CN103611567A - Regeneration method of methanol-to-olefin catalyst - Google Patents
Regeneration method of methanol-to-olefin catalyst Download PDFInfo
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- CN103611567A CN103611567A CN201310654118.1A CN201310654118A CN103611567A CN 103611567 A CN103611567 A CN 103611567A CN 201310654118 A CN201310654118 A CN 201310654118A CN 103611567 A CN103611567 A CN 103611567A
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Abstract
The invention relates to a regeneration method of a methanol-to-olefin catalyst. The regeneration method comprises the following steps: performing gas stripping on a molecular sieve catalyst aqueous solution with reduced activity in a methanol-to-olefin reaction to remove entrained organic matters, oxidizing the catalyst solution to further deoil, filtering impurities in the deoiled catalyst, and homogenizing and stabilizing the catalyst. The activity of the catalyst treated in the steps is recovered to the uttermost, and the catalyst is directly pumped into a hydration reaction system by a pump to be recycled. The regeneration method of the methanol-to-olefin catalyst provided by the invention can be used for recovering the catalyst activity to more than 99% of the initial activity so as to online regenerate the catalyst at the same state as slurry in a reactor.
Description
Technical field
The present invention relates to a kind of process of methanol to olefins reaction, be specifically related to the renovation process of methanol-to-olefins catalyst.
Background technology
Molecular sieve catalyst is because its special catalytic performance is used in preparing cyclohexanol by cyclohexene hydration reaction technique.Yet along with the carrying out of reaction, the activity of catalyst there will be reduction, this is the acid activated centre that organic matter in reaction system occupies catalyst on the one hand, causes the passivation of catalyst.In addition nitrogen-containing compound, metal ion etc. also have larger toxicity to catalyst, and the accumulation of various catalyst poisoning things also causes active decline.For maintaining the activity of catalyst, keep reaction to continue normally to carry out, need to take measures to recover catalyst performance.
Patent CN102284302A discloses a kind of methanol-to-olefins Catalysts and its preparation method, first molecular sieve is dispersed in the decentralized medium that contains binding agent, additive is added in the mixture that contains molecular sieve, binding agent again, after mixing, carry out grain refine, water slurry is sprayed dry, after dry, obtain microballoon, resulting catalyst has the catalytic activity of good methanol-to-olefins, higher olefine selective and excellent abrasion resisting performance.But wherein do not relate to inactivation and the regeneration of relevant catalyst.
Patent CN1071595C discloses a kind of preprocess method of zeolite catalyst and has prepared the method for alcohol with it.Proposition first contacted with water before zeolite catalyst is used carries out pretreatment to improve selectively, has proposed to adopt this catalyst to carry out the technological parameter of cyclohexene aquation.Do not relate to the life problems of relevant catalyst.
Patent CN1092626C discloses a kind of employing intumescence masonry catalyst, through cyclohexene hydration, manufacture the method for cyclohexanol, in the life-span that the content of proposition by impurity such as 2-cyclohexene-1 ketone in control loop hexene improves catalyst, do not relate to relevant catalyst activity and recover problem.
According to the mechanism of catalytic reaction of methanol-to-olefins, along with the carrying out of reaction, the active sites of catalyst is partly occupied, and is subject to the pollution of some Toxic.Therefore, want the steady in a long-term high activity that maintains catalyst, just need to eliminate the factor that reduces catalyst activity, the activity of catalyst is restored, completed on this basis the present invention.
Summary of the invention
The invention provides the renovation process of the catalyst that methanol-to-olefins uses, can make catalyst activity return to the more than 99% of initial activity, adopt catalyst bypass regeneration techniques scheme, make catalyst under the slurry condition with identical in reactor, realize the on-line regeneration of catalyst.
The technical solution used in the present invention is:
The renovation process of methanol-to-olefins catalyst, comprise the organic matter except deentrainment by the molecular sieve catalyst aqueous solution air lift of activity decreased in methanol to olefins reaction, catalyst solution is oxidized to further oil removing, the catalyst after oil removing is removed by filter impurity and is in harmonious proportion and stablize treatment step.
Each step detailed process is as follows:
In air lift step, first the catalyst slurry that autoreactor is drawn enters air lift device, with nitrogen or water vapour, carries out air lift, preferably adopts the method for indirect air lift during with water vapour, uses water vapour indirect, slurries is evaporated to air lift and remove organic matter.Process air lift is by the organic matter removal that dissolves in catalyst slurry, carries secretly, adsorbs.Air lift pressure is 0～0.1MPa, air lift temperature 95～110.C。While exporting content of organics lower than 0.1～1000ppm to air lift device, air lift finishes.
In oxidation step, through air lift, most of oil is removed, and is then delivered to oxidation tank, with air or hydrogen peroxide, is further oxidized remaining organic matter, adopts hydrogen peroxide to make oxidant and can avoid introducing other impurity.For preventing the excessively oxidated or dysoxidation of catalyst, need strict amount and the concentration of controlling reaction condition and oxidant.While adopting air, the volume ratio of air and catalyst slurry is 10～100Nm
3every cubic metre of catalyst slurry, for increasing treatment effect, air can adopt oxygen-enriched air, and Control for Oxygen Content is below 30%; While adopting hydrogen peroxide, its concentration is unsuitable too high or too low, and suitable concentration is 10～50%, and preferably 20～30%, the mass ratio of the dioxygen water yield and catalyst is 0.05～1.Oxidation processes pressure is 0～0.1MPa, 80～110 ℃ of temperature.Through peroxidating, organic matter is oxidized to acids, is dissolved in the water.
In filtration step, adopt filter method to remove part filtrate, add water washing, carry out circulating filtration, until acidity reaches desired value.Filter and adopt accurate filter, the impurity acid that in catalyst, oxidation produces is removed by filter.
Be in harmonious proportion and stablize in treatment step, filter rear catalyst and thicken, for keeping consistent with virgin pulp liquid, add high purity water to be in harmonious proportion and stablize processing.
Above-mentioned processing scheme, can be from extraction portion divided catalyst in reactor, and after regeneration is processed, recirculation is back to reactor.Methanol to olefins reaction is unaffected in catalyst regeneration process.According to the life requirements of catalyst, the ratio of taking out regenerated catalyst through setting is 0.5～5%, can complete within a certain period of time the regeneration of all catalyst in reaction system, make reaction system inner catalyst remain greater activity and selective, thereby realize long period, the continuous and steady operation of methanol to olefins reaction.
Through the catalyst of above step process, activity is recovered to greatest extent, directly sends hydration reaction systemic circulation back to use with pump.
The beneficial effect that the present invention has:
The renovation process of methanol-to-olefins catalyst of the present invention can make catalyst activity return to the more than 99% of initial activity, makes catalyst under the slurry condition with identical in reactor, realizes the on-line regeneration of catalyst.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.But the drawings and specific embodiments are not construed as limiting the invention.
From the catalyst of the part activity decreased of reaction system (be about catalyst total amount 1%), enter into air lift device, by water vapour air lift, remove the cyclohexene carried secretly and cyclohexanol etc., air lift pressure 10KPaG, 102 ℃ of temperature.When in analysis tail gas component, content of organics is lower than 10ppm, air lift finishes.Air lift rear slurry enters into oxidation tank, passes into 20% hydrogen peroxide and carries out oxidation processes, and the amount of hydrogen peroxide is catalytic amount 10%, and oxidative pressure is normal pressure, 90 ℃ of temperature.Catalyst after oxidation processes is removed by filter to sour water.After filtration completes, fill into high purity water, make catalyst concn and come the concentration of slurry of autoreactor identical, reach 30%.After stirring stable processing, catalyst activity is restored, with being pumped back to hydration reaction system.
Above-mentioned processing scheme, the ratio in 1%, from extraction portion divided catalyst in reactor, after regeneration is processed, then is back to reactor.Methanol to olefins reaction is unaffected in catalyst regeneration process.Can in 100 hours, complete the regeneration of all catalyst in reaction system, make reaction system inner catalyst remain greater activity and selective, thereby realize long period, the continuous and steady operation of methanol-to-olefins hydration reaction.
Above preferred embodiment of the present invention is had been described in detail, but described content is only preferred embodiment of the present invention, can not be considered to for limiting practical range of the present invention.All equalization variations of doing according to the present patent application scope and improvement etc., within all belonging to patent covering scope of the present invention.
Claims (9)
1. a renovation process for methanol-to-olefins catalyst, is characterized in that said method comprising the steps of: the organic matter that first the molecular sieve catalyst aqueous solution air lift of activity decreased in methanol to olefins reaction is removed to deentrainment; Again above-mentioned aqueous catalyst solution is oxidized to further oil removing; Finally the aqueous catalyst solution after above-mentioned oil removing is removed by filter impurity and is in harmonious proportion stable processing.
2. the renovation process of methanol-to-olefins catalyst according to claim 1, it is characterized in that: in described air lift step, first what autoreactor was drawn enters air lift device containing aqueous catalyst solution, with nitrogen or water vapour, carry out air lift, air lift pressure is 0～0.1MPa, 95～110 ℃ of air lift temperature, while exporting content of organics lower than 0.1～1000ppm to air lift device, air lift finishes.
3. the renovation process of methanol-to-olefins catalyst according to claim 2, is characterized in that: during with water vapour, adopt the method for indirect air lift, use water vapour indirect, solution is evaporated to air lift and remove organic matter.
4. the renovation process of methanol-to-olefins catalyst according to claim 1, is characterized in that: in described oxidation step, with air or hydrogen peroxide, be further oxidized remaining organic matter, oxidation processes pressure is 0～0.1MPa, 80～110 ℃ of temperature.
5. the renovation process of methanol-to-olefins catalyst according to claim 4, is characterized in that: while adopting air, the volume ratio of air and catalyst slurry is 10～100Nm
3every cubic metre of catalyst slurry, Control for Oxygen Content is below 30wt%.
6. the renovation process of methanol-to-olefins catalyst according to claim 4, is characterized in that: while adopting hydrogen peroxide, concentration is 10～50wt%, preferred 20～30wt%, and the mass ratio of the dioxygen water yield and catalyst is 0.05～1.
7. the renovation process of methanol-to-olefins catalyst according to claim 1, is characterized in that: in described filtration step, adopt accurate filter.
8. the renovation process of methanol-to-olefins catalyst according to claim 1, is characterized in that: described mediation is stablized in treatment step, adds high purity water to be in harmonious proportion and stablizes processing.
9. the renovation process of methanol-to-olefins catalyst according to claim 1, is characterized in that: the ratio of setting taking-up regenerated catalyst is 0.5～5wt%.
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| CN201310654118.1A CN103611567A (en) | 2013-12-04 | 2013-12-04 | Regeneration method of methanol-to-olefin catalyst |
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| CN201310654118.1A CN103611567A (en) | 2013-12-04 | 2013-12-04 | Regeneration method of methanol-to-olefin catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104128131A (en) * | 2014-07-01 | 2014-11-05 | 中国寰球工程公司 | Regeneration gas cycle recovery apparatus and method thereof |
| CN104826670A (en) * | 2015-04-14 | 2015-08-12 | 华东理工大学 | Method and apparatus for removing oil pollutants contained in catalyst micro-powder in MTO quenching wastewater |
-
2013
- 2013-12-04 CN CN201310654118.1A patent/CN103611567A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104128131A (en) * | 2014-07-01 | 2014-11-05 | 中国寰球工程公司 | Regeneration gas cycle recovery apparatus and method thereof |
| CN104128131B (en) * | 2014-07-01 | 2016-08-24 | 中国寰球工程公司 | A kind of device and method of regeneration gas circulation and stress |
| CN104826670A (en) * | 2015-04-14 | 2015-08-12 | 华东理工大学 | Method and apparatus for removing oil pollutants contained in catalyst micro-powder in MTO quenching wastewater |
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Application publication date: 20140305 |