyzer is housed, interstage cooler is provided with between described synthesis reactor, described interstage cooler adopts the heat exchanger of any suitable, the hot test tube road of described interstage cooler is serially connected on the material conveying pipe (connecting tube between the outlet of prime synthesis reactor and the import of rear class synthesis reactor) between corresponding synthesis reactor, in described synthesis reaction system, the output channel of last step synthesis reactor is through the three phase separation tank described in the connection of Reactive Synthesis Gas Cooler, described synthesis reaction system is provided with feed duct road, described feed duct road connects methanol source, such as methyl alcohol output channel or methanol tank, described feed duct road is connected in series the cold side ducts of the part or all of water cooler in described Reactive Synthesis Gas Cooler and described interstage cooler, when described feed duct road connecting the heat-absorbing medium pipeline of multiple interstage cooler, the serial connection sequence of heat-absorbing medium passage on described feed duct road of the multiple interstage coolers be connected in series is preferably backward (contrary through order with the streams of reaction system), described feed duct road connects the import of the first synthesis reactor, described feed duct road is also provided with or is not provided with the corresponding charging conveying arm of other synthesis reactor connected except the first synthesis reactor, the gas phase output channel of described three phase separation tank is divided into two-way, one tunnel connects the import of gas compressor, another road connects import at the bottom of the tower on the absorption tower for absorbing C3+, the output channel of described gas compressor accesses described feed duct road, before access position is at least positioned at a water cooler (with the importer of water cooler heat-absorbing medium to for front), the oil phase output channel of described three phase separation tank connects the import being used for the deethanizing column that C2-with C3+ is separated, the gas phase output channel of described deethanizer overhead connects import at the bottom of the tower on described absorption tower, liquid phase output channel at the bottom of described deethanizing column tower connects the import being used for the debutanizing tower (liquefied gas tower) that C4-with C5+ is separated, liquid phase output channel at the bottom of described absorbing tower connects the import of described deethanizing column, the gas phase output channel of described absorption tower tower top sends the main mixture containing C1 and C2, can be used as Sweet natural gas, the gas phase output channel of described debutanizing tower tower top sends the main mixture containing C3 and C4, can be used as liquefied gas, liquid phase output channel at the bottom of tower is divided into two-way, one tunnel connects the stable light hydrocarbon tower for removing heavy aromatics, another road connects the absorption liquid import of described absorption tower tower top, the output channel of described stable light hydrocarbon column overhead send and remove heavy aromatics after C5+ mixture, can be used as gasoline blending component, output channel at the bottom of tower connects the import of the heavy aromatics tower for separating of C10 heavy aromatics and C11 heavy aromatics, the mixture containing heavy aromatics component separated by stable light hydrocarbon tower sends into heavy aromatics tower, the output channel of described heavy aromatics column overhead connects the crystal system being used for the crystallization of C10 heavy aromatics, the mixture containing C10 heavy aromatics separated by described heavy aromatics tower sends into crystal system, described crystal system carries out crystallization to C10 heavy aromatics and is separated with xln, the xln produced is high purity durol, output channel at the bottom of described heavy aromatics tower tower sends C11 heavy aromatics.
Beneficial effect of the present invention: with the interstage cooler of synthesis reactor and Reactive Synthesis Gas Cooler, raw material is heated owing to have employed, take full advantage of reaction heat production, when not needing heating energy consumption, the raw material entering synthesis reactor is made to have suitable temperature, be conducive to carrying out smoothly of reaction, achieve heat-obtaining between reactor grade simultaneously, reaction heat is removed from reaction system, thus avoid the overheated harm brought, heating strength particularly due to correlated response is higher, it is larger that temperature controls difficulty, often because temperature controls the bad fluctuation causing quality product, and after adopting inter-stage heat-obtaining, reduce circulation gas consumption, reduce plant energy consumption, after adopting inter-stage heat-obtaining and circulation gas to carry out temperature control, significantly reduce control difficulty, be conducive to realizing stable and suitable reaction conditions, particularly effectively can control the component distribution of reaction product and the yield of target product, the lifting that the stability of quality product and quality product obtains by a relatively large margin can be made, also help the carbon distribution and coking that reduce catalyzer, enhance productivity, the regeneration period of extending catalyst and work-ing life, alleviate the load of catalyst regeneration system, with can other reactors of cyclic regeneration compare, moving-burden bed reactor is not high to catalytic mechanical performance requriements, there is good suitability to not same catalyst, add the suitability of moving bed reaction regeneration system rapidly to various catalyzer, reduce the difficulty of engineering construction, due to the combination of the separating technology and equipment that have employed adaptation, by the mutual coordination of each separating technology and equipment, resultant of reaction is separated into some useful products, achieves the object of Poly-generation, and the good product purity separated, quality is good.Present invention achieves continuous seepage and Poly-generation, and stable process conditions and be easy to control, good product quality.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of an embodiment of the present invention;
Fig. 2 is the schematic flow sheet of another embodiment of the present invention;
Fig. 3 is the schematic flow sheet of the third embodiment of the present invention.
Embodiment
See Fig. 1-3, the invention provides a kind of Methanol lighter hydrocarbons processing method of Poly-generation durol, it is to be equipped with the continuous generating moving-bed reactor of catalyzer for synthesis reactor, with the multistage synthesis reactor composition synthesis reaction system of mutually connecting, be raw material with methyl alcohol and mix with circulation gas, pass into reactive system and carry out catalyzed reaction, temperature of reaction is 250-450 DEG C, generation comprises the reaction product of C1-C11 lighter hydrocarbons (carbon one to carbon 11 hydrocarbon polymer), reaction product is carried out liquid-liquid three phase separation, isolate noncondensable gas, water and oily three-phase, using after three phase separation most of noncondensable gas pressurization out as described circulation gas Returning reacting system, oil phase produces gasoline blending component and high purity durol through being separated further, methyl alcohol and circulation gas heated separately and/or together heat after mixing before entering reactive system, the temperature making it reach the first synthesis reactor (first step synthesis reactor in described reactive system) to require, between each synthesis reactor, adopt inter-stage heat-obtaining mode to remove the part or all of reaction Heat of Formation of prime synthesis reactor, thermophore using circulation gas as reaction Heat of Formation, control synthesis reaction temperature with the yield of the component distribution and target product that control building-up reactions product, the mass ratio making durol in reaction hydrocarbon product account for hydro carbons is not less than 10%, preferably be not less than 20%, preferably be not less than 23% further.
Preferably, described catalyzer adopts ZSM-5 molecular sieve catalyzer (comprising the ZSM-5 Type Zeolites agent formed after carrying out modification to ZSM-5 molecular sieve catalyzer), the THP-1 type catalyzer of preferably Tianjin chemical research institute of CNOOC production further, to change silica alumina ratio, regulate surface acidity, improve pore structure, optimized choice, improve carbon accumulation resisting ability, the silica alumina ratio of described ZSM-5 molecular sieve catalyzer is preferably 40-60, molecular sieve bore diameter is preferably 0.4-0.5nm, and particle diameter is preferably about 1.6-2.0mm.According to the experiment of manufacturer, through this modified, be conducive to the productive rate improving durol, be conducive to extending catalyst regeneration period and work-ing life.
Optionally, described ZSM-5 Type Zeolites agent can loaded metal ion, such as loaded Cu/Zn, also can not loaded metal ion.
Preferably, when catalyzer be ZSM-5 molecular sieve catalyzer or ZSM-5 Type Zeolites agent, the weight hourly space velocity of synthesis reaction system is 0.5-8hr
-1, to obtain better reaction effect and transformation efficiency.
Optionally, in described synthesis reaction system, synthesis reactor quantity is 2-4, or other quantity, such as, is preferably 3.
Optionally, all enter synthesis reaction system from the first synthesis reactor (synthesis reactor of foremost) after methyl alcohol and circulation gas mixing, or methyl alcohol is divided into some stocks, enters synthesis reaction system respectively from each synthesis reactor.
Preferably, when methyl alcohol is divided into some stocks not enter each synthesis reactor, the methanol ratio entering the first synthesis reactor is preferably about 70%, such as, and 65-73%.
Preferably, the type of heating carrying out to methyl alcohol and circulation gas before entering synthesis reactor is: first the reacting synthesis gas that methyl alcohol and synthesis reaction system export is carried out heat exchange, again and the reaction mass carried between synthesis reactor carry out heat exchange and inter-stage heat-obtaining described in being realized by this heat exchange method, circulation gas is introduced in the heating path of methyl alcohol, together follow-up heating installation is carried out after making itself and methanol mixed, introduce the position of circulation gas at least before the first interstage cooler (water cooler between the first synthesis reactor and the second synthesis reactor).
Optionally, the methyl alcohol entering the first synthesis reactor first enters the first synthesis reactor again or directly enters the first synthesis reactor without methanol etherification reactor after methanol etherification reactor reaction, the preferred fixed-bed reactor of described methanol etherification reactor.
Preferably, the separation of oil after adopting following manner to carry out three phase separation, to produce gasoline blending component and high purity durol:
Oil phase that three phase separation goes out is sent into deethanizing column and is carried out C2-(bis-carbon and following hydrocarbon polymer) with C3+(tri-carbon and above hydrocarbon polymer) be separated, deethanizer overhead extraction C2-gas phase, extraction C3+ liquid phase at the bottom of tower, by the C3+ liquid phase of extraction at the bottom of deethanizing column tower send into debutanizing tower (liquefied gas tower) carry out C4-(tetra-carbon and following hydrocarbon polymer) with C5+(five carbon and above hydrocarbon polymer) be separated, debutanizing tower overhead extraction C3-C4 component, can be used as liquefied gas, extraction C5+ liquid phase at the bottom of tower, the C5+ liquid phase of extraction at the bottom of debutanizing tower tower is sent into stable light hydrocarbon tower and removes heavy aromatics, the extraction of stable light hydrocarbon column overhead removes the C5+ mixture after heavy aromatics, can be used as gasoline blending component, extraction at the bottom of tower is containing the mixture of heavy aromatics component, mixture containing heavy aromatics component is sent into heavy aromatics tower and carry out being separated of C10 heavy aromatics and C11+ heavy aromatics, extraction at the bottom of heavy aromatics tower tower is containing the mixture of C11+ heavy aromatics, overhead extraction is containing the mixture of C10 heavy aromatics, the mixture containing C10 heavy aromatics of heavy aromatics column overhead extraction is sent into the crystallization that crystal system carries out C10 heavy aromatics, isolate C10 heavy aromatics xln and crystalline mother solution, described C10 heavy aromatics xln is highly purified durol.
Preferably, the C2-gas phase of deethanizer overhead extraction is sent into absorption tower and carries out C3+ absorption, absorption liquid preferably adopts the C5+ liquid phase from extraction at the bottom of debutanizing tower tower, preferred further the major part in the C5+ liquid phase of extraction at the bottom of debutanizing tower tower is sent into absorption tower as absorption liquid, be more highly purified C2-gas from the noncondensable gas of absorption tower overhead extraction, can be used as lightweight gas or Sweet natural gas, extraction at the bottom of absorbing tower absorbs the absorption liquid after C3+, send the absorption liquid after the absorption C3+ of extraction at the bottom of absorbing tower back to deethanizing column and together carry out corresponding being separated to the oil phase formed through three phase separation.
Preferably, the part not being used as circulation gas in the noncondensable gas formed three phase separation is sent at the bottom of absorbing tower as periodic off-gases, counter-current absorption is carried out with absorption liquid in absorption tower, together enter deethanizing column with absorption liquid after C3+ component is wherein absorbed by liquid absorption, C2-component becomes the part in the noncondensable gas of absorption tower overhead extraction.
Present invention also offers a kind of Methanol lighter hydrocarbons production system adopting the Poly-generation durol of any one preparation method above-mentioned, this system comprises for the methyl alcohol reaction generation synthesis reaction system of lighter hydrocarbons and the lighter hydrocarbons separation system for producing gasoline blending component and high purity durol, described synthesis reaction system is provided with the synthesis reactor of connecting successively, also be provided with catalyst regeneration system, described catalyst regeneration system mainly comprises revivifier and catalyzer lifting system, described synthesis reactor is the continuous generating moving-bed reactor that catalyzer is housed, interstage cooler is provided with between each described synthesis reactor, described interstage cooler adopts the heat exchanger of any suitable, the hot test tube road of described interstage cooler is serially connected on the material conveying pipe (connecting tube between the outlet of prime synthesis reactor and the import of rear class synthesis reactor) between corresponding synthesis reactor, in described synthesis reaction system, the output channel of last step synthesis reactor is through the three phase separation tank described in the connection of Reactive Synthesis Gas Cooler, described synthesis reaction system is provided with feed duct road, described feed duct road connects methanol source, such as methyl alcohol output channel or methanol tank, described feed duct road is connected in series the cold test tube road of the part or all of water cooler in described Reactive Synthesis Gas Cooler and described interstage cooler, when described feed duct road is connected in series the cold side ducts of multiple interstage cooler, the serial connection sequence of heat-absorbing medium passage on described feed duct road of the multiple interstage coolers be connected in series is preferably backward (contrary through order with the streams of reaction system), described feed duct road connects the import of the first synthesis reactor, described feed duct road is also provided with or is not provided with the corresponding charging conveying arm of other synthesis reactor connected except the first synthesis reactor, the gas phase output channel of described three phase separation tank is divided into two-way, one tunnel connects the import of gas compressor, another road connects import at the bottom of the tower on the absorption tower for absorbing C3+, the output channel of described gas compressor accesses described feed duct road, before access position is at least positioned at a water cooler (with the importer of water cooler heat-absorbing medium to for front), the oil phase output channel of described three phase separation tank connects the import being used for the deethanizing column that C2-with C3+ is separated, the gas phase output channel of described deethanizer overhead connects import at the bottom of the tower on described absorption tower, liquid phase output channel at the bottom of described deethanizing column tower connects the import being used for the debutanizing tower (liquefied gas tower) that C4-with C5+ is separated, liquid phase output channel at the bottom of described absorbing tower connects the import of described deethanizing column, the gas phase output channel of described absorption tower tower top sends the main mixture containing C1 and C2, can be used as Sweet natural gas, the gas phase output channel of described debutanizing tower tower top sends the main mixture containing C3 and C4, can be used as liquefied gas, liquid phase output channel at the bottom of tower is divided into two-way, one tunnel connects the stable light hydrocarbon tower for removing heavy aromatics, another road connects the absorption liquid import of described absorption tower tower top, the output channel of described stable light hydrocarbon column overhead send and remove heavy aromatics after C5+ mixture, can be used as gasoline, output channel at the bottom of tower connects the import of the heavy aromatics tower for separating of C10 heavy aromatics and C11 heavy aromatics, the mixture containing heavy aromatics component separated by stable light hydrocarbon tower sends into heavy aromatics tower, the output channel of described heavy aromatics column overhead connects the crystal system being used for the crystallization of C10 heavy aromatics, the mixture containing C10 heavy aromatics separated by described heavy aromatics tower sends into crystal system, described crystal system carries out crystallization to C10 heavy aromatics and is separated with xln, the xln produced is high purity durol, output channel at the bottom of described heavy aromatics tower tower sends C11 heavy aromatics.
Preferably, described feed duct road is serially connected with methanol etherification reactor, the preferred fixed-bed reactor of described methanol etherification reactor, before the access position of described methanol etherification reactor on described feed duct road is at least positioned at a water cooler.
Preferably, described catalyzer adopts ZSM-5 molecular sieve catalyzer, preferably adopts the THP-1 type catalyzer of Tianjin chemical research institute of CNOOC development further, to change silica alumina ratio, regulates surface acidity, improves pore structure, optimized choice, improve carbon accumulation resisting ability.
Preferably, the silica alumina ratio of described ZSM-5 molecular sieve catalyzer is 40-60, and molecular sieve bore diameter is 0.4-0.5nm, and particle diameter is about 1.6-2.0mm.According to the experiment of applicant, through this modified, be conducive to the productive rate improving durol, be conducive to extending catalyst regeneration period and work-ing life.
Optionally, described ZSM-5 Type Zeolites agent can loaded metal ion, such as loaded Cu/Zn, also can not loaded metal ion.
Optionally, in described synthesis reaction system, synthesis reactor quantity is 2-4, or other quantity, such as, is preferably 3.
Preferably, the hot test tube road of part interstage cooler is connected on described feed duct road, and the hot test tube road of other interstage coolers connects steam generating conduit, and the water sent into entrance end carries out heating and become pressure or steam with no pressure and sent from exit end.
Here is several embodiments of the present invention:
Embodiment 1(is see Fig. 1): catalyzer adopts the THP-1 type catalyzer of Tianjin chemical research institute of CNOOC development, silica alumina ratio is 40, molecular sieve bore diameter is 0.4nm, particle diameter is 1.6mm, methanol etherification reactor is fixed-bed reactor, and synthesis reactor is 3 sections of moving-burden bed reactors and is provided with corresponding regeneration system rapidly.Vaporize after the reacting synthesis gas heat exchange of raw material refined methanol and high temperature, three strands are divided after being recycled gas heating again, the main raw material accounting for 70% send methanol etherification reactor to generate dme, moving-bed first synthesis reactor is sent into after circulation gas mixing, 20% methyl alcohol and synthesis pneumatic transmission second synthesis reactor going out the first synthesis reactor, 10% methyl alcohol send the 3rd synthesis reactor with the synthetic gas mixing going out the second synthesis reactor.Concrete temperature of reaction is 400 DEG C, and reaction pressure is 5MPaG, and weight hourly space velocity is 1h
-1, regenerative operation condition is service temperature 500 DEG C, working pressure 0.5MPaG.
Synthesis reactor inter-stage arranges the Reactive Synthesis Gas Cooler (interstage cooler) of inter-stage, and the high-temperature gas reaction mass utilizing reactor to carry carrys out preheating material, thus removes exothermic heat of reaction.Synthesis reaction system exports the high-temperature synthesis gas of (i.e. the outlet of last step synthesis reactor) after heat exchange cooling, three phase separation, waste water send stripper plant process, and gas phase is except partly speeding to put, enter synthesis reactor through compressor boosting Posterior circle, oil phase send subsequent separation system.Reaction generates oil after desorption desorb, and de-C2-non-condensable gas, takes off liquefied gas thereafter again, obtains gasoline component and heavy aromatics after de-heavy aromatics.After the heavy aromatics that obtains removes C11 heavy constituent, obtain the C10 aromatic hydrocarbons containing durol >=90%, send into follow-up freezing fusion-crystallization system, obtain durol product, crystalline mother solution is as byproduct extraction.Processing condition and reaction result and hydrocarbon component products distribution as shown in the table.
The processing condition of embodiment 1 and reaction result:
Embodiment 2(is see Fig. 2): primary condition is equal to embodiment 1, and difference is: cancel methanol etherification reactor, and adopt single stage method, methyl alcohol, after preheating, directly enters moving-burden bed reactor.Processing condition and reaction result and hydrocarbon component products distribution as shown in the table.
Embodiment 2 processing condition and reaction result:
Embodiment 3(is see Fig. 3): catalyzer adopts the THP-1 type catalyzer of Tianjin chemical research institute of CNOOC development, and silica alumina ratio is 60, and molecular sieve bore diameter is 0.5nm, and particle diameter is 2mm.Raw material is refined methanol, vaporize with after high-temperature synthesis gas heat exchange, four strands are divided after being recycled gas heating again, send the moving bed reaction regeneration system rapidly that HZSM-5 catalyzer is housed, synthesis reactor is 4 sections of moving-burden bed reactors, raw material feed postition is one 70% methyl alcohol and circulation gas mixing feeding first synthesis reactor, 10% methyl alcohol send the second synthesis reactor with the synthetic gas mixing going out the second synthesis reactor, 10% methyl alcohol send the 3rd synthesis reactor with the synthetic gas mixing going out the second synthesis reactor, 10% methyl alcohol send the 4th synthesis reactor with the synthetic gas mixing going out the 3rd synthesis reactor.Concrete temperature of reaction is 350 DEG C, and reaction pressure is 3MPaG, and weight hourly space velocity is 2h
-1.Regenerative operation condition is service temperature 450 DEG C, working pressure 0.4MPaG.
Synthesis reactor inter-stage arranges Reactive Synthesis Gas Cooler, utilizes high-temperature synthesis gas to carry out preheating material, and produces middle pressure steam, thus remove exothermic heat of reaction.Synthesis reactor outlet high-temperature synthesis gas is after heat exchange cooling, and three phase separation, waste water send stripper plant process, and gas phase is except partly speeding to put, and enter synthesis reactor through compressor boosting Posterior circle, oil phase send subsequent separation system.Reaction generation oil is received after parsing through desorption, and de-C2-non-condensable gas, takes off liquefied gas thereafter again, obtains gasoline component after de-heavy aromatics.After the heavy aromatics that obtains removes C11 heavy constituent, obtain the C10 aromatic hydrocarbons containing durol >=88%, send into follow-up freezing fusion-crystallization system and obtain durol product, crystalline mother solution is as byproduct extraction.Processing condition and reaction result and hydrocarbon component products distribution as shown in the table.
Embodiment 3 processing condition and reaction result:
Non-specifically illustrates or separately has outside clear and definite implication, and moving-burden bed reactor alleged by this specification sheets refers to the synthesis reactor adopting moving-bed form.
Each preferred and optional technique means disclosed by the invention, unless otherwise indicated and one preferably or alternatives means be outside the further restriction of another technique means, all can arbitrary combination, form some different technical schemes.
Claims (10)
1. the Methanol lighter hydrocarbons processing method of a Poly-generation durol, to be equipped with the continuous generating moving-bed reactor of catalyzer for synthesis reactor, with the multistage synthesis reactor composition synthesis reaction system of mutually connecting, it is characterized in that mixing with circulation gas for raw material with methyl alcohol or aqueous methanol, pass into synthesis reaction system and carry out catalyzed reaction, temperature of reaction is 250-450 DEG C, pressure is 1.0-6.0MPaG, generate the reaction product comprising C1-C11 lighter hydrocarbons, reaction product is carried out liquid-liquid three phase separation, isolate noncondensable gas, water and oily three-phase, using after three phase separation most of noncondensable gas pressurization out as described circulation gas Returning reacting system, oil phase produces gasoline blending component and high purity durol through being separated further, methyl alcohol and circulation gas heated separately and/or together heat after mixing before entering reactive system, reactor is entered after making it reach the temperature of reaction of the first synthesis reactor, between each synthesis reactor, adopt inter-stage heat-obtaining mode to remove the part or all of reaction Heat of Formation of prime synthesis reactor, thermophore using circulation gas as reaction Heat of Formation, by controlling building-up reactions pressure and temperature with the yield of the component distribution and target product that control building-up reactions product, the mass ratio making durol in reaction product account for hydro carbons is not less than 10%.
2. the method for claim 1, it is characterized in that described catalyzer adopts ZSM-5 molecular sieve catalyzer, the silica alumina ratio of described ZSM-5 molecular sieve catalyzer is 40-60, molecular sieve bore diameter is 0.4-0.5nm, particle diameter is about 1.6-2.0mm, load or not loaded metal component on molecular sieve, the weight hourly space velocity of described synthesis reaction system is 0.5-8hr
-1, in described synthesis reaction system, synthesis reactor quantity is 2-4, and the temperature of reaction of each reactor is identical or different.
3. the method for claim 1, it is characterized in that synthesis reaction system is provided with moving bed reaction regeneration system rapidly, described moving bed reaction regeneration system rapidly is can quantity-produced reaction-regeneration system, regeneration system rapidly regeneration is entered continuously from synthesis reactor catalyzer to be regenerated out, regenerate and entered synthesis reactor continuously afterwards, in described reaction-regeneration system, synthesis reactor quantity is 2-4, regeneration reactor 1-2.
4. the method as described in claim 1,3, is characterized in that methanol feedstock except passing into the first moving-burden bed reactor, also passes into or does not pass into other moving-burden bed reactors.
5. the method as described in claim 1,3, is characterized in that regeneration temperature is 350-600 DEG C, pressure 0.1-1.0MPaG, and the rare gas element of resurgent gases to be oxygen level be 0.1-21%, when catalyst cupport metal component, revivifier burns CO, CO in gas
2content <3%.
6. the method as described in claim 1,2,3 or 4, it is characterized in that the methyl alcohol entering the first synthesis reactor first enters the first synthesis reactor again or directly enters the first synthesis reactor without methanol etherification reactor after methanol etherification reactor reaction, described methanol etherification reactor is fixed-bed reactor.
7. the method as described in claim 1,5, it is characterized in that the molar ratio of the global cycle gas and methyl alcohol entering reactive system is 0-10, the mass ratio that durol accounts for total hydrocarbon is 10-30%.
8. the method for claim 1, the inter-stage heat-obtaining between it is characterized in that by synthesis reactor controls the temperature of reactor, and described inter-stage heat-obtaining mode comprises the modes such as heating process material, byproduct steam.
9. as claim 1, 2, method described in 3 or 4, it is characterized in that the separation of oil after adopting following manner to carry out three phase separation, to produce gasoline blending component and high purity durol: the oil phase that three phase separation goes out is sent into deethanizing column and carried out being separated of C2-with C3+, deethanizer overhead extraction C2-gas phase, extraction C3+ liquid phase at the bottom of tower, the C3+ liquid phase of extraction at the bottom of deethanizing column tower is sent into debutanizing tower and carries out being separated of C4-with C5+, debutanizing tower overhead extraction liquefied gas, extraction C5+ liquid phase at the bottom of tower, the C5+ liquid phase of extraction at the bottom of debutanizing tower tower is sent into stable light hydrocarbon tower and removes heavy aromatics, the extraction of stable light hydrocarbon column overhead removes the C5+ mixture after heavy aromatics, extraction C10+ heavy aromatics at the bottom of tower, C10+ heavy aromatics is sent into heavy aromatics tower and carry out being separated of C10 heavy aromatics and C11 heavy aromatics, the mixture of extraction C11+ heavy aromatics at the bottom of heavy aromatics tower tower, overhead extraction is containing C10 heavy aromatics, the Crystallization Separation that crystal system carries out C10 heavy aromatics is sent in the extraction of C10 heavy aromatics, isolate durol product and crystalline mother solution, described durol product is highly purified durol.
10. the Methanol lighter hydrocarbons production system of a Poly-generation durol, it is characterized in that comprising and generate the synthesis reaction system of lighter hydrocarbons and the lighter hydrocarbons separation system for producing gasoline blending component and high purity durol for methyl alcohol reaction, described synthesis reaction system is provided with the synthesis reactor of connecting successively, also be provided with catalyst regeneration system, described catalyst regeneration system mainly comprises revivifier and catalyst delivery system, described synthesis reactor is the continuous generating moving-bed reactor that catalyzer is housed, interstage cooler is provided with between described synthesis reactor, described interstage cooler adopts the heat exchanger of any suitable, the hot test tube road of described interstage cooler is serially connected on the material conveying pipe between corresponding synthesis reactor, in described synthesis reaction system, the output channel of last step synthesis reactor is through the three phase separation tank described in the connection of Reactive Synthesis Gas Cooler, described synthesis reaction system is provided with feed duct road, described feed duct road connects methanol source, such as methyl alcohol output channel or methanol tank, described feed duct road is connected in series the cold side ducts of the part or all of water cooler in described Reactive Synthesis Gas Cooler and described interstage cooler, when described feed duct road connecting the heat-absorbing medium pipeline of multiple interstage cooler, the serial connection sequence of heat-absorbing medium passage on described feed duct road of the multiple interstage coolers be connected in series is preferably backward, described feed duct road connects the import of the first synthesis reactor, described feed duct road is also provided with or is not provided with the corresponding charging conveying arm of other synthesis reactor connected except the first synthesis reactor, the gas phase output channel of described three phase separation tank is divided into two-way, one tunnel connects the import of gas compressor, another road connects import at the bottom of the tower on the absorption tower for absorbing C3+, the output channel of described gas compressor accesses described feed duct road, before access position is at least positioned at a water cooler, the oil phase output channel of described three phase separation tank connects the import being used for the deethanizing column that C2-with C3+ is separated, the gas phase output channel of described deethanizer overhead connects import at the bottom of the tower on described absorption tower, liquid phase output channel at the bottom of described deethanizing column tower connects the import being used for the debutanizing tower that C4-with C5+ is separated, liquid phase output channel at the bottom of described absorbing tower connects the import of described deethanizing column, the gas phase output channel of described absorption tower tower top sends the main mixture containing C1 and C2, can be used as Sweet natural gas, the gas phase output channel of described debutanizing tower tower top sends the main mixture containing C3 and C4, can be used as liquefied gas, liquid phase output channel at the bottom of tower is divided into two-way, one tunnel connects the stable light hydrocarbon tower for removing heavy aromatics, another road connects the absorption liquid import of described absorption tower tower top, the output channel of described stable light hydrocarbon column overhead send and remove heavy aromatics after C5+ mixture, can be used as gasoline blending component, output channel at the bottom of tower connects the import of the heavy aromatics tower for separating of C10 heavy aromatics and C11 heavy aromatics, the mixture containing heavy aromatics component separated by stable light hydrocarbon tower sends into heavy aromatics tower, the output channel of described heavy aromatics column overhead connects the crystal system being used for the crystallization of C10 heavy aromatics, the mixture containing C10 heavy aromatics separated by described heavy aromatics tower sends into crystal system, described crystal system carries out crystallization to C10 heavy aromatics and is separated with xln, the xln produced is high purity durol, output channel at the bottom of described heavy aromatics tower tower sends C11 heavy aromatics.
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| CN106927990A (en) * | 2017-05-05 | 2017-07-07 | 济南隆凯能源科技有限公司 | The system and method that a kind of utilization toluene and methyl alcohol prepare durol |
| CN107721798A (en) * | 2017-10-27 | 2018-02-23 | 济南隆凯能源科技有限公司 | A kind of apparatus and method for preparing durol using methanol and mixing C4 |
| CN108329186A (en) * | 2017-01-18 | 2018-07-27 | 中国石油化工股份有限公司 | A kind of methanol conversion process of tandem moving bed |
| CN115010567A (en) * | 2022-06-08 | 2022-09-06 | 明士新材料有限公司 | Novel process for preparing methanol and co-producing high-purity durene from synthesis gas |
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| CN103864562A (en) * | 2014-02-24 | 2014-06-18 | 中国海洋石油总公司 | Method for preparing durene by using methyl alcohol |
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| CN103864562A (en) * | 2014-02-24 | 2014-06-18 | 中国海洋石油总公司 | Method for preparing durene by using methyl alcohol |
| CN204503035U (en) * | 2015-03-27 | 2015-07-29 | 中国昆仑工程公司 | High Efficiency Thermal integrated-type moving bed Methanol hydrocarbon system |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108329186A (en) * | 2017-01-18 | 2018-07-27 | 中国石油化工股份有限公司 | A kind of methanol conversion process of tandem moving bed |
| CN106927990A (en) * | 2017-05-05 | 2017-07-07 | 济南隆凯能源科技有限公司 | The system and method that a kind of utilization toluene and methyl alcohol prepare durol |
| CN106927990B (en) * | 2017-05-05 | 2023-08-29 | 潍坊弘润新材料有限公司 | System and method for preparing durene by using toluene and methanol |
| CN107721798A (en) * | 2017-10-27 | 2018-02-23 | 济南隆凯能源科技有限公司 | A kind of apparatus and method for preparing durol using methanol and mixing C4 |
| CN115010567A (en) * | 2022-06-08 | 2022-09-06 | 明士新材料有限公司 | Novel process for preparing methanol and co-producing high-purity durene from synthesis gas |
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