CN102190542B - The coupling process of methanol-to-olefins and carbon more than four hydrocarbon catalytic pyrolysis - Google Patents
The coupling process of methanol-to-olefins and carbon more than four hydrocarbon catalytic pyrolysis Download PDFInfo
- Publication number
- CN102190542B CN102190542B CN201010116461.7A CN201010116461A CN102190542B CN 102190542 B CN102190542 B CN 102190542B CN 201010116461 A CN201010116461 A CN 201010116461A CN 102190542 B CN102190542 B CN 102190542B
- Authority
- CN
- China
- Prior art keywords
- reaction zone
- catalyzer
- carbon
- gas
- fluidized bed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of 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
-
- 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
- Y02P30/40—Ethylene production
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to the coupling process of a kind of methanol-to-olefins and carbon more than four hydrocarbon catalytic pyrolysis, mainly solve the problem that in prior art, yield of light olefins is not high.The present invention is by adopting the coupling process of a kind of methanol-to-olefins and carbon more than four hydrocarbon catalytic pyrolysis, mainly comprise the following steps: the raw material that (1) comprises methyl alcohol enters main reactor reaction zone, with comprise silicoaluminophosphamolecular molecular sieve catalyst and contact, generate the product stream I comprising low-carbon alkene, form the catalyzer of inactivation simultaneously; (2) catalyzer of described inactivation enters revivifier regeneration, the catalyzer regenerated enters riser reaction zone, with the contact raw comprising carbon more than four hydrocarbon, the product generated and catalyzer enter down-flow fluidized bed using ECT reaction zone behind catalyzer buffering fluidization regions, with the contact raw comprising carbon more than four hydrocarbon, generate the product stream II comprising low-carbon alkene, form the catalyzer of pre-carbon deposit simultaneously; (3) described product stream II is mixed into centrifugal station with product stream I after gas solid separation, and the technical scheme that the catalyzer of described pre-carbon deposit returns to main reactor reaction zone solves the problems referred to above preferably, can be used in the industrial production of low-carbon alkene.
Description
Technical field
The present invention relates to the coupling process of a kind of methanol-to-olefins and carbon more than four hydrocarbon catalytic pyrolysis.
Technical background
Low-carbon alkene, i.e. ethene and propylene, be two kinds of important basic chemical industry raw materials, its demand is in continuous increase.Usually, ethene, propylene are produced by petroleum path, but due to the limited supply of petroleum resources and higher price, produce ethene by petroleum resources, the cost of propylene constantly increases.In recent years, people start to greatly develop the technology that alternative materials transforms ethene processed, propylene.Wherein, the important alternative materials for light olefin production of one class is oxygenatedchemicals, such as alcohols (methyl alcohol, ethanol), ethers (dme, methyl ethyl ether), ester class (methylcarbonate, methyl-formiate) etc., these oxygenatedchemicalss can be transformed by coal, Sweet natural gas, biomass equal energy source.Some oxygenatedchemicals can reach fairly large production, and as methyl alcohol, can be obtained by coal or Sweet natural gas, technique is very ripe, can realize the industrial scale of up to a million tonnes.Due to the popularity in oxygenatedchemicals source, add the economy transforming and generate light olefin technique, so by the technique of oxygen-containing compound conversion to produce olefine (OTO), be particularly subject to increasing attention by the technique of preparing olefin by conversion of methanol (MTO).
Be applied to preparing olefin by conversion of methanol technique to silicoaluminophosphamolecular molecular sieve catalyst in US4499327 patent to study in detail, think that SAPO-34 is the first-selected catalyzer of MTO technique.SAPO-34 catalyzer has very high light olefin selectivity, and activity is also higher, methanol conversion can be made to be less than the degree of 10 seconds in reaction times of light olefin, more even reach in the reaction time range of riser tube.
Technology and reactor that a kind of oxygenate conversion is low-carbon alkene is disclosed in US6166282, adopt fast fluidized bed reactor, gas phase is after the lower Mi Xiangfanyingqu of gas speed has reacted, after rising to the fast subregion that internal diameter diminishes rapidly, special gas-solid separation equipment initial gross separation is adopted to go out most entrained catalyst.Due to reaction after product gas and catalyzer sharp separation, effectively prevent the generation of secondary reaction.Through analog calculation, compared with traditional bubbling fluidization bed bioreactor, needed for this fast fluidized bed reactor internal diameter and catalyzer, reserve all greatly reduces.
The multiple riser reaction unit disclosed in CN1723262 with central catalyst return is low-carbon alkene technique for oxygenate conversion, this covering device comprises multiple riser reactor, gas solid separation district, multiple offset components etc., each riser reactor has the port of injecting catalyst separately, be pooled to the disengaging zone of setting, catalyzer and gas product are separated.
A kind of method improving yield of light olefins is disclosed in Chinese invention patent 200810043971.9, the method adopts and arranges a second reaction zone on the first top, reaction zone that methanol conversion is low-carbon alkene, and this second reaction zone diameter is greater than the first reaction zone, to increase the residence time of gas product in second reaction zone of the first reaction zone outlet, make unreacted methyl alcohol, the dme generated and carbon more than four hydrocarbon continue reaction, reach the object improving yield of light olefins, the charging that the method also comprises second reaction zone can be through freshening carbon more than four hydrocarbon of separation.Although the method can improve the yield of low-carbon alkene to a certain extent, but because the first reaction zone catalyzer is out with more carbon distribution, and carbon more than four hydrocarbon pyrolysis needs higher catalyst activity, carbon more than the four hydrocarbon changing effect therefore in the method in second reaction zone is still on the low side.
Therefore, need a kind of novel method, to reach the object being converted into low-carbon alkene making carbon more than four hydrocarbon as far as possible many, finally reach the object improving yield of light olefins and process economy.The present invention solves the problems referred to above targetedly.
Summary of the invention
Technical problem to be solved by this invention is the problem that the yield of light olefins that exists in prior art is not high, provides the coupling process of a kind of new methanol-to-olefins and carbon more than four hydrocarbon catalytic pyrolysis.The method is used for, in the production of low-carbon alkene, having the advantage of yield of light olefins more high and low carbon olefin production technique better economy.
For solving the problem, the technical solution used in the present invention is as follows: the coupling process of a kind of methanol-to-olefins and carbon more than four hydrocarbon catalytic pyrolysis, mainly comprise the following steps: the raw material that (1) comprises methyl alcohol enters main reactor reaction zone, with comprise silicoaluminophosphamolecular molecular sieve catalyst and contact, generate the product stream I comprising low-carbon alkene, form the catalyzer of inactivation simultaneously; (2) catalyzer of described inactivation enters revivifier regeneration, the catalyzer regenerated enters riser reaction zone, with the contact raw comprising carbon more than four hydrocarbon, the product generated and catalyzer enter down-flow fluidized bed using ECT reaction zone behind catalyzer buffering fluidization regions, with the contact raw comprising carbon more than four hydrocarbon, generate the product stream II comprising low-carbon alkene, form the catalyzer of pre-carbon deposit simultaneously; (3) described product stream II is mixed into centrifugal station with product stream I after gas solid separation, and the catalyzer of described pre-carbon deposit returns to main reactor reaction zone.
In technique scheme, described silicoaluminophosphamolecular molecular sieves is selected from least one in SAPO-5, SAPO-11, SAPO-18, SAPO-20, SAPO-34, SAPO-44, SAPO-56, and preferred version is SAPO-34; Temperature of reaction in described main reactor reaction zone is 400 ~ 500 DEG C, preferred version is 430 ~ 480 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and preferred version is 0.1 ~ 0.2MPa, linear gas velocity is 0.8 ~ 2.5 meter per second, and preferred version is 1.0 ~ 1.5 meter per seconds; Temperature of reaction in riser reaction zone is 510 ~ 650 DEG C, preferred version is 550 ~ 600 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and preferred version is 0.1 ~ 0.2MPa, linear gas velocity is 3.0 ~ 10.0 meter per seconds, and preferred version is 5.0 ~ 7.0 meter per seconds; Temperature of reaction in down-flow fluidized bed using ECT reaction zone is 500 ~ 630 DEG C, preferred version is 530 ~ 580 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and preferred version is 0.1 ~ 0.2MPa, linear gas velocity is 5.0 ~ 15.0 meter per seconds, and preferred version is 7.0 ~ 10.0 meter per seconds; The carbon deposition quantity of the catalyzer of described pre-carbon deposit is 0.1 ~ 1.8% weight, and preferred version is 0.5 ~ 1.2% weight.
The preparation method of silicoaluminophosphamolecular molecular sieve of the present invention is: first prepare molecular sieve precursor, is 0.03 ~ 0.6R by mol ratio: (Si 0.01 ~ 0.98: Al 0.01 ~ 0.6: P 0.01 ~ 0.6): 2 ~ 500H
2o, wherein R represents template, and constitutive material mixed solution, obtains at a certain temperature after the crystallization of certain hour; Again, after molecular sieve precursor, phosphorus source, silicon source, aluminium source, organic formwork agent, water etc. being mixed according to certain ratio, at 110 ~ 260 DEG C, hydrothermal crystallizing, after at least 0.1 hour, finally obtains SAPO molecular sieve.
Mixed with a certain proportion of binding agent by the molecular sieve of preparation, after the operation steps such as spraying dry, roasting, obtain final SAPO catalyzer, the weight percentage of binding agent in molecular sieve is generally between 10 ~ 90%.
Three reaction zones are provided with in the method for the invention, main reactor reaction zone is relatively independent, for preparing olefin by conversion of methanol, riser reaction zone and the series connection of down-flow fluidized bed using ECT reaction zone, for transforming carbon more than four hydrocarbon and being the methyl alcohol of reaction or dme etc., reach the object improving feed stock conversion and yield of light olefins.Wherein, down-flow fluidized bed using ECT reaction zone is except ensure that the enough reaction times, also because the characteristic of approximate gas-solid plug flow, reduce the occurrence probability of side reaction, the significantly selectivity of low-carbon alkene, maximized conversion carbon more than four hydrocarbon is low-carbon alkene, and in addition, its parameter such as material level, temperature of reaction can independently control.And the catalyzer in riser reaction zone is directly from revivifier, the activity of the temperature of carrying and catalyzer self is all higher, is conducive to the conversion of carbon more than four hydrocarbon to low-carbon alkene.In addition, after being regenerated catalyst through riser reaction zone and down-flow fluidized bed using ECT reaction zone, a certain amount of carbon deposit can be accumulated after reaction, the present inventor is found by research, carbon more than four hydrocarbon be converted in low carbon olefin hydrocarbon a certain amount of carbon distribution accumulated on a catalyst be conducive to improve methanol conversion be the selectivity of low-carbon alkene, so after this part catalyzer with a certain amount of carbon distribution returns to main reactor reaction zone, the selectivity of light olefin in main reactor reaction zone can be significantly improved.Simultaneously, be strong endothermic reaction because carbon more than four hydrocarbon pyrolysis is low-carbon alkene, the heat of the catalyst entrainment therefore after riser reaction zone and down-flow fluidized bed using ECT reaction zone have been reacted declines, after returning to main reactor reaction zone, alleviate the heat-obtaining load of main reactor reaction zone, effectively make use of heat.A catalyzer buffering fluidization regions is also had between riser reaction zone and down-flow fluidized bed using ECT reaction zone, not only play the uniform object of catalyst mix, and this region can enter methanol feedstock, ensured the temperature of the catalyzer before entering down-flow fluidized bed using ECT reaction zone and gaseous mixture by reaction liberated heat.Therefore, adopt described method of the present invention, both effectively improve the yield of object product low-carbon alkene, optimize again energy distribution and utilization.
Adopt technical scheme of the present invention: described silicoaluminophosphamolecular molecular sieves is selected from least one in SAPO-5, SAPO-11, SAPO-18, SAPO-20, SAPO-34, SAPO-44, SAPO-56; Temperature of reaction in described main reactor reaction zone is 400 ~ 500 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and linear gas velocity is 0.8 ~ 2.5 meter per second; Temperature of reaction in riser reaction zone is 510 ~ 650 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and linear gas velocity is 3.0 ~ 10.0 meter per seconds; Temperature of reaction in down-flow fluidized bed using ECT reaction zone is 500 ~ 630 DEG C, and reaction pressure counts 0.01 ~ 0.3MPa with gauge pressure, and linear gas velocity is 5.0 ~ 15.0 meter per seconds; The carbon deposition quantity of the catalyzer of described pre-carbon deposit is 0.1 ~ 1.8% weight, and selectivity of light olefin can reach 90.75% weight, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for the invention.
In Fig. 1,1 is main reactor reaction zone bottom feed; 2 is main reactor reaction zone; 3 is gas-solid sharp separation equipment; 4 is stripping stage; 5 return the line of pipes of main reactor reaction zone for stripping stage catalyzer; 6 is reclaimable catalyst inclined tube; 7 is main reactor reaction zone external warmer; 8 is gas-solid cyclone separator; 9 is reactor gas solid separation district; 10 is collection chamber; 11 is reactor product outlet line; 12 is revivifier gas solid separation district; 13 is regenerating medium source line; 14 is revivifier breeding blanket; 15 is external catalyst cooler for regenerator; 16 is revivifier gas-solid cyclone separator; 17 is regenerated flue gas outlet line; 18 is regenerated catalyst inclined tube; 19 is riser reaction zone charging; 20 cushion mixing zone for bottom riser reaction zone; 21 is riser reaction zone; 22 is catalyzer buffering fluidization regions; 23 is catalyzer buffering fluidization regions bottom feed; 24 is down-flow fluidized bed using ECT reaction zone upper side opening for feed; 25 is down-flow fluidized bed using ECT reaction zone its top feed; 26 is down-flow fluidized bed using ECT reaction zone; 27 is down-flow fluidized bed using ECT outlet gas-solid Cyclonic separating apparatus; 28 return the line of pipes of main reactor reaction zone for catalyzer; 29 is the pipeline in down-flow fluidized bed using ECT exit gas product introduction main reactor gas solid separation district.
Raw material enters in main reactor reaction zone 2 through feeding line 1, contact with molecular sieve catalyst, reaction generates the product stream I containing low-carbon alkene, after gas-solid sharp separation equipment 3, enter gas solid separation district 9, and decaying catalyst enters revivifier regeneration from reclaimable catalyst inclined tube 6.Catalyzer after having regenerated enters the catalyzer buffer zone 20 bottom riser reaction zone 21 from regenerated catalyst inclined tube 18, riser reaction zone 21 is entered with after the contact raw of pipeline 19, the product that riser reaction zone 21 exports and catalyzer enter in down-flow fluidized bed using ECT reaction zone 26 behind catalyzer buffering fluidization regions 22, again with the contact raw comprising carbon more than four hydrocarbon, generate low-carbon alkene product stream II, after gas-solid separator 27 is separated, product enters reactor disengaging zone 9 from pipeline 29, centrifugal station is entered from outlet line 11 after mixing with product stream I.In down-flow fluidized bed using ECT reaction zone 26, reacted catalyzer returns main reactor reaction zone 2 from pipeline 28.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
In reaction unit as shown in Figure 1, main reactor reaction zone medial temperature is 480 DEG C, and reaction pressure counts 0.1MPa with gauge pressure, and linear gas velocity is 1.5 meter per seconds; Riser reaction zone medial temperature is 550 DEG C, and reaction pressure counts 0.1MPa with gauge pressure, and linear gas velocity is 5.0 meter per seconds; Down-flow fluidized bed using ECT reaction zone medial temperature is 500 DEG C, and reaction pressure counts 0.1MPa with gauge pressure, and linear gas velocity is 7.0 meter per seconds.The carbon deposition quantity of pre-carbon deposition catalyst is 0.5% weight.Main reactor reaction zone bottom feed is pure methyl alcohol, and charging is 2 kgs/hr, and catalyzer is SAPO-34, wherein SiO in molecular sieve
2: A1
2o
3: P
2o
5=0.1: 1: 1, in catalyzer, binder content is 60%.Riser reaction zone bottom feed is mixed c 4, C 4 olefin content 87%, down-flow fluidized bed using ECT reaction zone its top feed is identical with riser reaction zone bottom feed, keep the stability of catalyst flow control, reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 87.23% weight.
[embodiment 2]
According to the condition described in embodiment 1, main reactor reaction zone medial temperature is 500 DEG C, and reaction pressure counts 0.2MPa with gauge pressure, and linear gas velocity is 2.5 meter per seconds; Riser reaction zone medial temperature is 650 DEG C, and reaction pressure counts 0.2MPa with gauge pressure, and linear gas velocity is 10.0 meter per seconds; Down-flow fluidized bed using ECT reaction zone medial temperature is 630 DEG C, and reaction pressure counts 0.2MPa with gauge pressure, and linear gas velocity is 15.0 meter per seconds.The carbon deposition quantity of pre-carbon deposition catalyst is 1.8% weight.Riser reaction zone bottom feed is mixed c 4, C 4 olefin content 58%, and keep the stability of catalyst flow control, reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 84.78% weight.
[embodiment 3]
According to the condition described in embodiment 1, main reactor reaction zone medial temperature is 400 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and linear gas velocity is 0.8 meter per second; Riser reaction zone medial temperature is 600 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and linear gas velocity is 3.0 meter per seconds; Down-flow fluidized bed using ECT reaction zone medial temperature is 530 DEG C, and reaction pressure counts 0.01MPa with gauge pressure, and linear gas velocity is 10.0 meter per seconds.The carbon deposition quantity of pre-carbon deposition catalyst is 0.1% weight.Keep the stability of catalyst flow control, reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 85.14% weight.
[embodiment 4]
According to the condition described in embodiment 1, main reactor reaction zone medial temperature is 430 DEG C, and reaction pressure counts 0.3MPa with gauge pressure, and linear gas velocity is 1.0 meter per seconds; Riser reaction zone medial temperature is 510 DEG C, and reaction pressure counts 0.3MPa with gauge pressure, and linear gas velocity is 7.0 meter per seconds; Down-flow fluidized bed using ECT reaction zone medial temperature is 500 DEG C, and reaction pressure counts 0.3MPa with gauge pressure, and linear gas velocity is 5.0 meter per seconds.The carbon deposition quantity of pre-carbon deposition catalyst is 1.2% weight.Keep the stability of catalyst flow control, reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 86.84% weight.
[embodiment 5]
According to the condition described in embodiment 1, main reactor reaction zone linear gas velocity is 1.2 meter per seconds; Riser reaction zone medial temperature is 600 DEG C; Down-flow fluidized bed using ECT reaction zone medial temperature is 580 DEG C.The carbon deposition quantity of pre-carbon deposition catalyst is 0.8% weight.Riser reaction zone bottom feed is mixed c 4, C 4 olefin content 95%, and keep the stability of catalyst flow control, reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 88.41% weight.
[embodiment 6]
According to the condition described in embodiment 5, riser reaction zone bottom feed is mixed c 4, C 4 olefin content 75%, down-flow fluidized bed using ECT reaction zone its top feed is mixed c 4, C 4 olefin content 95%, keep the stability of catalyst flow control, reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 88.27% weight.
[embodiment 7]
According to the condition described in embodiment 5, down-flow fluidized bed using ECT reaction zone its top feed is mixed c 4 and methyl alcohol, and the olefin(e) centent in mixed c 4 is 95%, and the weight ratio of mixed c 4 and methyl alcohol is 4: 1.Keep the stability of catalyst flow control, reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 90.75% weight.
[embodiment 8 ~ 11]
According to the condition described in embodiment 1, just change the type of catalyzer Middle molecule sieve, experimental result is in table 1.
Table 1
| Parameter | Molecular sieve type | Yield of light olefins, % (weight) |
| Embodiment 8 | SAPO-20 | 78.54 |
| Embodiment 9 | SAPO-18 | 86.27 |
| Embodiment 10 | SAPO-56 | 69.01 |
| Embodiment 11 | SAPO-34+SAPO-18 (weight ratio is 2: 1) | 87.85 |
[embodiment 12]
According to the condition described in embodiment 1, SiO in molecular sieve
2: Al
2o
3: P
2o
5=0.2: 1: 1, in catalyzer, binder content is 70%., light olefin carbon base absorption rate is 84.96% (weight).
[comparative example 1]
According to the condition described in embodiment 1, do not establish riser reaction zone and down-flow fluidized bed using ECT reaction zone, regenerated catalyst directly turns back to the bottom of main reactor reaction zone, and low-carbon alkene carbon base absorption rate is 79.5% weight.
Obviously, adopt method of the present invention, the object improving yield of light olefins can be reached, there is larger technical superiority, can be used in the industrial production of low-carbon alkene.
Claims (1)
1. a coupling process for methanol-to-olefins and carbon more than four hydrocarbon catalytic pyrolysis, comprising main reactor reaction zone bottom feed line (1), main reactor reaction zone (2), gas-solid sharp separation equipment (3), stripping stage (4), stripping stage catalyzer returns the line of pipes (5) of main reactor reaction zone, reclaimable catalyst inclined tube (6), main reactor reaction zone external warmer (7), gas-solid cyclone separator (8), reactor gas solid separation district (9), collection chamber (10), reactor product outlet line (11), revivifier gas solid separation district (12), regenerating medium source line (13), revivifier breeding blanket (14), external catalyst cooler for regenerator (15), revivifier gas-solid cyclone separator (16), regenerated flue gas outlet line (17), regenerated catalyst inclined tube (18), riser reaction zone feeding line (19), catalyzer buffer zone (20) bottom riser reaction zone, riser reaction zone (21), catalyzer buffering fluidization regions (22), catalyzer buffering fluidization regions bottom feed (23), down-flow fluidized bed using ECT reaction zone upper side opening for feed (24), down-flow fluidized bed using ECT reaction zone its top feed (25), down-flow fluidized bed using ECT reaction zone (26), down-flow fluidized bed using ECT outlet gas-solid Cyclonic separating apparatus (27), catalyzer returns the line of pipes (28) of main reactor reaction zone, the pipeline (29) in down-flow fluidized bed using ECT exit gas product introduction main reactor gas solid separation district,
Raw material enters in main reactor reaction zone (2) through main reactor reaction zone bottom feed line (1), contact with molecular sieve catalyst, reaction generates the product stream I containing low-carbon alkene, after gas-solid sharp separation equipment (3), enter gas solid separation district (9), decaying catalyst enters revivifier regeneration from reclaimable catalyst inclined tube (6), catalyzer after having regenerated enters the catalyzer buffer zone (20) bottom riser reaction zone from regenerated catalyst inclined tube (18), riser reaction zone (21) is entered with after the contact raw come from riser reaction zone feeding line (19), the product that riser reaction zone (21) exports and catalyzer cushion behind fluidization regions (22) through catalyzer and enter in down-flow fluidized bed using ECT reaction zone (26), again with the contact raw comprising carbon more than four hydrocarbon, generate low-carbon alkene product stream II, form pre-carbon deposition catalyst simultaneously, after down-flow fluidized bed using ECT outlet gas-solid Cyclonic separating apparatus (27) is separated, product enters reactor gas solid separation district (9) from the pipeline (29) in down-flow fluidized bed using ECT exit gas product introduction main reactor gas solid separation district, centrifugal station is entered from reactor product outlet line (11) after mixing with product stream I, the line of pipes (28) that in down-flow fluidized bed using ECT reaction zone (26), reacted catalyzer returns to main reactor reaction zone from catalyzer returns main reactor reaction zone (2),
Described main reactor reaction zone medial temperature is 480 DEG C, and reaction pressure counts 0.1MPa with gauge pressure, and linear gas velocity is 1.2 meter per seconds; Riser reaction zone medial temperature is 600 DEG C, and reaction pressure counts 0.1MPa with gauge pressure, and linear gas velocity is 5.0 meter per seconds; Down-flow fluidized bed using ECT reaction zone medial temperature is 580 DEG C, and reaction pressure counts 0.1MPa with gauge pressure, and linear gas velocity is 7.0 meter per seconds; The carbon deposition quantity of pre-carbon deposition catalyst is 0.8% weight; Main reactor reaction zone bottom feed is pure methyl alcohol, and charging is 2 kgs/hr, and molecular sieve catalyst is SAPO-34, wherein SiO in molecular sieve
2: Al
2o
3: P
2o
5=0.1: 1: 1, in catalyzer, binder content is 60%; Riser reaction zone bottom feed is mixed c 4 and methyl alcohol, the olefin(e) centent 95% in mixed c 4, and the weight ratio of mixed c 4 and methyl alcohol is 4: 1; Down-flow fluidized bed using ECT reaction zone its top feed is identical with riser reaction zone bottom feed, and keep the stability of catalyst flow control, reactor outlet product adopts online gas chromatographic analysis, and yield of light olefins reaches 90.75% weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010116461.7A CN102190542B (en) | 2010-03-03 | 2010-03-03 | The coupling process of methanol-to-olefins and carbon more than four hydrocarbon catalytic pyrolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010116461.7A CN102190542B (en) | 2010-03-03 | 2010-03-03 | The coupling process of methanol-to-olefins and carbon more than four hydrocarbon catalytic pyrolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102190542A CN102190542A (en) | 2011-09-21 |
| CN102190542B true CN102190542B (en) | 2015-09-09 |
Family
ID=44599509
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010116461.7A Active CN102190542B (en) | 2010-03-03 | 2010-03-03 | The coupling process of methanol-to-olefins and carbon more than four hydrocarbon catalytic pyrolysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102190542B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739419B (en) * | 2012-10-17 | 2015-09-09 | 中国石油化工股份有限公司 | The method of preparing light olefins from methanol |
| CN107529620A (en) * | 2017-06-08 | 2018-01-02 | 内蒙古中煤蒙大新能源化工有限公司 | The analysis method of carbonyls in a kind of product of methanol-to-olefins device carbon four |
| CN110511773B (en) * | 2018-08-16 | 2021-02-26 | 中国石油大学(华东) | Device and method for coupling biomass pyrolysis and catalytic cracking reaction |
| CN109503309A (en) * | 2018-12-10 | 2019-03-22 | 中石化上海工程有限公司 | The method that light hydrocarbon cracking predepropanization technique is coupled with MTO technique |
| CN111423302B (en) * | 2019-01-09 | 2023-09-19 | 国家能源投资集团有限责任公司 | Method and device for preparing olefin from methanol |
| CN115304442A (en) * | 2021-05-08 | 2022-11-08 | 国家能源投资集团有限责任公司 | Preparation of C from methanol 2 -C 3 Process and apparatus for olefins |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279877A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for increasing yield of ethylene and propone in conversion process of oxocompound |
| CN101348404A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Method for improving ethylene and propene yield in methyl alcohol or dimethyl ether conversion process |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089640C (en) * | 1999-05-19 | 2002-08-28 | 中国石油化工集团公司 | Regeneration process of hydrocarbon converting catalyst |
| FR2835201B1 (en) * | 2002-01-25 | 2004-04-09 | Inst Francais Du Petrole | INTEGRATING THE CATALYST REDUCTION OF A CATALYTIC CONVERSION PROCESS AND THE REGENERATION OF ADSORBENT MASSES INTERVENING IN THE PURIFICATION OF THE HYDROGEN NECESSARY FOR REDUCTION |
-
2010
- 2010-03-03 CN CN201010116461.7A patent/CN102190542B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279877A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Method for increasing yield of ethylene and propone in conversion process of oxocompound |
| CN101348404A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Method for improving ethylene and propene yield in methyl alcohol or dimethyl ether conversion process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102190542A (en) | 2011-09-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102190550B (en) | The production method of low-carbon alkene | |
| CN102276386B (en) | Production method of light olefins | |
| CN101941876B (en) | Method for increasing production of light olefin | |
| CN102190548B (en) | Method for enhancing yield of light olefins in MTO technology | |
| CN102464532B (en) | Method for preparing low-carbon olefins | |
| CN102190542B (en) | The coupling process of methanol-to-olefins and carbon more than four hydrocarbon catalytic pyrolysis | |
| CN102464524B (en) | Method for producing low-carbon olefins from methanol | |
| CN102276406B (en) | Method for increasing yield of propylene | |
| CN103739420A (en) | Method of increasing the yield of low-carbon olefins | |
| CN102464523B (en) | Method for producing light olefins | |
| CN102464522B (en) | Method for producing low-carbon olefins | |
| CN102190538B (en) | Method for Catalytic pyrolysis of hydrocarbons with more than 4 carbon atoms in process of preparing olefins from methanol | |
| CN102276390A (en) | Method for adjusting product proportion in process of preparing olefin from methanol | |
| CN102190540B (en) | Method for producing propylene | |
| CN102464528B (en) | Method for increasing yields of ethylene and propylene | |
| CN102464526B (en) | Method for producing low-carbon olefins from methanol | |
| CN103772089A (en) | Reaction device for improving yield of ethylene and propylene | |
| CN103739428A (en) | Device for producing low-carbon olefins from methanol | |
| CN102295504B (en) | Method for preparing low-carbon olefin by using methanol | |
| CN103772088B (en) | Improve the method for ethene, propene yield | |
| CN103772105B (en) | Improve the reaction unit of yield of light olefins | |
| CN103772091B (en) | By the method for preparing low carbon olefin hydrocarbon with methanol | |
| CN102190547B (en) | Improve the method for yield of light olefin products | |
| CN102464527B (en) | Method for producing low-carbon olefins from low-carbon alcohols | |
| CN103664449A (en) | Method for preparing low carbon olefin through oxygenated chemicals |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |