CN102649088B - Treatment method for catalyst escaping from reactor during preparing low-carbon alkene from methanol or dimethyl ether - Google Patents
Treatment method for catalyst escaping from reactor during preparing low-carbon alkene from methanol or dimethyl ether Download PDFInfo
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- CN102649088B CN102649088B CN201110045521.5A CN201110045521A CN102649088B CN 102649088 B CN102649088 B CN 102649088B CN 201110045521 A CN201110045521 A CN 201110045521A CN 102649088 B CN102649088 B CN 102649088B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
Abstract
The invention relates to a treatment method for a catalyst escaping from a reactor during preparing low-carbon alkene from methanol or dimethyl ether, which mainly solves the problem of high consumption of the catalyst in the prior art. By the adoption of the treatment method for the catalyst escaping from the reactor during preparing low-carbon alkene from methanol or dimethyl ether, raw materials mainly comprising methanol or dimethyl ether are contacted with the catalyst containing molecular sieve of aluminosilicophosphate in a fluidized bed reactor to generate products fluid, after a gas-solid separation, the products fluid carrying a few of the catalyst enter into a third cyclone separator arranged out of the reactor, at least 60 percent of the catalyst is extracted, and the catalyst extracted from the third cyclone separator is transmitted to a thin-phase section of a regenerator. According to the technical scheme, the problem is better solved, and the method can be applied in the industrial production of low-carbon alkene.
Description
Technical field
The present invention relates to the low carbon olefin hydrocarbon reactor escaping lost catalyst produced processing method of a kind of methyl alcohol or dimethyl ether.
Technical background
Low-carbon alkene, ethene and propylene, be two kinds of important basic chemical industry raw materials, its demand is in continuous increase.Usually, ethene, propylene are to produce by petroleum path, but due to the limited supply of petroleum resources and higher price, the cost of being produced ethene, propylene by petroleum resources 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 (dimethyl ether, ethyl methyl ether), ester class (dimethyl carbonate, methyl formate) etc., these oxygenatedchemicals can be transformed by coal, natural gas, living beings equal energy source.Some oxygenatedchemicals can reach fairly large production, as methyl alcohol, can be made by coal or natural gas, and technique is very ripe, can realize the production scale of up to a million tonnes.Popularity due to oxygenatedchemicals source, add and transform the economy that generates light olefin technique, so by the technique of oxygen-containing compound conversion to produce olefine (OTO), particularly the technique by preparing olefin by conversion of methanol (MTO) is subject to increasing attention.
In US4499327 patent, silicoaluminophosphamolecular molecular sieve catalyst is applied to preparing olefin by conversion of methanol technique and studies in detail, think that SAPO-34 is the first-selected catalyst of MTO technique.It is selective that SAPO-34 catalyst has very high light olefin, and activity is also higher, and can make methanol conversion is reaction time of light olefin to be less than the degree of 10 seconds, more even reaches in the reaction time range of riser.
Technology and reactor that a kind of oxygenate conversion is low-carbon alkene in US6166282, have been announced, adopt fast fluidized bed reactor, gas phase is after the lower Mi Xiangfanyingqu of gas speed has reacted, rise to after the fast subregion that internal diameter diminishes rapidly, adopt special gas-solid separation equipment initial gross separation to go out most entrained catalyst.Because reaction afterproduct gas is separated fast with catalyst, effectively prevented the generation of secondary response.Through analog computation, to compare with traditional bubbling fluidization bed bioreactor, this fast fluidized bed reactor internal diameter and the required reserve of catalyst all greatly reduce.
The multiple riser reaction unit of having announced in CN1723262 with central catalyst return is low-carbon alkene technique for oxygenate conversion, this covering device comprises a plurality of riser reactors, gas solid separation district, a plurality of offset components etc., each riser reactor has the port of injecting catalyst separately, be pooled to the Disengagement zone of setting, catalyst and gas product are separated.
CN 200810043615 has announced a kind of methyl alcohol or the low carbon olefin hydrocarbon reactor escaping lost catalyst produced processing method of dimethyl ether, in autoreactor, run the catalyst damaging and enter separative element, through washing, after filtering, form the slag slurry that catalyst concn is higher, then this part slag slurry is delivered to the dilute phase section of regenerator, most of catalyst is run out of and is entered fines collection tank from regenerator outlet after regenerator is dry, obtain dry catalyst fines, but because reactor race damage catalytic amount is larger, make later separation unit quench tower, catalyst detergent and filter progress need catalytic amount to be processed very large, can cause the problems such as quench tower tower tray obstruction, in addition, due to the acidic materials that conventionally adopt the method for note alkali to go out in product stream in separative element, cause the activity of catalyst fines in the final catalyst slag slurry obtaining to be subject to large havoc, cause the value of this partially catalyzed agent to be had a greatly reduced quality.
Known in the field, fluid catalyst exists race to damage phenomenon, and the catalyst cost of methyl alcohol or dimethyl ether producing light olefins is higher, and how as far as possible damage catalyst is run in utilization how becomes a difficult problem.The present invention has solved this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention is the higher problem of catalyst attrition existing in prior art, and a kind of new methyl alcohol or the low carbon olefin hydrocarbon reactor escaping lost catalyst produced processing method of dimethyl ether are provided.The method, for the production of low-carbon alkene, has advantages of that catalyst attrition is lower.
For addressing the above problem, the technical solution used in the present invention is as follows: the processing method that a kind of methyl alcohol or dimethyl ether are low carbon olefin hydrocarbon reactor escaping lost catalyst produced, the raw material that is mainly methyl alcohol or dimethyl ether contacts with the catalyst that comprises silicoaluminophosphamolecular molecular sieve in fluidized-bed reactor, the product stream generating, after gas solid separation, carry a small amount of catalyst and enter the external third-stage cyclone separator of reactor, isolate at least 60% catalyst, then the dilute phase section to regenerator by the isolated catalyst transport of described third-stage cyclone separator.
In technique scheme, described silicoaluminophosphamolecular molecular sieve is selected from SAPO-34; Described reactor and regenerator are fluid bed; In the described product stream entering before described third-stage cyclone separator, catalyst content is less than 0.4 gram/meter
3; The close phase section temperature of regenerator is 600～700 ℃, and regenerator dilute phase Duan Yumi mutually section temperature difference is less than 100 ℃.
Known in the field, because of its wider size consist and more violent wearing and tearing, can there is the less fine powder of partially catalyzed agent particle diameter in fluid catalyst, and these fine powders can not separatedly be run out of reactor with gas product down in conventional gas-solid cyclone separator.For the higher methyl alcohol of price or dimethyl ether alkene catalyst processed, run this part fine powder damaging and be necessary to recycle, to reduce the cost of catalyst.The inventor finds by research, and running this part catalyst fines damaging is can be added in catalyst preparation flow, again utilizes, and as regenerator, outlet is run the catalyst fines damaging and can be transported to catalyst manufacturer and carry out preparing again of catalyst.Therefore, the solution of the present invention is exactly to have solved the recycling problem that reactor outlet runs the most of catalyst fines damaging.At reactor, third-stage cyclone separator is set outward, recovery is back to few 60% race damage catalyst, because this part catalyst activity is higher, and contain a certain amount of carbon distribution, so be delivered in regenerator dilute phase section, after high temperature and rapid drying, most of catalyst fines directly exports out from regenerator and enters catalyst fines collecting tank, in this catalyst fines collecting tank, comprising regenerator runs the catalyst fines damaging and from reactor outlet, runs the dry catalyst fine powder damaging, then the catalyst fines in catalyst fines collecting tank being transported to catalyst manufacturer recycles.Adopt technical scheme of the present invention, except above-mentioned advantage, also effectively utilized energy, the reactor that temperature is lower runs damage catalyst and enters after regenerator dilute phase section, can play the effect that reduces regenerator dilute phase section temperature, effectively reduced in regenerated flue gas CO in " tail combustion " phenomenon of dilute phase section, thereby shortened the temperature difference of the close phase section of regenerator and dilute phase section, guaranteed that regenerator device moves under security context.
Adopt technical scheme of the present invention: described silicoaluminophosphamolecular molecular sieve is selected from SAPO-34; Described reactor and regenerator are fluid bed; In the described product stream entering before described third-stage cyclone separator, catalyst content is less than 0.4 gram/meter
3; The close phase section temperature of regenerator is 600～700 ℃, regenerator dilute phase Duan Yumi mutually section temperature difference is less than 100 ℃, the catalyst fines of recovery is added in catalyst preparation again, the catalyst reactivity worth that contains catalyst fines obtaining is good, low-carbon alkene carbon base absorption rate, all more than 82%, had both reduced the loss of catalyst, took full advantage of to run to damage catalyst fines, improve again low-carbon alkene carbon base absorption rate, obtained good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
The specific embodiment
[embodiment 1]
At recirculating fluidized bed, react in a regenerating unit, reactor is fast fluidized bed, and regenerator is bubbling fluidized bed bed, and catalyst is SAPO-34 molecular sieve, and the mean temperature of reactor reaction zone is 470 ℃, and the mean temperature of regenerator renewing zone is 650 ℃.The catalyst having reacted is after gas-solid separation fast, sedimentation, the separation of built-in two-stage gas-solid cyclone, most of dipleg by built-in cyclone separator returns to stripping zone, the catalyst fines not being separated enters external third-stage cyclone separator from reactor head outlet with gas product, and entering catalyst content in the product stream before described third-stage cyclone separator is 0.19 gram/meter
3, third-stage cyclone separator is recovered to approximately 75% catalyst fines, and residual catalyst fine powder enters centrifugal station with product stream.The isolated catalyst fines of third-stage cyclone separator is transported to the dilute phase section of regenerator, approximately 53 ℃ of the dilute phase Duan Yumi phase section temperature difference of regenerator, this part catalyst fines is after high temperature drying, approximately 70% catalyst fines enters the external third-stage cyclone separator of regenerator with flue gas, through isolated catalyst fines, enters fines collection tank.The cooling rear barrelling of catalyst fines is transported catalyst manufacturer back and is prepared.Add the finished catalyst reactivity worth of preparing after catalyst fines good, ethene+propylene carbon base absorption rate is 82.47% weight.
[embodiment 2]
According to method and the step described in embodiment 1, the mean temperature of regenerator renewing zone changes 602 ℃ into, and regenerator dilute phase Duan Yumi mutually section temperature difference is 98 ℃, and entering catalyst content in the product stream before reactor third-stage cyclone separator is 0.39 gram/meter
3, through third-stage cyclone separator, isolate approximately 61% catalyst fines, catalyst fines is delivered to regenerator dilute phase section.Adding the finished catalyst reactivity worth of preparing after catalyst fines is: ethene+propylene carbon base absorption rate is 82.71% weight.
[embodiment 3]
According to method and the step described in embodiment 1, the mean temperature of regenerator renewing zone is 700 ℃, and regenerator dilute phase Duan Yumi mutually section temperature difference is 34 ℃, and entering catalyst content in the product stream before reactor third-stage cyclone separator is 0.24 gram/meter
3, through third-stage cyclone separator, isolate approximately 82% catalyst fines, catalyst fines is delivered to regenerator dilute phase section.Add the finished catalyst reactivity worth of preparing after catalyst fines good, ethene+propylene carbon base absorption rate is 82.22% weight.
[comparative example 1]
Method and step according to described in embodiment 1, do not arrange reactor third-stage cyclone separator, and reactor runs the catalyst damaging and directly enters separative element, obtains catalyst slag slurry after washing, filtration, slag slurry is delivered to the dilute phase section of regenerator.Add the finished catalyst reactivity worth of preparing after catalyst fines good, ethene+propylene carbon base absorption rate is 81.32% weight.
Obviously, adopt method of the present invention, not only recycle reactor and run the most of catalyst damaging, and the catalyst of recycling activity after regenerator is dry is higher, obtained higher low-carbon alkene carbon base absorption rate, there is larger technical advantage, can the industrial production for low-carbon alkene in.
Claims (4)
1. a methyl alcohol or the low carbon olefin hydrocarbon reactor escaping lost catalyst produced processing method of dimethyl ether, the raw material that is mainly methyl alcohol or dimethyl ether contacts with the catalyst that comprises silicoaluminophosphamolecular molecular sieve in fluidized-bed reactor, the product stream generating, after gas solid separation, carry a small amount of catalyst and enter the external third-stage cyclone separator of reactor, isolate at least 60% catalyst, then the dilute phase section to regenerator by the isolated catalyst transport of described third-stage cyclone separator;
Wherein enter catalyst content in the product stream before third-stage cyclone separator and be less than 0.4 gram/meter
3.
2. the low carbon olefin hydrocarbon reactor escaping lost catalyst produced processing method of methyl alcohol or dimethyl ether according to claim 1, is characterized in that described silicoaluminophosphamolecular molecular sieve is selected from SAPO-34.
3. the low carbon olefin hydrocarbon reactor escaping lost catalyst produced processing method of methyl alcohol or dimethyl ether according to claim 1, is characterized in that described reactor and regenerator are fluid bed.
4. the low carbon olefin hydrocarbon reactor escaping lost catalyst produced processing method of methyl alcohol or dimethyl ether according to claim 1, is characterized in that the close phase section temperature of regenerator is 600～700 ℃, and a regenerator dilute phase Duan Yumi mutually section temperature difference is less than 100 ℃.
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| CN201110045521.5A CN102649088B (en) | 2011-02-25 | 2011-02-25 | Treatment method for catalyst escaping from reactor during preparing low-carbon alkene from methanol or dimethyl ether |
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| CN201110045521.5A CN102649088B (en) | 2011-02-25 | 2011-02-25 | Treatment method for catalyst escaping from reactor during preparing low-carbon alkene from methanol or dimethyl ether |
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| CN108840786A (en) * | 2018-07-27 | 2018-11-20 | 国家能源投资集团有限责任公司 | Methanol-to-olefins device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165018A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene |
| CN101332434A (en) * | 2008-07-08 | 2008-12-31 | 中国石油化工股份有限公司 | Processing method of low carbon olefin hydrocarbon reactor escaping lost catalyst produced by methanol or dimethyl ether |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101165018A (en) * | 2006-10-20 | 2008-04-23 | 中国石油化工股份有限公司 | Method for producing ethylene and propylene |
| CN101332434A (en) * | 2008-07-08 | 2008-12-31 | 中国石油化工股份有限公司 | Processing method of low carbon olefin hydrocarbon reactor escaping lost catalyst produced by methanol or dimethyl ether |
Non-Patent Citations (2)
| Title |
|---|
| MTO技术的发展情况及工艺简介;张善全;《内蒙古石油化工》;20061231(第11期);第52-53页 * |
| 张善全.MTO技术的发展情况及工艺简介.《内蒙古石油化工》.2006,(第11期),第52-53页. |
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