CN104841494A - Positioned regeneration method of structured catalyst in fixed-bed reactor - Google Patents
Positioned regeneration method of structured catalyst in fixed-bed reactor Download PDFInfo
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- CN104841494A CN104841494A CN201510123259.XA CN201510123259A CN104841494A CN 104841494 A CN104841494 A CN 104841494A CN 201510123259 A CN201510123259 A CN 201510123259A CN 104841494 A CN104841494 A CN 104841494A
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Abstract
The present invention discloses a positioned regeneration method of a structured catalyst in a fixed-bed reactor. The method comprises the following steps: feed gases enter a structured fixed-bed reactor in a manner of periodic flow reversal, and reactions are carried out under the conditions of 400-700 DEG C and 0.15-1.00 MPa A until catalysts deactivate; regenerating gases are subjected to in-situ coke-burning regeneration of the deactivated catalysts with a carbon deposit catalyst in the same manner of the periodic flow reversal under the conditions of 350 DEG C-700 DEG C and 0.15-1.50 MPa A, wherein the flow reversal period of the oxygen-containing gases lasts 0.5-20.0 h. With the method according to the present invention, the positioned regeneration of the carbon deposit catalysts can be achieved, and in addition, the problems that the charcoal burning of catalysts is not uniform and the temperature of beds runs away in the process of burning charcoal are solved, the controllable carbon predeposition of regenerating agents can be realized, and the yield of target products is greatly improved. The method provided by the present invention can be used in the industrial production of preparing propylene using methanol.
Description
Technical field
The present invention relates to structural catalyst fixed point renovation process in fixed bed reactors, be specially adapted to radial fixed-bed preparing propylene from methanol field.
Background technology
It is one of Main way of chemical process strengthening that traditional molecular sieve is applied to catalytic reaction with structurized form.Structural method mainly refers to load on the regular medium carrier with the physical property such as excellent heat conductivity and compression strength and has the active component of catalytic action, and is positioned in an orderly manner in reactor according to specific macroscopical geometric configuration by this structuring unit.Compared to the grade catalyst particle size used in traditional packed bed, by the catalyst coat thickness of structuring load at micron order even nanoscale, substantially increase reactant and product diffusion rate in the catalyst, for the complex reaction system that secondary response can occur target product, significantly can promote catalyst choice.Meanwhile, the good physical that structured supports self has also can the Momentum Transfer of intensifies process and heat transmission, for the carrier of structure-controllable, can also realize Catalyst Design design with reactor between be coupled.
At present, structured supports mainly contains fibrage body, honeycomb and foam three macrostructure type, and wherein, honeycomb and foaming structure carrier are the main carriers made for molecular sieve coating.Compared to honeycomb carrier, foaming structure carrier has three-dimensional networks passage, its shape can according to the form design of reactor, can perforate or fluting, while its Pressure Drop is close with honeycomb carrier, geometric area improves greatly, can realize fully contacting of material and catalyst, radial heat-transfer capability is strong, is specially adapted to the strong exothermal reaction that preparing propylene from methanol, this kind of side reaction of Methanol aromatic hydrocarbons are more.
In catalytic reforming, preparing propylene from methanol, this kind of catalytic conversion reaction process of Methanol aromatic hydrocarbons, along with the generation of the high-carbon accessory substances such as condensed-nuclei aromatics, these species adsorbs at active catalyst sites and deep dehydrogenation form carbon deposit and cover activated centre or blocking catalyst duct and cause its inactivation.Find after deliberation, the generating rate of carbon deposit is relevant to reactant concentration, and coking deactivation presents the feature of parallel deactivation.Therefore, the coke content in beds flows to along reactant and reduces gradually.The catalyst of coking deactivation can pass through oxygen containing regeneration gas burn off carbon deposit in-situ regeneration in the reactor, and in the process along with a large amount of combustions heat, the bed temperature rise brought thus is the main cause of catalyst activity permanent loss.The beds that coke content is different is everywhere made charcoal everywhere speed difference in the process of coke-burning regeneration, not only can cause the inequality of Temperature Distribution in bed, and can not realize being uniformly distributed of coke content on regenerated catalyst.
Regenerative agent with certain coke content can significantly improve the performance of catalyst for this kind of reaction of preparing propylene from methanol.As Chinese patent CN200810161675.9 discloses a kind of method using moving bed technique oxygenatedchemicals to be converted into propylene.This patent is passed through part C
5 +component passes into after second reaction zone makes the pre-carbon deposit of catalyst and passes into the first reaction zone, improves selective to propylene of the first reaction zone inner catalyst thus, thus improves the yield of propylene.Therefore develop the fixed point regeneration techniques of catalyst, realize the carbon deposit content fixed point regulation and control of regenerated catalyst and be uniformly distributed, having great importance.
Chinese patent CN102218354A discloses a kind of method and regenerator scorch region structure of hydrocarbon conversion catalyst coke burning regeneration, and the scorch region of this moving bed regenerator is divided into the section of burning, changeover portion and superheat section soon from top to bottom successively.Although this novel scorch region structure can solve the problem of catalyst scorch region temperature runaway in existing hydrocarbon transformation technology, the fixed point coke-burning regeneration of carbon deposited catalyst can not be realized.
Under identical reaction condition, catalyst activity is higher, and reaction zone length is shorter, and the coke content gradient flowed on Unit Scale bed along reactant is less.Increased by its external surface area of molecular sieve catalyst of porous carrier structure, thing followed benefit is the raising of catalyst activity, the gradient disparities of coke content in beds can be reduced thus, but still can not solve the fixed point of stable homogeneous in structure catalyst and to make charcoal problem.
At present, the fixed point regeneration techniques of deactivation catalyst of carbon deposit in structuring bed is still belonged to blank.
Summary of the invention
The object of the invention is in existing structure fixed-bed process, on the regenerated catalyst that catalyst regeneration techniques exists coke content uneven with bed temperature gradient the problem such as excessive, structural catalyst fixed point renovation process in a kind of fixed bed reactors is provided.
In fixed bed reactors, structural catalyst fixed point renovation process is: unstripped gas enters by the structural catalyst bed entered in the mode of flow-reversal after the first-class flow-reversal regulating system formed to change over valve (2) and second to change over valve (3) in fixed bed reactors (4) by air inlet (1), at 400-700 DEG C, react under the condition of 0.15-1.00 MPaA, product gas leaves after gas outlet (5), and the cycle of unstripped gas flow-reversal is 0.1-0.8 times of catalyst single pass life;
Stop after structural catalyst inactivation passing into unstripped gas, oxysome volume concentrations is entered fixed bed reactors (4) in the mode of flow-reversal after the oxygen-containing gas of 0.01%-21.00% sends into flow-reversal regulating system from air inlet (1), with spent agent at 350 DEG C-700 DEG C, original position coke-burning regeneration is carried out under the condition of 0.15-1.50 MPaA, regeneration air stream is 0.5-20.0 h to transformation period, with the weight of structural catalyst for benchmark, on spent agent, carbon deposit mass percentage is 1.00%-60.00%, on regenerative agent after regeneration, carbon deposit mass percentage is 0.01%-15.00%.
Described flow-reversal regulating system is one or two.The form of described fixed bed reactors (4) is axis or radial fixed-bed reactor.The form of described structural catalyst is honeycomb or foaming structure.The described structural catalyst thickness of bed layer flowed to along reactant is 1-50 times of reaction zone length.Described structural catalyst is thickness at the molecular sieve coating of 5-1000 μm.Described oxygen-containing gas is from air, nitrogen or both mixtures.
The beneficial effect that the present invention compared with prior art has:
1) catalyst fixed point renovation process in structuring fixed bed reactors of the present invention, the feature that in structure based bed, catalyst activity is high, realizes the fixed point regeneration of carbon deposited catalyst by the flow-reversal technology two aspect synergy in reaction process and regeneration technology.On the one hand, in structuring bed, catalyst activity is high, and effecting reaction section length is short, carbon deposit narrow distribution range on catalyst, and carbon deposit is more evenly distributed; On the other hand, by reacting the flow-reversal of logistics, change coke content gradient direction in bed, again make up the problem of carbon deposit inequality on catalyst fixed bed bed from technology angle, for fixed point coke combustion uniform in regenerative section provides the homogeneous raw material of character; Finally, the flow direction of exchange-column shift regeneration gas, makes carbon deposit on regenerative agent equably by burn off.
2) catalyst fixed point renovation process in structuring fixed bed reactors of the present invention, the cycle flowed to by regeneration gas is switched avoids the combustion heat to accumulate along airflow direction, thus effectively to solve in carbon deposit burn off process beds due to the excessive and problem of temperature runaway of the combustion heat, ensure the stability of reaction bed temperature, avoid too high regeneration temperature, reduce the severity of regenerative process, greatly delay the destruction of molecular sieve catalyst skeleton structure, extend the entire life of molecular sieve catalyst;
3) catalyst fixed point renovation process in structuring fixed bed reactors of the present invention, by the incomplete burn off regulating the flow-reversal cycle of regeneration gas and the oxygen content of regeneration gas to realize coke on regenerative agent, make catalyst average coke level reach target set point, this catalyst with pre-carbon deposit is used for can improving the selective of target product in catalytic reaction.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of catalyst fixed point renovation process in structuring fixed bed reactors.
Detailed description of the invention
In fixed bed reactors, structural catalyst fixed point renovation process is: unstripped gas enters by the structural catalyst bed entered in the mode of flow-reversal after the first-class flow-reversal regulating system formed to change over valve 2 and second to change over valve 3 in fixed bed reactors 4 by air inlet 1, at 400-700 DEG C, react under the condition of 0.15-1.00 MPaA, product gas leaves behind gas outlet 5, and the cycle of unstripped gas flow-reversal is 0.1-0.8 times of catalyst single pass life;
Stop after structural catalyst inactivation passing into unstripped gas, oxysome volume concentrations is entered fixed bed reactors 4 in the mode of flow-reversal after the oxygen-containing gas of 0.01%-21.00% sends into flow-reversal regulating system from air inlet 1, with spent agent at 350 DEG C-700 DEG C, original position coke-burning regeneration is carried out under the condition of 0.15-1.50 MPaA, regeneration air stream is 0.5-20.0 h to transformation period, with the weight of structural catalyst for benchmark, on spent agent, carbon deposit mass percentage is 1.00%-60.00%, on regenerative agent after regeneration, carbon deposit mass percentage is 0.01%-15.00%.
Described flow-reversal regulating system is one or two.The form of described fixed bed reactors 4 is axis or radial fixed-bed reactor.The form of described structural catalyst is honeycomb or foaming structure.The described structural catalyst thickness of bed layer flowed to along reactant is 1-50 times of reaction zone length.Described structural catalyst is thickness at the molecular sieve coating of 5-1000 μm.Described oxygen-containing gas is from air, nitrogen or both mixtures.
With detailed description of the invention, the renovation process of fixing a point of catalyst in structuring fixed bed reactors of the present invention is described in further detail by reference to the accompanying drawings.Accompanying drawing and detailed description of the invention do not limit the scope of protection of present invention.
As shown in Figure 1, unstripped gas is connected through first-class to import and export with the top of fixed bed reactors 4 or bottom to change over valve 2 or second to change over valve 3 after air inlet 1, and product gas leaves from gas outlet 5; Oxygen-containing gas is connected through first-class to import and export with reactor bottom or top to change over valve 2 or second to change over valve 3 after air inlet 1, and circular regeneration gas is emptying from gas outlet 5; Structural catalyst bed is provided with in fixed bed reactors 4.
Embodiment 1
Methanol feedstock gas enters by the structural catalyst bed entered in the mode of flow-reversal after the first-class flow-reversal regulating system formed to change over valve 2 and second to change over valve 3 in fixed bed reactors 4 by air inlet 1, at 400 DEG C, react under the condition of 0.15 MPaA, product gas leaves behind gas outlet 5, and the cycle of unstripped gas flow-reversal is 0.8 times of catalyst single pass life;
Stop after structural catalyst inactivation passing into unstripped gas, by oxysome volume concentrations 21.00% oxygen-containing gas send into flow-reversal regulating system from air inlet 1 after enter fixed bed reactors 4 in the mode of flow-reversal, with spent agent at 350 DEG C, original position coke-burning regeneration is carried out under the condition of 0.15 MPaA, regeneration air stream is 0.5 h to transformation period, with the weight of structural catalyst for benchmark, on spent agent, carbon deposit mass percentage is 1.00%, and on the regenerative agent after regeneration, carbon deposit mass percentage is 0.01%.
Described flow-reversal regulating system is one.The form of described fixed bed reactors 4 is axial restraint bed bioreactor.The form of described structural catalyst is honeycomb.The described structural catalyst thickness of bed layer flowed to along reactant is 50 times of reaction zone length.Described structural catalyst is thickness at the molecular sieve coating of 5 μm.Described oxygen-containing gas is from air.
Embodiment 2
Heavy hydrocarbon feedstocks gas enters by the structural catalyst bed entered in the mode of flow-reversal after the first-class flow-reversal regulating system formed to change over valve 2 and second to change over valve 3 in fixed bed reactors 4 by air inlet 1, at 700 DEG C, react under the condition of 1.00 MPaA, product gas leaves behind gas outlet 5, and the cycle of unstripped gas flow-reversal is 0.1 times of catalyst single pass life;
Stop after structural catalyst inactivation passing into unstripped gas, by oxysome volume concentrations 0.01% oxygen-containing gas send into flow-reversal regulating system from air inlet 1 after enter fixed bed reactors 4 in the mode of flow-reversal, with spent agent at 700 DEG C, original position coke-burning regeneration is carried out under the condition of 1.50 MPaA, regeneration air stream is 20.0 h to transformation period, with the weight of structural catalyst for benchmark, on spent agent, carbon deposit mass percentage is 60.00%, and on the regenerative agent after regeneration, carbon deposit mass percentage is 15.00%.
Described flow-reversal regulating system is two.The form of described fixed bed reactors 4 is radial fixed-bed reactor.The form of described structural catalyst is foaming structure.The described structural catalyst thickness of bed layer flowed to along reactant is 1 times of reaction zone length.Described structural catalyst is thickness at the molecular sieve coating of 1000 μm.Described oxygen-containing gas is from the mixture of air, nitrogen.
Embodiment 3
Methanol feedstock gas enters by the structural catalyst bed entered in the mode of flow-reversal after the first-class flow-reversal regulating system formed to change over valve 2 and second to change over valve 3 in fixed bed reactors 4 by air inlet 1, at 460-490 DEG C, react under the condition of 0.30 MPaA, product gas leaves behind gas outlet 5, and the cycle of unstripped gas flow-reversal is 0.2 times of catalyst single pass life;
Stop after structural catalyst inactivation passing into unstripped gas, by oxysome volume concentrations 10.00% oxygen-containing gas send into flow-reversal regulating system from air inlet 1 after enter fixed bed reactors 4 in the mode of flow-reversal, with spent agent at 450 DEG C-500 DEG C, original position coke-burning regeneration is carried out under the condition of 0.20 MPaA, regeneration air stream is 4.0 h to transformation period, with the weight of structural catalyst for benchmark, on spent agent, carbon deposit mass percentage is 20.00%-25.00%, and on the regenerative agent after regeneration, carbon deposit mass percentage is 2.50%-3.00%.
Described flow-reversal regulating system is two.The form of described fixed bed reactors 4 is radial fixed-bed reactor.The form of described structural catalyst is foaming structure.The described structural catalyst thickness of bed layer flowed to along reactant is 10 times of reaction zone length.Described structural catalyst is thickness at the molecular sieve coating of 20 μm.Described oxygen-containing gas is from the mixture of air, nitrogen.
Claims (7)
1. a structural catalyst fixed point renovation process in fixed bed reactors, is characterized in that:
Unstripped gas enters by the structural catalyst bed entered in the mode of flow-reversal after the first-class flow-reversal regulating system formed to change over valve (2) and second to change over valve (3) in fixed bed reactors (4) by air inlet (1), at 400-700 DEG C, react under the condition of 0.15-1.00 MPaA, product gas leaves after gas outlet (5), and the cycle of unstripped gas flow-reversal is 0.1-0.8 times of catalyst single pass life;
Stop after structural catalyst inactivation passing into unstripped gas, oxysome volume concentrations is entered fixed bed reactors (4) in the mode of flow-reversal after the oxygen-containing gas of 0.01%-21.00% sends into flow-reversal regulating system from air inlet (1), with spent agent at 350 DEG C-700 DEG C, original position coke-burning regeneration is carried out under the condition of 0.15-1.50 MPaA, regeneration air stream is 0.5-20.0 h to transformation period, with the weight of structural catalyst for benchmark, on spent agent, carbon deposit mass percentage is 1.00%-60.00%, on regenerative agent after regeneration, carbon deposit mass percentage is 0.01%-15.00%.
2. structural catalyst fixed point renovation process in fixed bed reactors as claimed in claim 1, it is characterized in that, described flow-reversal regulating system is one or two.
3. structural catalyst fixed point renovation process in fixed bed reactors as claimed in claim 1, it is characterized in that, the form of described fixed bed reactors (4) is axis or radial fixed-bed reactor.
4. catalyst fixed point renovation process in structuring fixed bed reactors as claimed in claim 1, it is characterized in that, the form of described structural catalyst is honeycomb or foaming structure.
5. catalyst fixed point renovation process in structuring fixed bed reactors as claimed in claim 1, is characterized in that, the described structural catalyst thickness of bed layer flowed to along reactant is 1-50 times of reaction zone length.
6. catalyst fixed point renovation process in structuring fixed bed reactors as claimed in claim 1, is characterized in that, described structural catalyst is thickness at the molecular sieve coating of 5-1000 μm.
7. catalyst fixed point renovation process in structuring fixed bed reactors as claimed in claim 1, it is characterized in that, described oxygen-containing gas is from air, nitrogen or both mixtures.
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| CN201510123259.XA CN104841494B (en) | 2015-03-20 | 2015-03-20 | Structural catalyst pinpoints renovation process in fixed bed reactors |
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| CN201510123259.XA CN104841494B (en) | 2015-03-20 | 2015-03-20 | Structural catalyst pinpoints renovation process in fixed bed reactors |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008128A (en) * | 2016-05-25 | 2016-10-12 | 上海交通大学 | Methanol-to-propylene reaction regeneration system and method |
| CN110013887A (en) * | 2018-01-09 | 2019-07-16 | 中国石油化工股份有限公司 | The in situ regeneration method of catalyst inactivation |
| CN110013886A (en) * | 2018-01-09 | 2019-07-16 | 中国石油化工股份有限公司 | Catalyst situ regeneration device |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654458A (en) * | 1985-09-26 | 1987-03-31 | Amoco Corporation | Conversion of a lower alkane |
| CN101735872A (en) * | 2008-11-12 | 2010-06-16 | 中科合成油技术有限公司 | Non-steady state reactor and method for producing synthesis gas |
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- 2015-03-20 CN CN201510123259.XA patent/CN104841494B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4654458A (en) * | 1985-09-26 | 1987-03-31 | Amoco Corporation | Conversion of a lower alkane |
| CN101735872A (en) * | 2008-11-12 | 2010-06-16 | 中科合成油技术有限公司 | Non-steady state reactor and method for producing synthesis gas |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008128A (en) * | 2016-05-25 | 2016-10-12 | 上海交通大学 | Methanol-to-propylene reaction regeneration system and method |
| CN106008128B (en) * | 2016-05-25 | 2018-06-26 | 上海交通大学 | The reaction-regeneration system and method for a kind of preparing propylene from methanol |
| CN110013887A (en) * | 2018-01-09 | 2019-07-16 | 中国石油化工股份有限公司 | The in situ regeneration method of catalyst inactivation |
| CN110013886A (en) * | 2018-01-09 | 2019-07-16 | 中国石油化工股份有限公司 | Catalyst situ regeneration device |
| CN110013886B (en) * | 2018-01-09 | 2021-11-02 | 中国石油化工股份有限公司 | Catalyst in-situ regeneration device |
| CN110013887B (en) * | 2018-01-09 | 2021-11-05 | 中国石油化工股份有限公司 | In-situ regeneration method for catalyst deactivation |
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| CN104841494B (en) | 2017-07-11 |
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