CN104140839B - A kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction and reclaiming process - Google Patents
A kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction and reclaiming process Download PDFInfo
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- CN104140839B CN104140839B CN201410356951.2A CN201410356951A CN104140839B CN 104140839 B CN104140839 B CN 104140839B CN 201410356951 A CN201410356951 A CN 201410356951A CN 104140839 B CN104140839 B CN 104140839B
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 727
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 284
- 239000003502 gasoline Substances 0.000 title claims abstract description 142
- 238000000034 method Methods 0.000 title claims abstract description 119
- 230000008569 process Effects 0.000 title claims abstract description 80
- 239000003054 catalyst Substances 0.000 claims abstract description 86
- 230000008929 regeneration Effects 0.000 claims abstract description 40
- 238000011069 regeneration method Methods 0.000 claims abstract description 40
- 230000002779 inactivation Effects 0.000 claims abstract description 22
- 238000009826 distribution Methods 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 34
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 12
- 230000008676 import Effects 0.000 claims description 11
- 230000001172 regenerating effect Effects 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000000694 effects Effects 0.000 abstract description 29
- 239000007789 gas Substances 0.000 description 34
- 239000002808 molecular sieve Substances 0.000 description 30
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 29
- 239000004215 Carbon black (E152) Substances 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 150000002430 hydrocarbons Chemical class 0.000 description 23
- 229930195733 hydrocarbon Natural products 0.000 description 22
- 239000000047 product Substances 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 8
- 229960004217 benzyl alcohol Drugs 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- 239000003915 liquefied petroleum gas Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005243 fluidization Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
A kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction and reclaiming process are that two fixed bed adiabatic reactors work alone separately, the first reactor independence methanol conversion gasoline reaction, and the second reactor is in stand-by state; When the catalyzer in the first reactor is close to inactivation, make two reactors in mutual tandem working by valve transfer, until " remaining activity " of catalyzer in the first reactor is fully used; Again by switch valve, two reactors are worked with respective stand-alone mode, reacted by the second reactor complete independently methanol conversion gasoline, the first reactor complete independently catalyst regeneration operates and enters stand-by state.So repeatedly.The present invention has simple to operate, the advantage that in reaction process, the active utilization ratio of catalyst reaction is high.
Description
Technical field
The invention belongs to methanol conversion technique for preparing gasoline.Be specifically related to a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction and reclaiming process.
Background technology
Mobil company of the U.S. in last century the seventies first found that, under ZSM-5 molecular sieve katalysis, methyl alcohol can be converted into hydrocarbon products.In September, 1974, Mobil company has applied for first patent (USP3931349 of its MTG technology, Conversion of methanol to gasoline components), the discovery of this process is the new process of FT technology industrialization five another new synthetic oil during the last ten years of continuing, and provides a new path of being synthesized stop bracket gasoline by coal or Sweet natural gas.
So far, technique and the catalyzer of producing the hydrocarbon products comprising gasoline component about methanol conversion have a large amount of documents to record.The technology of the hydrocarbon productss such as methanol conversion gasoline, from reactor angle, can be divided into bed technology and the large class of fluidization two.
There is a large amount of technical patents in fixed bed methanol conversion technique for preparing gasoline, as United States Patent (USP) 3931349,4998899 is patents of the methanol conversion hydro carbons of Mobil company alerting bulletin, these patents adopt fixed bed two sections of conversion process, wherein first paragraph reaction is dimethyl ether by methanol dehydration, and one section outlet material, comprises the mixture of methyl alcohol, dme and water, enter second stage reactor, under the effect of molecular sieve catalyst, generate gasoline fraction section product.United States Patent (USP) 4788365,4835329,4885421,5001292,5130101,5167937,5080691,5095159,4767604,4788042,4788369,4808764,4814535,4814536,4826662,4898717,5146032,4973784 etc., all relate to fixed bed methanol conversion technique for preparing gasoline.Adopt the built many covers of the methanol conversion gasoline apparatus of fixed-bed reactor so far.
Fluidized-bed methanol conversion technique for preparing gasoline has a large amount of Patent Publication, as United States Patent (USP) 368549, and 4513160,4689205,4929780,6784330 etc., all refer to and adopted fluidization to complete the technology that methanol conversion produces the hydrocarbon products comprising gasoline component.Fluidization not yet builds up any factory.
The fixed bed methanol conversion technique for preparing gasoline that document is recorded mostly adopts two sections of conversion process, wherein first paragraph reaction is dimethyl ether by methanol dehydration, one section outlet material, comprise the mixture of methyl alcohol, dme and water, enter second stage reactor, under the effect of molecular sieve catalyst, generate gasoline fraction section product.
Chinese patent ZL200610048298.9 then discloses a kind of technology of preparing hydrocarbons produce from methanol by one-step method, the method that this patent describes is different from Exxon-Mobil house journal, eliminate the technological process that methyl alcohol is converted into dme in advance, methyl alcohol is in the reactor that ZSM-5 molecular sieve catalyzer is housed, and a step is converted into C
5 +it is main hydrocarbon product.The method that this patent describes further simplify the technical process of preparing hydrocarbon products by methanol conversion.
No matter be two sections of early stage transformation technologies, or the fixed bed adiabatic reactor one trip technique described by Chinese patent ZL200610048298.9, the process being hydrocarbon product at methanol/dimethyl ether conversion all adopts molecular sieve catalyst, particularly adopts ZSM-5 molecular sieve catalyzer.The series reaction such as methanol molecules is dewatered under the katalysis of molecular sieve surface acidic site, carbochain generation, carbochain growth, cyclisation, dehydrogenation, aromizing, finally generate C
1~ C
11hydrocarbon compound.Under the katalysis of molecular sieve catalyst surface acidity position, there is coking reaction simultaneously, cause surface acidity catalytic center carbon distribution inactivation, after carbon deposition quantity acquires a certain degree, need stopped reaction, carry out the process of molecular sieve catalyst coke burning regeneration in methyl alcohol.Methanol conversion hydrocarbon compound technology has following common drawback:
1. catalyzer is short for continuous duration of service, and coke burning regeneration is frequent, complex operation; In general, the single pass life of ZSM-5 molecular sieve is 500 ~ 1000 tons of methyl alcohol/ton catalyzer, namely, catalyzer per ton is after completing 500 ~ 1000 tons of methyl alcohol processing, just must switch to regeneration system rapidly from reactive system, carry out coke burning regeneration operation, not only cause the raising of energy consumption thus, also make operation more loaded down with trivial details;
2. need to arrange the separate reactor of multiple stage, cause reactive system huge, investment increases; For making plant capacity continous-stable, existing methanol conversion gasoline apparatus is all realized by the method arranging standby reactor.Usually except online reactor, at least arrange 1 standby reactor, in the process that online reactor is produced, standby reactor completes catalyst regeneration.
For avoiding above-mentioned defect, Chinese patent ZL201010138973.3 proposes a kind of continuous processing without standby reactor methanol conversion hydrocarbon products.The invention provides a kind of continuous processing of preparing hydrocarbon products through methanol transformation without standby reactor, it is characterized in that in the technical process of preparing hydrocarbon products by methanol conversion, arrange two group reaction devices, open two group reaction devices respectively, when the catalyzer in a group reaction device wherein reaches single pass life latter stage, catalyzer in another group reaction device is in the mid-term of single pass life just, now by total overall reaction load transfer on the reactor being in catalyzer single pass life mid-term, the catalyzer be in catalyzer in the reactor in single pass life latter stage regenerates simultaneously, after having regenerated, open immediately, and make two group reaction devices bear the reaction load of 50% separately.So repeatedly, realize without the reaction process serialization under standby reactor condition.
The continuous processing of the preparing hydrocarbon products through methanol transformation without standby reactor that foregoing invention provides compared with the prior art comparatively, decreases the quantity of reactor, reduces facility investment; Simplify automatic control, reduce the investment of automatic control section; Simplify the operation of catalyst regeneration process, improve stability and the reliability of system operation.
The method that Chinese patent ZL201010138973.3 provides in fact is solve the problem independently arranging more than 3 reactors that fixed bed methanol conversion technique for preparing gasoline adopts usually, change into and 2 group reaction devices are set, and the ingenious feature utilizing short, reaction process operating time regenerative process operating time long, make all reactors of most of time section all be in response behaviour.But the method that Chinese patent ZL201010138973.3 provides still does not help for the problem solving catalyzer frequent regeneration.
In fixed bed adiabatic reactor methanol conversion gasoline process, the heat of chemical reaction release makes temperature of charge streamwise in reactor constantly raise, along with reaction is carried out, the catalyzer first inactivation of reaction mass entrance one end, the temperature of catalyst deactivation section no longer rises, but maintenance steady temperature, " the front constant temperature zone " of formation temperature distribution.Methyl alcohol reacts at the beds of non-inactivation, and cause bed temperature to occur rising, this section is called " the temperature rise section " of bed temperature.The point that bed temperature changes " temperature rise section " into from " front constant temperature zone " is called bed temperature " front flex point ".Reaction raw materials methyl alcohol is after " temperature rise section " completes reaction, and reaction bed temperature peaks, and bed temperature no longer continues to raise, and forms " the rear constant temperature zone " of bed temperature.Temperature of reaction transfers the point of " rear constant temperature zone " to by " temperature rise section ", is called " rear flex point "." front constant temperature zone ", " front flex point ", " the temperature rise section " of temperature distribution history in methanol conversion gasoline adiabatic reactor, " rear flex point " and " rear constant temperature zone " together form " S " type curve of bed temperature distribution.
Along with the continuous carbon distribution inactivation of catalyzer, " S " type curve of adiabatic reactor temperature distribution constantly moves to reactor outlet direction.When " the rear flex point " of " S " type temperature curve is close to reactor exit, methanol crossover bed, reaction terminates, and reactor switching enters reproduced state.
Chinese patent ZL200710185469.7 proposes the concept of methanol conversion gasoline process catalyzer " remaining activity " first.This patent is pointed out, when end close to bed of " the rear flex point " of temperature curve, although methyl alcohol penetrates bed, but the inwhole inactivation of the catalyzer in fact loaded in reactor, the catalyzer that " S " type temperature curve is contained still is in the state that can react, but because methyl alcohol penetrates bed, the catalyst activity of this part cannot obtain utilization, and its activity is " remaining activity ".
For making full use of catalyzer " remaining activity ", Chinese patent ZL200710185469.7 proposes method and the reactor that a kind of methanol conversion draws hydrocarbon products, its core increases the total catalyst bed length of reactor, increase some to material import and export at the sidewall of reactor, the beds in reactor is divided into the beds of some sections shorter by these material import and exports simultaneously.The switch of the valve that the material import and export arranged by sidewall of reactor is installed and switching, make reaction mass by experiencing shorter beds all the time during reactor, realizing while methyl alcohol transforms completely, reducing bed pressure drop, the object of extending catalyst regeneration period.The essence of Chinese patent ZL200710185469.7 is together in series by multiple bed, realized the utilization of a upper bed catalyst " remaining activity " by the switching of the material import and export of sidewall of reactor.
Chinese patent ZL200710185469.7 proposes the concept of " remaining activity ", it is also proposed one and can utilize catalyzer " remaining activity ", the method for extending catalyst regeneration period, but the method that this patent provides still exists following problem:
1. the catalyzer " remaining activity " of reactor lower end can not be utilized, and does not thoroughly solve the problem that catalyzer " remaining activity " is wasted;
2. some methods to importing and exporting being set in sidewall of reactor, adding the difficulty that reactor manufactures, and distribution problem when causing material to enter reactor from sidewall, the practical application difficulty of inventing is increased;
Summary of the invention
The object of this invention is to provide a kind of simple to operate, the fixed bed adiabatic reactor methanol conversion gasoline successive reaction that in reaction process, the active utilization ratio of catalyst reaction is high and reclaiming process, the catalyzer " remaining activity " existed to solve fixed bed adiabatic reactor methanol conversion gasoline prior art is difficult to the problem utilized, and reaches the object improving catalyst activity and the method that simplifies the operation.
The present inventor finds, existing fixed bed adiabatic reactor methanol conversion technique for preparing gasoline is when methanol crossover beds, catalyzer in fixed bed adiabatic reactor not complete deactivation, the catalyzer being in bed end still has reactive behavior, and the activity of this partially catalyzed agent can be referred to as " remaining activity ".The ratio that catalyzer " remaining activity " accounts for catalyzer gross activity is relevant with the feed space velocity that reaction process adopts, feed space velocity is lower, the ratio of " remaining activity " is lower, feed space velocity is higher, the ratio of " remaining activity " is higher, under normal circumstances, catalyzer " remaining activity " can account for 20% ~ 40% of catalyzer gross activity.
Catalyzer " remaining activity " can not obtain utilization, and the catalyst utilization that result in existing fixed bed adiabatic reactor methanol conversion technique for preparing gasoline is low, the problems such as catalyst regeneration frequent operation.Simultaneously; the switching time of existing fixed bed adiabatic reactor methanol conversion technique for preparing gasoline reactor when actually operating is difficult to appropriate grasp: too early carries out reactor switching and catalyst regeneration; the further decline of catalyst use efficiency will be caused; and excessively evening carry out reactor switching and catalyst regeneration; methanol crossover beds can be caused again to enter reaction product aqueous phase; not only cause the increase of methanol consumption, also result in cost for wastewater treatment and rise and environmental protection problem.
The working method of fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and reclaiming process is: first two fixed bed adiabatic reactors work with respective stand-alone mode, wherein the first reactor complete independently methanol conversion gasoline reaction, the catalyst regeneration operation of the second reactor complete independently catalyzer is in stand-by state; When the catalyzer in the first reactor is about to penetrate beds close to inactivation, methyl alcohol, by valve transfer, two reactors are worked under mutual series model, two reactors complete the reaction of methanol conversion gasoline jointly, until " remaining activity " of catalyzer in the first reactor is fully used; Again by switch valve, two reactors are worked with respective stand-alone mode, reacted by the second reactor complete independently methanol conversion gasoline, the first reactor complete independently catalyst regeneration operates and enters stand-by state.So repeatedly, fixed bed adiabatic reactor methanol conversion gasoline successive reaction and regenerative operation can be realized.
The working method of fixed bed adiabatic reactor methanol conversion gasoline successive reaction-reclaiming process provided by the invention can further describe according to the following steps.
(1), first two fixed bed adiabatic reactors work with respective stand-alone mode, wherein the first reactor complete independently methanol conversion gasoline reaction, and the second reactor is in stand-by state;
(2), be about to penetrate beds close to inactivation, methyl alcohol when the methanol conversion gasoline reaction in the first reactor proceeds to catalyzer, namely when " the rear flex point " of the serpentine curve of the first reactor batch temperature distribution is close to beds end, by the switching of valve, two reactors are worked with mutual series model, namely the first reactor outlet material enters the entrance of the second reactor, and proceeds the reaction of methanol conversion gasoline in the second reactor;
(3), the serpentine curve of the first reactor batch temperature distribution continues to move to bed Way out, and be extended in the second reactor gradually, until " the front flex point " of the serpentine curve of the first reactor batch temperature distribution arrives the end of the first reactor catalyst bed, pass through valve transfer, entrance reaction mass being entered reactive system switches to the second reactor inlet by the first reactor inlet, close import and the outlet of the first reactor reaction material, two reactors work with respective stand-alone mode again, now reacted by the second reactor complete independently methanol conversion gasoline,
(4), by valve transfer, make the first reactor independently carry out catalyst regeneration operation, regenerative operation is complete, switch valve, and the first reactor is in stand-by state;
(5), when the methanol conversion gasoline reaction in the second reactor proceeds to catalyzer close to inactivation, methyl alcohol is about to penetrate beds, namely when " the rear flex point " of the serpentine curve of the second reactor batch temperature distribution is close to beds end, by the switching of valve, two reactors are worked with mutual series model, namely the second reactor outlet material enters the entrance of the first reactor, and in the first reactor, proceed the reaction of methanol conversion gasoline, the serpentine curve of the second reactor batch temperature distribution continues to move to bed Way out, and be extended in the first reactor gradually, until " the front flex point " of the serpentine curve of the second reactor batch temperature distribution is close to the end of the second reactor catalyst bed,
(6), by the switching of valve, entrance reaction mass being entered reactive system is switched to the entrance of the first reactor by the entrance of the second reactor, close import and the outlet of the second reactor reaction material, two reactors work with respective stand-alone mode, the first reactor complete independently methanol conversion gasoline reaction;
(7), by the switching of valve, the second reactor is made independently to carry out catalyst regeneration operation.Regenerative operation is complete, switch valve, and the second reactor is in stand-by state;
(8), repeating step (2) to the operation of step (7), fixed bed adiabatic reactor methanol conversion gasoline successive reaction-regenerative operation can be realized.
As mentioned above, the reaction raw materials of fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and regeneration system rapidly is the mixture of methanol steam and circulation dry gas, also can be generate dme and water by methyl alcohol by transform portion in advance after the mixture that formed with circulation dry gas again.
As mentioned above, the reaction raw materials of fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and reclaiming process can be refined methanol, also can be crude carbinol.Wherein in crude carbinol, the mass content of water can between 0.5 ~ 12wt%, preferably between 0.5 ~ 8wt%.
As mentioned above, methanol conversion catalyst in two fixed bed adiabatic reactors of fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and regeneration system rapidly is selected from ZSM-5, ZSM-11, ZSM-12 catalyzer, preferably adopts ZSM-5 or FeZrZSM-5 catalyzer.The FeZrZSM-5 molecular sieve catalyst that the method particularly preferably announced according to Chinese patent ZL200610012810.4 manufactures, this catalyzer can be bought from Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences and obtain.
As mentioned above, the working pressure scope of fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and reclaiming process is 0.5 ~ 6.0MPa, preferred working pressure scope is 1.0 ~ 4.0MPa, and optimum working pressure scope is 1.2 ~ 2.5MPa.
As mentioned above, fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and reclaiming process, the temperature in of fixed bed adiabatic reactor is 280 ~ 360 DEG C, and preferred temperature in is 300 ~ 340 DEG C, and optimum temperature in is 315 ~ 330 DEG C.
As mentioned above, fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and reclaiming process, the temperature out of fixed bed adiabatic reactor is 380 ~ 460 DEG C, and preferred temperature out is 390 ~ 440 DEG C, and optimum temperature out is 400 ~ 425 DEG C.
As mentioned above, fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and reclaiming process, in reaction raw materials, the mass space velocity of methyl alcohol is 0.2 ~ 5.5h
-1, preferred methanol quality air speed is 0.6 ~ 2.5h
-1, optimum methanol quality air speed is 0.9 ~ 2.0h
-1.
As mentioned above, fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and reclaiming process, the dry gas that circulates in reaction raw materials is 4.0 ~ 12.0 with the ratio of the volume of methanol steam, preferred recycle gas is 5.0 ~ 9.0 with the ratio of the volume of methanol steam, and optimum recycle gas is 6.0 ~ 8.0 with the ratio of the volume of methanol steam.
The present invention compared with prior art has the following advantages:
1. catalyzer effective rate of utilization improves, single-pass operation life;
2. working method is simple, and processing parameter is stablized;
3. avoid the methanol crossover phenomenon caused due to catalyst deactivation, be conducive to reducing wastage of material and reducing environmental pollution;
4. reduce the regeneration times of catalyzer, be conducive to reducing energy consumption;
Accompanying drawing explanation
Fig. 1 is process flow sheet of the present invention.
As shown in the figure, R-a is the first reactor, and R-b is the second reactor, 1,2a, 2b, 4a, 4b, 5a, 5b, 6a, 6b, 8a, 8b, and 9,11a, 11b, 13a, 13b, 16a, 16b are pipelines, and 3a, 3b, 7a, 7b, 10a, 10b, 12a, 12b, 14a, 14b, 15a, 15b are valves.
Fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and reclaiming process can by reference to the accompanying drawings 1, are described according to the following steps further:
1. valve 3a, 7a is in opened condition, and valve 3b, 7b, 10a, 10b, 12a, 12b, 14a, 14b, 15a, 15b are in closing condition.The mixture of the methanol steam and circulation dry gas that are heated to certain temperature enters system by pipeline 1, through pipeline 2a, valve 3a and pipeline 4a enters the first reactor R-a that catalyzer is housed, the reaction of methanol conversion gasoline is completed in the first reactor R-a, and through pipeline 5a, pipeline 6a, valve 7a, pipeline 8a and pipeline 9 leave system.First reactor R-b is in stand-by state;
2. when the methanol conversion gasoline reaction in the first reactor R-a proceeds to catalyzer close to inactivation, methyl alcohol is about to penetrate beds, when " the rear flex point " of the temperature distribution serpentine curve namely in the first reactor R-a is close to beds end, open valve 12a, valve 10b and valve 7b, valve-off 7a, make the first reactor R-a outlet material through pipeline 5a, valve 12a, pipeline 11b, valve 10b and pipeline 4b enters the second reactor R-b, forming reactions device tandem working pattern, two reactor R-a and R-b complete the reaction of methanol conversion gasoline jointly, from the second reactor R-b material out through pipeline 5b, pipeline 6b, valve 7b, pipeline 8b and pipeline 9 leave system,
3. the serpentine curve of the first reactor R-a bed temperature distribution continues to move to bed Way out, and is extended to the second reactor R-b gradually.When in the first reactor R-a, " the front flex point " of the serpentine curve of bed temperature distribution arrives the end of beds, open valve 3b, valve-off 3a, 12a and valve 10b, make mixture from pipeline 1 through pipeline 2b, valve 3b and pipeline 4b enters the second reactor R-b, and two reactors work with respective stand-alone mode, the second reactor R-b complete independently methanol conversion gasoline reaction;
4. open valve 14a and valve 15a, the first reactor R-a is connected with regeneration system rapidly.Rare gas element (as nitrogen) is through pipeline 13a, and valve 14a, pipeline 4a enter the first reactor R-a, then through pipeline 5a, valve 15a and pipeline 16a, replaces reactor, be replaced.Import a certain proportion of oxygen-containing gas, through above-mentioned route by the first reactor R-a, to in the first reactor R-a the catalyzer of inactivation regenerate, after having regenerated, rare gas element (as nitrogen) is again used to replace oxygen-containing gas in the first reactor R-a, be replaced valve-off 15a and valve 16a, the first reactor R-a is in stand-by state;
5. when the methanol conversion gasoline reaction in the second reactor R-b proceeds to catalyzer close to inactivation, methyl alcohol is about to penetrate beds, when " the rear flex point " of the temperature distribution serpentine curve namely in the second reactor R-b is close to beds end, open valve 12b, valve 10a and valve 7a, valve-off 7b, make the second reactor R-b outlet material through pipeline 5b, valve 12b, pipeline 11a, valve 10a and pipeline 4a enters the first reactor R-a, forming reactions device tandem working pattern, two reactor R-b and R-a complete the reaction of methanol conversion gasoline jointly, from the first reactor R-a material out through pipeline 5a, pipeline 6a, valve 7a, pipeline 8a and pipeline 9 leave system,
6. the serpentine curve of the second reactor R-b bed temperature distribution continues to move to bed Way out, and is extended to the first reactor R-a gradually.When in the second reactor R-b, " the front flex point " of the serpentine curve of bed temperature distribution arrives the end of beds, open valve 3a, valve-off 3b, 12b and valve 10a, make mixture from pipeline 1 through pipeline 2a, valve 3a and pipeline 4a enters the first reactor R-a, and two reactors work with respective stand-alone mode, the first reactor R-a complete independently methanol conversion gasoline reaction;
7. open valve 14b and valve 15b, the second reactor R-b is connected with regeneration system rapidly.Rare gas element (as nitrogen) is through pipeline 13b, valve 14b, pipeline 4b enters the second reactor R-b, again through pipeline 5b, valve 15b and pipeline 16b, reactor is replaced, be replaced, make oxygen-containing gas through above-mentioned route by the second reactor R-b, to in the second reactor R-b the catalyzer of inactivation regenerate, after having regenerated, again use rare gas element (as nitrogen) to replace oxygen-containing gas in the second reactor R-b, be replaced valve-off 15b and valve 16b, the second reactor R-b is in stand-by state;
8. repeating step 2 is to step 7, can realize fixed bed adiabatic reactor methanol conversion gasoline successive reaction-regenerative operation.
Embodiment
Fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and reclaiming process further illustrate by following examples.But fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and reclaiming process are not limited to embodiment.
Embodiment 1
2 fixed bed adiabatic reactors are connected by flow process shown in accompanying drawing 1 with valve by some pipelines.
R-a and R-b is the fixed bed adiabatic reactor adopting stainless steel to manufacture, internal diameter 3200mm.The FeZrZSM-5 molecular sieve catalyst 23.29 tons of the method manufacture of announcing according to Chinese patent ZL200610012810.4 is housed respectively, the free height 4830mm of beds in two reactors.In two reactors, the inventory of FeZrZSM-5 molecular sieve catalyst is 46.58 tons.
Total system is through nitrogen purging, and detect and confirm that oxygen level is less than 0.5%, system pressure controls at 1.8MPa.
Valve 3a, 7a is in opened condition, and valve 3b, 7b, 10a, 10b, 12a, 12b, 14a, 14b, 15a, 15b are in closing condition.
Set up system nitrogen circulation by external circulating system, through pipeline 1,2a, and the nitrogen flow that pipeline 3a enters fixed bed adiabatic reactor R-a is 150000Nm
3/ h is 8.05h relative to the mass space velocity of catalyzer in reactor R-a
-1, volume space velocity is 3864h
-1.By indirect heating system, reactor R-a temperature is increased to 320 DEG C.Introduce methanol steam in pipeline 1 ingress, flow is 25000 Nm
3/ h, mass rate is 35.71t/h, is 644h relative to the volume space velocity of catalyzer in reactor R-a
-1, mass space velocity is 1.53h
-1.Methyl alcohol reacts under the effect of the FeZrZSM-5 molecular sieve catalyst loaded in R-a reactor, is converted into hydrocarbon product and a small amount of CO, CO
2, H
2deng product, reaction product leaves reactor R-a inlet pipe road 5a, 6a, valve 7a, and pipeline 8a and pipeline 9, leave system.Outside system, complete being separated of gasoline component and liquefied petroleum gas (LPG) (LPG) and dry gas, part nitrogen and dry gas leave system as periodic off-gases, and another part dry gas is by outside condenser Returning reacting system, and the volumetric flow rate of recycle gas is 180000Nm
3/ h, recycle ratio is 7.2.
Along with constantly carrying out of above-mentioned reaction, the nitrogen in system is replaced gradually, and it is CH that recycle gas finally becomes main component
4, C
2h
4, C
2h
6, C
3h
6, C
3h
8, CO, CO
2, H
2in the mixture of gas.
In the process that above-mentioned reaction is carried out, reactor R-a completes the reaction of methanol conversion gasoline with independent working mode.The reactor R-b that fresh FeZrZSM-5 molecular sieve catalyst is housed is in stand-by state.
React in reactor R-a in the process of carrying out, release heat due to reaction and cause the temperature of reaction mass constantly to rise and form serpentine temperature curve, " rear constant temperature zone " temperature is 420 DEG C.
Along with reaction is carried out, the carrying out reacted in reactor R-a, " S " type temperature curve of bed temperature distribution moves from reactor inlet to Way out gradually, when the methanol conversion gasoline reaction in reactor R-a proceeds to catalyzer close to inactivation, methyl alcohol is about to penetrate beds, when " the rear flex point " of the temperature distribution serpentine curve namely in reactor R-a is close to beds end, specifically, when " rear flex point " is 500mm from beds distance from bottom, open valve 12a, valve 10b and valve 7b, valve-off 7a, make reactor R-a outlet material through pipeline 5a, valve 12a, pipeline 11b, valve 10b and pipeline 4b enters reactor R-b, two reactors work with mutual series model, jointly complete the reaction of methanol conversion gasoline.Autoreactor R-b material is out through pipeline 5b, and pipeline 6b, valve 7b, pipeline 8b and pipeline 9 leave system.
The serpentine curve of reactor R-a bed temperature distribution continues to move to bed Way out, and is extended to reactor R-b gradually.When in reactor R-a, " the front flex point " of the serpentine curve of bed temperature distribution arrives the end of beds, open valve 3b, valve-off 3a, 12a and valve 10b, make mixture from pipeline 1 through pipeline 2b, valve 3b and pipeline 4b enters reactor R-b, and two reactors work with respective stand-alone mode, and reactor R-b complete independently methanol conversion gasoline reacts.
Open valve 14a and valve 15a, reactor R-a is connected with regeneration system rapidly, make system pressure constant in 0.8MPa by the material in release system.Flow is 69875.8Nm
3the nitrogen of/h through pipeline 13a, valve 14a, pipeline 4a enters reactor R-a, again through pipeline 5a, valve 15a and pipeline 16a, replaces reactor, and bed temperature is reduced to 350 DEG C, constant temperature is replaced, until the volume content of inflammable gas is less than 0.5% in gas.Import a certain proportion of air, the oxygen volume content in mixed gas is made to be 0.8%, in reactor R-a, the carbon distribution of the catalyst surface of inactivation takes fire, therefore raising appears in bed temperature again, by regulating air capacity, controlling reaction bed temperature and being no more than 490 DEG C, until there is no obvious temperature rise, again by indirect heating system, bed inlet temperatures is increased to 480 DEG C, makes catalyst surface area carbon burning further, until without obvious temperature rise.Control the flow importing air, make reactor R-a ingress oxygen volume content bring up to 7%, control reaction bed temperature and be no more than 490 DEG C, until after there is no obvious temperature rise, bed temperature is increased to 490 DEG C, constant temperature 4 hours.Catalyst regeneration in reactor R-a is complete, and nitrogen purge system cools to normal temperature simultaneously, and valve-off 15a and valve 16a, reactor R-a is in stand-by state.Reactor R-b completes separately the reaction of methanol conversion gasoline with independent working mode.
When the methanol conversion gasoline reaction in reactor R-b proceeds to catalyzer close to inactivation, methyl alcohol is about to penetrate beds, when " the rear flex point " of the temperature distribution serpentine curve namely in reactor R-b is close to beds end, specifically, when " rear flex point " is 500mm from beds distance from bottom, open valve 12b, valve 10a and valve 7a, valve-off 7b, make reactor R-b outlet material through pipeline 5b, valve 12b, pipeline 11a, valve 10a and pipeline 4a enters reactor R-a, two reactors work with mutual series model, jointly complete the reaction of methanol conversion gasoline.Autoreactor R-a material is out through pipeline 5a, and pipeline 6a, valve 7a, pipeline 8a and pipeline 9 leave system.
The serpentine curve of reactor R-b bed temperature distribution continues to move to bed Way out, and is extended to reactor R-a gradually.When in reactor R-b, " the front flex point " of the serpentine curve of bed temperature distribution arrives the end of beds, open valve 3a, valve-off 3b, 12b and valve 10a, make mixture from pipeline 1 through pipeline 2a, valve 3a and pipeline 4a enters reactor R-a, and two reactors work with respective stand-alone mode, and reactor R-a complete independently methanol conversion gasoline reacts;
Open valve 14b and valve 15b, reactor R-b is connected with regeneration system rapidly.That system pressure is constant in 0.8MPa by the material in release system.Flow is 69875.8Nm
3the nitrogen of/h through pipeline 13b, valve 14b, pipeline 4b enters reactor R-b, again through pipeline 5b, valve 15b and pipeline 16b, replaces reactor, and bed temperature is reduced to 350 DEG C, constant temperature is replaced, until the volume content of inflammable gas is less than 0.5% in gas.Import a certain proportion of air, the oxygen volume content in mixed gas is made to be 0.8%, in reactor R-b, the carbon distribution of the catalyst surface of inactivation takes fire, therefore raising appears in bed temperature again, by regulating air capacity, controlling reaction bed temperature and being no more than 490 DEG C, until there is no obvious temperature rise, again by indirect heating system, bed inlet temperatures is increased to 480 DEG C, makes catalyst surface area carbon burning further, until without obvious temperature rise.Control the flow importing air, make reactor R-b ingress oxygen volume content bring up to 7%, control reaction bed temperature and be no more than 490 DEG C, until after there is no obvious temperature rise, bed temperature is increased to 490 DEG C, constant temperature 4 hours.Catalyst regeneration in reactor R-b is complete, and nitrogen purge system cools to normal temperature simultaneously, and valve-off 15b and valve 16b, reactor R-b is in stand-by state.Reactor R-a completes separately the reaction of methanol conversion gasoline with independent working mode.
When catalyzer in reactor R-a is again close to inactivation, repeat above operation, two fixed bed adiabatic reactors switch between independent working mode and mutual series model, realize successive reaction and the regenerative operation of fixed bed adiabatic reactor methanol conversion gasoline.
The significant parameter of embodiment 1 and the significant parameter common column of the comparative example 1 of description are below in Table 1.
The key technical indexes of embodiment 1 and the key technical indexes common column of the comparative example 1 of description are below in table 2.
Comparative example 1
The reactive system that comparative example 1 adopts prior art usually to adopt and working method, be convenient to adopt fixed bed adiabatic reactor methanol conversion technique for preparing gasoline provided by the invention to compare, so that the advance of technology provided by the invention to be described with this.
The reactive system of comparative example 1 arranges 3 with the fixed bed adiabatic reactor of respective stand-alone mode work.Reactor adopts stainless steel manufacture, internal diameter 3200mm, and every platform reactor loads the FeZrZSM-5 molecular sieve catalyst 15.53 tons of the method manufacture of announcing according to Chinese patent ZL200610012810.4 respectively, the free height 3220mm of beds.In 3 reactors, the inventory of FeZrZSM-5 molecular sieve catalyst is 46.58 tons.
The concrete operation method of this comparative example 1 is, 2 priorities in 3 reactors drop into reaction, and the reactor dropping into reaction is called online reactor.2 online reactor parallel connections complete methanol conversion gasoline task.Controlling System pressure is 1.8MPa, and controlling by the total amount of the methanol steam of 2 reactors is 25000NM
3/ h, mass rate is 35.71t/h, is 483h relative to the methyl alcohol volume space velocity of 2 online catalyst reactors
-1, mass space velocity is 1.15
-1, the dry gas volumetric flow rate as recycle gas is 180000Nm
3/ h, recycle ratio is 7.2.Beds temperature in is 320 DEG C, and vertex temperature is 420 DEG C.
React under the effect of the FeZrZSM-5 molecular sieve catalyst that methyl alcohol loads in online reactor, be converted into hydrocarbon product and a small amount of CO, CO
2, H
2deng product, reaction product is left online reactor and is completed being separated of gasoline component and liquefied petroleum gas (LPG) (LPG) and dry gas, and part dry gas leaves system as periodic off-gases, and another part dry gas is by outside condenser Returning reacting system.
Due to exothermic heat of reaction in online reactor, bed temperature distribution is in serpentine curve, and along with reaction is carried out, bed temperature distribution serpentine curve moves to reactor outlet direction gradually.
When the catalyzer of a reactor in online reactor is about to penetrate beds close to inactivation, methyl alcohol, this reactor is switched stopped reaction, 3rd reactor for subsequent use drops into reaction, the decaying catalyst switched in the reactor of stopped reaction independently regenerates, reproducer is identical with embodiment 1, catalyst regeneration is complete, and this reactor is in stand-by state.Switching like this, carrying out continuously of realization response.
The significant parameter of comparative example 1 is in table 1.
The key technical indexes of comparative example 1 is in table 2.
The significant parameter of table 1 embodiment 1 and comparative example 1
| Project | Embodiment 1 | Comparative example 1 |
| Reactor quantity, platform | 2 | 3 |
| Catalyzer forms | FeZrZSM-5 molecular sieve | FeZrZSM-5 molecular sieve |
| Separate unit reactor catalyst loading amount, ton | 23.29 | 15.53 |
| Catalyst loading total mass, ton | 46.58 | 46.58 |
| Reactor inside diameter, mm | 3200 | 3200 |
| Catalyst bed layer height, mm | 4830 | 3220 |
| Specific surface area of catalyst, m 2/g | 360 | 360 |
| Molecular sieve Si/Al ratio | 95 | 95 |
| Catalyst bulk density, ton/m 3 | 0.60 | 0.60 |
| Material benzenemethanol mass content, % | 99.9 | 99.9 |
| Material benzenemethanol mass space velocity, h -1 | 1.53 | 1.15 |
| Reactor inlet pressure, MPa | 1.8 | 1.8 |
| Reactor outlet pressure, MPa | 1.7 | 1.7 |
| Reactor inlet temperature, DEG C | 320 | 320 |
| Reactor outlet temperature, DEG C | 420 | 420 |
The key technical indexes of table 2 embodiment 1 and comparative example 1
| Project | Embodiment 1 | Comparative example 1 |
| Reactor outlet methyl alcohol average content, ppm | 10 | 100 |
| The most high-content of reactor outlet methyl alcohol, ppm | 20 | 1000 |
| Methanol feeding amount, ton/hour | 35.71 | 35.71 |
| Separate unit reactor line duration, sky | 25 | 25 |
| Separate unit reactor monocycle process quantity of methyl alcohol, ton | 22011 | 10870 |
| Year process quantity of methyl alcohol (8000 hours), ten thousand tons | 28.57 | 28.57 |
| The annual reactor platform switching regeneration | 13 | 26 |
| The catalyst regeneration timed interval, sky | 25 | 12.7 |
| Catalyzer duration of service, year (1 year=8000 hours) | 2.77 | 2.05 |
| Methyl alcohol process total amount, ten thousand tons | 79.2 | 58.7 |
| Reactor outlet C 5 +Hydrocarbon (gasoline) mass rate, ton/hour | 12.50 | 12.49 |
| Reactor outlet C 3～C 4Hydrocarbon mass rate, ton/hour | 2.68 | 2.67 |
Table 1 data declaration, embodiment 1 and comparative example 1 employ the FeZrZSM-5 molecular sieve of same model, and total loaded catalyst is identical, and the quantity of methyl alcohol of process is also identical.Embodiment 1 and comparative example 1 unlike, comparative example 1 adopts existing fixed bed adiabatic reactor methanol conversion technique for preparing gasoline, 3 fixed bed adiabatic reactors are set, embodiment 1 have employed fixed bed adiabatic reactor provided by the invention successive reaction-reclaiming process, arranges 2 fixed bed adiabatic reactors.
The data declaration of table 2, adopt the embodiment 1 of fixed bed adiabatic reactor methanol conversion gasoline successive reaction-reclaiming process provided by the invention, the methyl alcohol residual volume average out to 10ppm of reactor outlet, maximum 20ppm, and adopt the comparative example 1 of existing fixed bed adiabatic reactor methanol conversion technique for preparing gasoline, reactor outlet methyl alcohol residual volume average out to 100ppm, when catalyzer is close to inactivation, methyl alcohol maximum reaches 1000ppm.
The reduction of embodiment 1 methyl alcohol residual volume, show that fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and reclaiming process effectively can avoid the problem of methanol crossover, reduce methanol consumption, and be conducive to reducing cost for wastewater treatment, eliminate environmental pollution.
The data declaration of table 2, adopt the embodiment 1 of fixed bed adiabatic reactor methanol conversion gasoline successive reaction-reclaiming process provided by the invention, separate unit reactor line duration is 25 days, monocycle process quantity of methyl alcohol is 22011 tons, monocycle average catalyst treatment methyl alcohol per ton 945 tons (single pass life), and adopt the comparative example 1 of existing fixed bed adiabatic reactor methanol conversion technique for preparing gasoline, although separate unit reactor line duration is also 25 days, but its monocycle process quantity of methyl alcohol is only 10870 tons, monocycle average catalyst treatment methyl alcohol per ton 700 tons (single pass life).
Embodiment 1 catalyzer per ton, in the increase of each one way period treatment quantity of methyl alcohol, shows that fixed bed adiabatic reactor successive reaction provided by the invention and reclaiming process effectively make use of catalyzer " remaining activity ", improves the effective rate of utilization of catalyzer.
The data declaration of table 2, adopts the embodiment 1 of fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and reclaiming process, the C of production per hour
5 +hydrocarbon is 12.5 tons, C
3~ C
4hydrocarbon is 2.68 tons, and adopts the comparative example 1 of existing fixed bed adiabatic reactor methanol conversion technique for preparing gasoline, the C of production per hour
5 +hydrocarbon is 12.49 tons, C
3~ C
4hydrocarbon is 2.67 tons.
C in embodiment 1
5 +hydrocarbon and C
3~ C
4hydrocarbon output is greater than comparative example 1, shows that fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and reclaiming process are conducive to improving the yield of target product, avoids the waste of raw material.
The data declaration of table 2, adopt the embodiment 1 of fixed bed adiabatic reactor methanol conversion gasoline successive reaction-reclaiming process provided by the invention, often operate 1 year (8000 hours), device needs the reactor platform of regeneration to be 13 times, be spaced apart 25 days switching time, and adopt the comparative example 1 of existing fixed bed adiabatic reactor methanol conversion technique for preparing gasoline, often operate 1 year (8000 hours), device needs the reactor platform of regeneration to be 26 times, and regeneration intervals is 12.7 days.
Fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and reclaiming process are compared with existing fixed bed adiabatic reactor methanol conversion technique for preparing gasoline, within a certain period of time, the reactor platform switching regeneration is needed significantly to reduce, and the energy consumption that catalyst regeneration process needs is very high, fixed bed adiabatic reactor methanol conversion gasoline successive reaction-reclaiming process provided by the invention is therefore adopted to be conducive to saving energy and reduce the cost.
The data of table 2 also illustrate, adopt the embodiment 1 of fixed bed adiabatic reactor methanol conversion gasoline successive reaction provided by the invention and reclaiming process, catalyzer can use 2.77 (every year by 8000 hours) continuously, process methyl alcohol 79.2 ten thousand tons, and adopt the comparative example 1 of existing fixed bed adiabatic reactor methanol conversion technique for preparing gasoline, catalyzer can only use 2.05 (every year by 8000 hours) continuously, and process methyl alcohol also can only reach 58.7 ten thousand tons.
Catalyzer uses the increase of total time and process methyl alcohol total amount, illustrate that fixed bed adiabatic reactor methanol conversion gasoline successive reaction-reclaiming process provided by the invention improves catalyst activity utilising efficiency, decrease the consumption of catalyzer, decrease because more catalyst changeout needs the every other loss brought of stopping simultaneously, improve the production efficiency of factory.
Embodiment 2
Catalyst loading condition is completely identical with embodiment 1 with operational condition, but catalyzer adopts ZSM-5 molecular sieve catalyzer.
The significant parameter of embodiment 2 is in table 3.
The key technical indexes of embodiment 2 is in table 4.
Comparative example 2
Catalyst loading condition is completely identical with comparative example 1 with operational condition, but catalyzer adopts the ZSM-5 molecular sieve catalyzer identical with embodiment 2.
The significant parameter of comparative example 2 is in table 3.
The key technical indexes of comparative example 2 is in table 4.
The significant parameter of table 3 embodiment 2 and comparative example 2
| Project | Embodiment 2 | Comparative example 2 |
| Reactor quantity, platform | 2 | 3 |
| Catalyzer forms | ZSM-5 molecular sieve | ZSM-5 molecular sieve |
| Separate unit reactor catalyst loading amount, ton | 42.86 | 28.57 |
| Catalyst loading total mass, ton | 85.71 | 85.71 |
| Reactor inside diameter, mm | 3600 | 3600 |
| Catalyst bed layer height, mm | 6910 | 4600 |
| Specific surface area of catalyst, m 2/g | 410 | 410 |
| Molecular sieve Si/Al ratio | 95 | 95 |
| Catalyst bulk density, ton/m 3 | 0.61 | 0.61 |
| Material benzenemethanol mass content, % | 99.9 | 99.9 |
| Material benzenemethanol mass space velocity, h -1 | 1.67 | 1.25 |
| Reactor inlet pressure, MPa | 2.5 | 2.5 |
| Reactor outlet pressure, MPa | 2.3 | 2.4 |
| Reactor inlet temperature, DEG C | 315 | 315 |
| Reactor outlet temperature, DEG C | 430 | 430 |
The key technical indexes of table 4 embodiment 2 and comparative example 2
| Project | Embodiment 2 | Comparative example 2 |
| Reactor outlet methyl alcohol average content, ppm | 10 | 100 |
| The most high-content of reactor outlet methyl alcohol, ppm | 20 | 1000 |
| Methanol feeding amount, ton/hour | 71.43 | 71.43 |
| Separate unit reactor line duration, sky | 34 | 33 |
| Separate unit reactor monocycle process quantity of methyl alcohol, ton | 58286 | 28571 |
| Year process quantity of methyl alcohol (8000 hours), ten thousand tons | 57.14 | 57.14 |
| The annual reactor platform switching regeneration | 10 | 20 |
| The catalyst regeneration timed interval, sky | 34 | 17 |
| Catalyzer duration of service, year (1 year=8000 hours) | 4.1 | 3.0 |
| Methyl alcohol process total amount, ten thousand tons | 233 | 171 |
| Reactor outlet C 5 +Hydrocarbon (gasoline) mass rate, ton/hour | 25.00 | 24.80 |
| Reactor outlet C 3～C 4Hydrocarbon mass rate, ton/hour | 5.36 | 5.35 |
Embodiment 3
With embodiment 1, but catalyzer adopts ZSM-12 molecular sieve catalyst.
The significant parameter of embodiment 3 is in table 5.
The key technical indexes of embodiment 3 is in table 6.
The significant parameter of table 5 embodiment 3
| Project | Embodiment 3 |
| Reactor quantity, platform | 2 |
| Catalyzer forms | ZSM-12 |
| Separate unit reactor catalyst loading amount, ton | 112.5 |
| Catalyst loading total mass, ton | 225 |
| Reactor inside diameter, mm | 4500 |
| Catalyst bed layer height, mm | 11410 |
| Specific surface area of catalyst, m 2/g | 390 |
| Molecular sieve Si/Al ratio | 93 |
| Catalyst bulk density, ton/m 3 | 0.62 |
| Material benzenemethanol mass content, % | 99.9 |
| Material benzenemethanol mass space velocity, h -1 | 2.00 |
| Reactor inlet pressure, MPa | 2.5 |
| Reactor outlet pressure, MPa | 2.4 |
| Reactor inlet temperature, DEG C | 320 |
| Reactor outlet temperature, DEG C | 420 |
The key technical indexes of table 6 embodiment 3
| Project | Embodiment 3 |
| Reactor outlet methyl alcohol average content, ppm | 10 |
| The most high-content of reactor outlet methyl alcohol, ppm | 20 |
| Methanol feeding amount, ton/hour | 225 |
| Separate unit reactor line duration, sky | 34 |
| Separate unit reactor monocycle process quantity of methyl alcohol, ton | 183600 |
| Year process quantity of methyl alcohol (8000 hours), ten thousand tons | 180 |
| The annual reactor platform switching regeneration | 10 |
| The catalyst regeneration timed interval, sky | 34 |
| Catalyzer duration of service, year (1 year=8000 hours) | 4.1 |
| Methyl alcohol process total amount, ten thousand tons | 734 |
| Reactor outlet C 5 +Hydrocarbon (gasoline) mass rate, ton/hour | 78.75 |
| Reactor outlet C 3～C 4Hydrocarbon mass rate, ton/hour | 16.88 |
Embodiment 4-6
Catalyzer model is completely identical with embodiment 1 with filling condition, and working method is also identical with embodiment 1, but have adjusted relevant operating parameters.
The significant parameter of embodiment 4-6 is in table 7.
The key technical indexes of embodiment 4-6 is in table 8.
The significant parameter of table 7 embodiment 4-6
| Project | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| Reactor quantity, platform | 2 | 2 | 2 |
| Catalyzer forms | FeZrZSM-5 | FeZrZSM-5 | FeZrZSM-5 |
| Separate unit reactor catalyst loading amount, ton | 112.5 | 112.5 | 112.5 |
| Catalyst loading total mass, ton | 225 | 225 | 225 |
| Reactor inside diameter, mm | 4500 | 4500 | 4500 |
| Catalyst bed layer height, mm | 11410 | 11410 | 11410 |
| Specific surface area of catalyst, m 2/g | 390 | 390 | 390 |
| Molecular sieve Si/Al ratio | 93 | 93 | 93 |
| Catalyst bulk density, ton/m 3 | 0.62 | 0.62 | 0.62 |
| Material benzenemethanol mass content, % | 99.9 | 99.9 | 92.5 |
| Material benzenemethanol mass space velocity, h -1 | 1.2 | 1.5 | 1.5 |
| Circulation dry gas and methanol steam volume ratio | 9.0 | 7.5 | 5.5 |
| Reactor inlet pressure, MPa | 1.8 | 2.0 | 2.0 |
| Reactor outlet pressure, MPa | 1.7 | 1.9 | 1.9 |
| Reactor inlet temperature, DEG C | 290 | 310 | 320 |
| Reactor outlet temperature, DEG C | 390 | 410 | 430 |
The key technical indexes of table 8 embodiment 4-6
Claims (23)
1. fixed bed adiabatic reactor methanol conversion gasoline successive reaction and a reclaiming process, is characterized in that comprising the steps:
(1), first two fixed bed adiabatic reactors work with respective stand-alone mode, wherein the first reactor complete independently methanol conversion gasoline reaction, and the second reactor is in stand-by state;
(2), be about to penetrate beds close to inactivation, methyl alcohol when the methanol conversion gasoline reaction in the first reactor proceeds to catalyzer, namely when " the rear flex point " of the serpentine curve of the first reactor batch temperature distribution is close to beds end, by the switching of valve, two reactors are worked with mutual series model, namely the first reactor outlet material enters the entrance of the second reactor, and proceeds the reaction of methanol conversion gasoline in the second reactor;
(3), the serpentine curve of the first reactor batch temperature distribution continues to move to bed Way out, and be extended in the second reactor gradually, until " the front flex point " of the serpentine curve of the first reactor batch temperature distribution arrives the end of the first reactor catalyst bed, pass through valve transfer, entrance reaction mass being entered reactive system switches to the second reactor inlet by the first reactor inlet, close import and the outlet of the first reactor reaction material, two reactors work with respective stand-alone mode again, now reacted by the second reactor complete independently methanol conversion gasoline,
(4), by valve transfer, make the first reactor independently carry out catalyst regeneration operation, regenerative operation is complete, switch valve, and the first reactor is in stand-by state;
(5), when the methanol conversion gasoline reaction in the second reactor proceeds to catalyzer close to inactivation, methyl alcohol is about to penetrate beds, namely when " the rear flex point " of the serpentine curve of the second reactor batch temperature distribution is close to beds end, by the switching of valve, two reactors are worked with mutual series model, namely the second reactor outlet material enters the entrance of the first reactor, and in the first reactor, proceed the reaction of methanol conversion gasoline, the serpentine curve of the second reactor batch temperature distribution continues to move to bed Way out, and be extended in the first reactor gradually, until " the front flex point " of the serpentine curve of the second reactor batch temperature distribution is close to the end of the second reactor catalyst bed,
(6), by the switching of valve, entrance reaction mass being entered reactive system is switched to the entrance of the first reactor by the entrance of the second reactor, close import and the outlet of the second reactor reaction material, two reactors work with respective stand-alone mode, the first reactor complete independently methanol conversion gasoline reaction;
(7), by the switching of valve, make the second reactor independently carry out catalyst regeneration operation, regenerative operation is complete, switch valve, and the second reactor is in stand-by state;
(8), repeating step (2) to the operation of step (7), fixed bed adiabatic reactor methanol conversion gasoline successive reaction and regenerative operation can be realized.
2. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 1 and reclaiming process, it is characterized in that the mixture of described methyl alcohol or methanol steam and circulation dry gas, or the mixture formed with circulation dry gas again after generating dme and water by methyl alcohol by transform portion in advance.
3. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 1 and reclaiming process, is characterized in that described methyl alcohol is refined methanol or crude carbinol.
4. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 3 and reclaiming process, is characterized in that the mass content of water in described crude carbinol is between 0.5 ~ 12wt%.
5. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 4 and reclaiming process, is characterized in that the mass content of water in described crude carbinol is between 0.5 ~ 8wt%.
6. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 1 and reclaiming process, is characterized in that the methanol conversion catalyst in described two fixed bed adiabatic reactors is selected from ZSM-5, ZSM-11, ZSM-12 or FeZrZSM-5 catalyzer.
7. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 6 and reclaiming process, is characterized in that described methanol conversion catalyst adopts ZSM-5 or FeZrZSM-5 catalyzer.
8. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 7 and reclaiming process, is characterized in that described methanol conversion catalyst adopts FeZrZSM-5 catalyzer.
9. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 1 and reclaiming process, is characterized in that the working pressure scope of described fixed bed adiabatic reactor methanol conversion gasoline is 0.5 ~ 6.0MPa.
10. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 9 and reclaiming process, is characterized in that the working pressure scope of described fixed bed adiabatic reactor methanol conversion gasoline is 1.0 ~ 4.0MPa.
11. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 10 and reclaiming procesies, is characterized in that the working pressure scope of described fixed bed adiabatic reactor methanol conversion gasoline is 1.2 ~ 2.5MPa.
12. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 1 and reclaiming procesies, is characterized in that the temperature in of fixed bed adiabatic reactor in described fixed bed adiabatic reactor methanol conversion gasoline process is 280 ~ 360 DEG C.
13. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 12 and reclaiming procesies, is characterized in that the temperature in of fixed bed adiabatic reactor in described fixed bed adiabatic reactor methanol conversion gasoline process is 300 ~ 340 DEG C.
14. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 13 and reclaiming procesies, is characterized in that the temperature in of fixed bed adiabatic reactor in described fixed bed adiabatic reactor methanol conversion gasoline process is 315 ~ 330 DEG C.
15. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 1 and reclaiming procesies, is characterized in that the temperature out of fixed bed adiabatic reactor in described fixed bed adiabatic reactor methanol conversion gasoline process is 380 ~ 460 DEG C.
16. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 15 and reclaiming procesies, is characterized in that the temperature out of fixed bed adiabatic reactor in described fixed bed adiabatic reactor methanol conversion gasoline process is 390 ~ 440 DEG C.
17. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 16 and reclaiming procesies, is characterized in that the temperature out of fixed bed adiabatic reactor in described fixed bed adiabatic reactor methanol conversion gasoline process is 400 ~ 425 DEG C.
18. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 1 and reclaiming procesies, is characterized in that the mass space velocity of methyl alcohol in described fixed bed adiabatic reactor methanol conversion gasoline is 0.2 ~ 5.5h
-1.
19. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 18 and reclaiming procesies, is characterized in that the mass space velocity of methyl alcohol in described fixed bed adiabatic reactor methanol conversion gasoline is 0.6 ~ 2.5h
-1.
20. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 19 and reclaiming procesies, is characterized in that the mass space velocity of methyl alcohol in described fixed bed adiabatic reactor methanol conversion gasoline is 0.9 ~ 2.0h
-1.
21. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 2 and reclaiming procesies, the dry gas that it is characterized in that circulating in described fixed bed adiabatic reactor methanol conversion gasoline process is 4.0 ~ 12.0 with the ratio of the volume of methanol steam.
22. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 21 and reclaiming procesies, the dry gas that it is characterized in that circulating in described fixed bed adiabatic reactor methanol conversion gasoline process is 5.0 ~ 9.0 with the ratio of the volume of methanol steam.
23. a kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction as claimed in claim 22 and reclaiming procesies, the dry gas that it is characterized in that circulating in described fixed bed adiabatic reactor methanol conversion gasoline process is 6.0 ~ 8.0 with the ratio of the volume of methanol steam.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410356951.2A CN104140839B (en) | 2014-07-25 | 2014-07-25 | A kind of fixed bed adiabatic reactor methanol conversion gasoline successive reaction and reclaiming process |
Applications Claiming Priority (1)
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| CN105738148B (en) * | 2014-12-06 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of solid catalyst on-line period method |
| CN104774637A (en) * | 2015-03-23 | 2015-07-15 | 七台河宝泰隆煤化工股份有限公司 | Synthesis method for stable light hydrocarbon |
| CN107446636B (en) * | 2017-09-06 | 2019-12-20 | 新地能源工程技术有限公司 | High-temperature methane synthesis system and process |
| CN107721799A (en) * | 2017-10-20 | 2018-02-23 | 中石化上海工程有限公司 | The method that parallel reactor pattern automatically switches |
| CN108329188A (en) * | 2018-01-04 | 2018-07-27 | 中石化上海工程有限公司 | The efficiently method of switching methanol-to-olefins device hydrogenation reactor |
| CN108191598A (en) * | 2018-01-04 | 2018-06-22 | 中石化上海工程有限公司 | The method of handoff-security ethylene unit C_3 hydrogenation reactor |
| CN108191597A (en) * | 2018-01-04 | 2018-06-22 | 中石化上海工程有限公司 | The method of ethylene unit Acetylene converter handoff-security |
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| CN101811921A (en) * | 2010-04-01 | 2010-08-25 | 中国科学院山西煤炭化学研究所 | Continuous process for preparing hydrocarbon products through methanol transformation without standby reactor |
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