CN103736518B - A kind of methane arenes catalytic agent activation method in ciculation fluidized response system - Google Patents
A kind of methane arenes catalytic agent activation method in ciculation fluidized response system Download PDFInfo
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- CN103736518B CN103736518B CN201310744964.2A CN201310744964A CN103736518B CN 103736518 B CN103736518 B CN 103736518B CN 201310744964 A CN201310744964 A CN 201310744964A CN 103736518 B CN103736518 B CN 103736518B
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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
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Abstract
The invention discloses a kind of methane arenes catalytic agent activation method in ciculation fluidized response system, the method makes catalyst under fluidizing agent, the cyclic process of partial activation, the regeneration of part surface de-carbon, partial activation is experienced successively, it is achieved in ciculation fluidized response system, catalyst is carried out activation processing in ciculation fluidized response system.What this method solve the ciculation fluidized reaction initial activity catalyst of methane aromatic hydrocarbons carrys out source problem, when avoiding independent activating catalytic agent outside circulating reaction system, the processes such as catalyst storage, filling, conveying cause loss of catalyst activity, to excavate the reactivity worth of methane arenes catalytic agent to greatest extent, meanwhile, it is also beneficial to pilot scale and commercial plant saves space, reduces equipment investment.
Description
Technical field
The invention belongs to catalyst technical field, relate to the catalyst of a kind of methane aromatic hydrocarbons, especially a kind of methane arenes catalytic agent activation method in ciculation fluidized response system.
Background technology
Methane is the main component of natural gas, coal bed gas and shale gas etc., and worldwide increasing methane is used to produce the chemical products of the high added value such as ethylene and aromatic hydrocarbons.By means of the effect of the aromatized catalyst being representative with Mo based molecular sieve, methane aromatization can obtain a certain amount of aromatic hydrocarbon product under normal pressure, high temperature, it is believed that is a key areas of following methane conversion.Methane arenes catalytic agent, while promoting aromatic hydrocarbons to generate, also can produce considerable amount of carbon distribution in catalyst surface and duct, cause catalyst to inactivate gradually, and the conversion ratio of reaction, arenes selectivity and yield constantly reduce.Ciculation fluidized response system carries out raw material convert and two processes of catalyst regeneration simultaneously, can farthest recover reactivity and the stability of catalyst, be easily achieved again, and treating capacity is big.But aromatized catalyst needs to carry out activation processing before the reaction, generate the active component of catalytic action, for ciculation fluidized system, this generates and adopt the problem of activation or the interior activation of system outside antigravity system, though activation is easily achieved outside system, but the catalyst after activation is not easy to preserve, and needs the catalyst migration equipment between independent activation device and activation device and reaction unit, not only catalyst activity is produced impact, and equipment and operating cost can be increased.Therefore, the activation of catalyst in ciculation fluidized response system becomes a kind of new approach solving problem above.
Summary of the invention
It is an object of the invention to the shortcoming overcoming above-mentioned prior art, a kind of methane arenes catalytic agent activation method in ciculation fluidized response system is provided, the method is it can be avoided that outside circulating reaction system during independent activating catalytic agent, the processes such as catalyst storage, filling, conveying cause loss of catalyst activity, it is possible to excavate the reactivity worth of methane arenes catalytic agent to greatest extent.
It is an object of the invention to be achieved through the following technical solutions:
This methane arenes catalytic agent activation method in ciculation fluidized response system, make catalyst under fluidizing agent, the cyclic process of partial activation, the regeneration of part surface de-carbon, partial activation is experienced successively, it is achieved in ciculation fluidized response system, catalyst is carried out activation processing in ciculation fluidized response system.
Further, above-mentioned ciculation fluidized response system by reactor, riser or circulation pipe, gas-solid separator, regenerator, material pipe drops or circulation pipe, all or part of of catalyst circulation rate controller, accomplished continuously or intermittently feeding device, accomplished continuously or intermittently device for discharging combine.
Further, above-mentioned catalyst temperature under fluidizing agent is 450-750 DEG C.
Further, in the reactor of above-mentioned ciculation fluidized response system, suitable fluidizing agent is CH4、CH4/ noble gas, CH4/ weak oxide gas, CH4/H2In one or more combination；Being suitable in described reactor fluidizing linear velocity is 1-8cm/s.
Further, in the regenerator of above-mentioned ciculation fluidized response system, suitable fluidizing agent is H2、H2/CH4、H2/CO2In one or more combination；Being suitable in regenerator fluidizing linear velocity is 0.5-6cm/s.
The method have the advantages that
What the methane arenes catalytic agent of present invention activation method in ciculation fluidized response system solved the ciculation fluidized reaction initial activity catalyst of methane aromatic hydrocarbons carrys out source problem, when avoiding independent activating catalytic agent outside circulating reaction system, the processes such as catalyst storage, filling, conveying cause loss of catalyst activity, to excavate the reactivity worth of methane arenes catalytic agent to greatest extent, meanwhile, it is also beneficial to pilot scale and commercial plant saves space, reduces equipment investment.
Accompanying drawing explanation
Fig. 1 is that the ciculation fluidized response system of one of which being applicable to the inventive method connects block diagram.
Wherein: 1 is reactor；2 is gas-solid separator；3 is regenerator；4 is catalyst circulation rate controller；5 is accomplished continuously or intermittently feeding device；6 is accomplished continuously or intermittently device for discharging.
Detailed description of the invention
The methane arenes catalytic agent of present invention activation method in ciculation fluidized response system is to make fresh catalyst at preference temperature, suitable fluidizing agent and be suitable for fluidizing under linear velocity, the cyclic process of " partial activation-part surface de-carbon regeneration-partial activation " is experienced successively, it is achieved in ciculation fluidized response system, catalyst is carried out activation processing in ciculation fluidized response system.Described catalyst temperature under fluidizing agent is 450-750 DEG C.
Described ciculation fluidized response system by reactor (or reaction zone), riser (or circulation pipe), gas-solid separator, regenerator (or renewing zone), drop material pipe all or part of of (or circulation pipe), catalyst circulation rate controller, accomplished continuously or intermittently feeding device, accomplished continuously or intermittently device for discharging etc. combine.As Fig. 1 applies to the ciculation fluidized response system connection block diagram of one of which of the inventive method: reactor 1 connects accomplished continuously or intermittently device for discharging 6, catalyst circulation rate controller 4 and gas-solid separator 2；Regenerator 3 is connected with accomplished continuously or intermittently feeding device 5, and gas-solid separator 2 is connected to regenerator 3 and accomplished continuously or intermittently on pipeline between feeding device 5, catalyst circulation rate controller 4 is connected on regenerator 3.
Needing special declaration, in the annexation shown in figure 1 above, regenerator 3 both can be independent equipment or system, it is also possible to is same equipment or intrasystem reaction zone and renewing zone.Gas-solid separator 2 both can be independent conventional gas solid separation system or special gas solid separation system, it is also possible to is the gas solid separation district in successive reaction-regenerative system.The circulation rate that catalyst circulation rate controller 4 both can be independent controls device, it is also possible to be that the catalyst transport in successive reaction-regenerative system controls valve.Accomplished continuously or intermittently device for discharging 6 its both can independent of continuously-reaction-regeneration system outside, it is also possible to be a part therein or region.
In the reactor of described ciculation fluidized response system, suitable fluidizing agent is CH4、CH4/ noble gas, CH4/ weak oxide gas, CH4/H2In one or more combination；Being suitable in described reactor fluidizing linear velocity is 1-8cm/s.In the regenerator of described ciculation fluidized response system, suitable fluidizing agent is H2、H2/CH4、H2/CO2In one or more combination；Being suitable in regenerator fluidizing linear velocity is 0.5-6cm/s.
In sum, methane arenes catalytic agent is placed in ciculation fluidized response system and activates by the method for the present invention first, make its active component in the temperature range of suitable generation, in the reactor of ciculation fluidized response system, first partial activation generates active component, the catalyst surface carbon distribution then produced when the internal regenerator of ciculation fluidized response system divides reduction removing activation, at utmost activity recovery catalytic ability, the reactor returning again to ciculation fluidized response system continues the active component that activation generation is new, the catalyst surface carbon distribution being newly formed when then continuing partial reduction activation in the regenerator of ciculation fluidized response system, such iterative cycles, the final activation completely realizing all initial fresh catalysts, for the ciculation fluidized reaction preparation active catalyst of methane aromatic hydrocarbons.
Below in conjunction with embodiment, the present invention is described in further detail:
Embodiment one
Fresh Mo/HZSM-5 catalyst 100g, adopts the ciculation fluidized response system shown in Fig. 1, and catalyst is all filled in regenerator in advance, and in reactor, fluidizing agent is CH4/ Ar, in regenerator, fluidizing agent is H2/CH4, not take out of in reactor and regenerator under fluidized state, system is warming up to 550 DEG C, adjusts rate-of flow subsequently, when fluidizing fluidisation linear velocity 1.2cm/s in linear velocity 2cm/s, regenerator in reactor, ON cycle speed control.Activation of catalyst deadline and final methane conversion, aromatic hydrocarbons (benzene, naphthalene) selectivity result are in Table 1.
Embodiment two
Fresh Mo/HZSM-5 catalyst 200g, adopts the ciculation fluidized response system shown in Fig. 1, pre-installs 20g and 180g catalyst in reactor, regenerator respectively, and in reactor, fluidizing agent is CH4/ CO, in regenerator, fluidizing agent is H2/CO2, not take out of in reactor and regenerator under fluidized state, system is warming up to 680 DEG C, adjusts rate-of flow subsequently, when fluidizing fluidisation linear velocity 3cm/s in linear velocity 4cm/s, regenerator in reactor, ON cycle speed control.Activation of catalyst deadline and final methane conversion, aromatic hydrocarbons (benzene, naphthalene) selectivity result are in Table 1.
Embodiment three
Fresh Mo/HZSM-5 catalyst 300g, adopts the ciculation fluidized response system shown in Fig. 1, pre-installs 40g and 260g catalyst in reactor, regenerator respectively, and in reactor, fluidizing agent is CH4/H2, in regenerator, fluidizing agent is H2, not take out of in reactor and regenerator under fluidized state, system is warming up to 750 DEG C, adjusts rate-of flow subsequently, when fluidizing fluidisation linear velocity 5cm/s in linear velocity 7cm/s, regenerator in reactor, ON cycle speed control.Activation of catalyst deadline and final methane conversion, aromatic hydrocarbons (benzene, naphthalene) selectivity result are in Table 1.
Embodiment four
Fresh Mo/HZSM-5 catalyst 400g, adopts the ciculation fluidized response system shown in Fig. 1, pre-installs 60g and 340g catalyst in reactor, regenerator respectively, and in reactor, fluidizing agent is CH4, in regenerator, fluidizing agent is H2/CH4, not take out of in reactor and regenerator under fluidized state, system is warming up to 700 DEG C, adjusts rate-of flow subsequently, when fluidizing fluidisation linear velocity 2cm/s in linear velocity 8cm/s, regenerator in reactor, ON cycle speed control.Activation of catalyst deadline and final methane conversion, aromatic hydrocarbons (benzene, naphthalene) selectivity result are in Table 1.
Embodiment five
Fresh Mo/HZSM-5 catalyst 450g, adopts the ciculation fluidized response system shown in Fig. 1, pre-installs 50g and 400g catalyst in reactor, regenerator respectively, and in reactor, fluidizing agent is CH4/N2, in regenerator, fluidizing agent is H2, not take out of in reactor and regenerator under fluidized state, system is warming up to 450 DEG C, adjusts rate-of flow subsequently, when fluidizing fluidisation linear velocity 6cm/s in linear velocity 1cm/s, regenerator in reactor, ON cycle speed control.Activation of catalyst deadline and final methane conversion, aromatic hydrocarbons (benzene, naphthalene) selectivity result are in Table 1.
Table 1Mo/HZSM-5 activation of catalyst deadline and end reaction result
The above; it it is only presently preferred embodiments of the present invention; not the present invention is done any restriction, every any simple modification, change and equivalent structure change above example made according to inventive technique essence, all still falls within the protection domain of technical solution of the present invention.
Claims (3)
1. the methane arenes catalytic agent activation method in ciculation fluidized response system, it is characterized in that, make catalyst under fluidizing agent, the cyclic process of partial activation, the regeneration of part surface de-carbon, partial activation is experienced successively, it is achieved in ciculation fluidized response system, catalyst is carried out activation processing in ciculation fluidized response system；Described ciculation fluidized response system by reactor, riser or circulation pipe, gas-solid separator, regenerator, material pipe drops or circulation pipe, the whole of catalyst circulation rate controller, accomplished continuously or intermittently feeding device, accomplished continuously or intermittently device for discharging combine；In the reactor of described ciculation fluidized response system, suitable fluidizing agent is CH4、CH4/ noble gas, CH4/ weak oxide gas, CH4/H2In one or more combination；Being suitable in described reactor fluidizing linear velocity is 1-8cm/s.
2. the methane arenes catalytic agent according to claim 1 activation method in ciculation fluidized response system, it is characterised in that described catalyst temperature under fluidizing agent is 450-750 DEG C.
3. the methane arenes catalytic agent according to claim 1 activation method in ciculation fluidized response system, it is characterised in that in the regenerator of described ciculation fluidized response system, suitable fluidizing agent is H2、H2/CH4、H2/CO2In one or more combination；Being suitable in regenerator fluidizing linear velocity is 0.5-6cm/s.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102359A (en) * | 1993-11-04 | 1995-05-10 | 中科院大连化学物理研究所 | Catalyzer for direct synthesis of aromatic hydrocarbon from methane and its application of in building-up reaction |
| CN101580449A (en) * | 2008-05-15 | 2009-11-18 | 中国石油天然气股份有限公司 | Method and device for preparing aromatics through methane aromatization |
| CN102883811A (en) * | 2010-05-12 | 2013-01-16 | 国际壳牌研究有限公司 | Methane aromatization catalyst, method of making and method of using the catalyst |
| CN103338860A (en) * | 2011-01-26 | 2013-10-02 | 国际壳牌研究有限公司 | A zinc-containing methane aromatization catalyst, method of making and method of using the catalyst |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102359A (en) * | 1993-11-04 | 1995-05-10 | 中科院大连化学物理研究所 | Catalyzer for direct synthesis of aromatic hydrocarbon from methane and its application of in building-up reaction |
| CN101580449A (en) * | 2008-05-15 | 2009-11-18 | 中国石油天然气股份有限公司 | Method and device for preparing aromatics through methane aromatization |
| CN102883811A (en) * | 2010-05-12 | 2013-01-16 | 国际壳牌研究有限公司 | Methane aromatization catalyst, method of making and method of using the catalyst |
| CN103338860A (en) * | 2011-01-26 | 2013-10-02 | 国际壳牌研究有限公司 | A zinc-containing methane aromatization catalyst, method of making and method of using the catalyst |
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