CN1160150C - Low-temp reaction catalyst for preparing ethylene by selectively oxidizing mixture of raw methane and ethane gases - Google Patents

Low-temp reaction catalyst for preparing ethylene by selectively oxidizing mixture of raw methane and ethane gases Download PDF

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Publication number
CN1160150C
CN1160150C CNB001102605A CN00110260A CN1160150C CN 1160150 C CN1160150 C CN 1160150C CN B001102605 A CNB001102605 A CN B001102605A CN 00110260 A CN00110260 A CN 00110260A CN 1160150 C CN1160150 C CN 1160150C
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China
Prior art keywords
catalyst
mno
ethane
binding agent
reaction catalyst
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CNB001102605A
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CN1315310A (en
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于春英
李文钊
徐恒泳
葛庆杰
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The present invention relates to a low temperature reaction catalyst used for preparing ethylene from the mixed feed gas of methane and ethane through selective oxidation. The present invention is characterized in that MnO<x> with an added binding agent is used as a supporter of the catalyst; an alkali metal element is used as an auxiliary agent. The low temperature reaction catalyst can be represented by a general formula ABMnO<x>, wherein a represents the alkali metal Li as the auxiliary agent; B represents the binding agent; x equals to 1.5. Measured by MnO<x> accounting for 100%, the low temperature reaction catalyst comprises 0.6 to 2.4 wt% of A and 10 wt % of B, and has the advantages of high activity and high selectivity.

Description

The low-temp reaction catalyst that is used for first, ethane mixed material gas Selective Oxidation ethene
Technical field
The present invention relates to the low-temp reaction catalyst that a class is used for oil field and oil refinery dry gas Selective Oxidation ethene, specifically being exactly provides a kind of catalyst that has high activity, high selectivity at a lower temperature for methane in the dry gas and ethane selective oxidation.
Background technology
Be accompanied by a large amount of refinery gas in the petroleum refining process and produce, take off C 3Later oil refinery dry gas mainly is provided by the oil refinery dry gas that provides with the Fushun second branch factory of oil is example, about methane 30%, about ethane 20%, about ethene 15%, hydrogen about 15% and about 20% nitrogen, take off wherein rare ethene and also contain methane and ethane later on, how further to utilize these methane and ethane to produce ethene, have crucial industrial application value undoubtedly with high added value up to about 50%.
Making ethylene from ethane oxidative dehydrogenation is a new technology, with the technical process of traditional ethane or naphtha steam heat cracking ethylene preparation relatively, it has advantages such as energy consumption of reaction is low, product is easily separated, the investment of founding the factory is little, has therefore caused people's attention in the last few years.The catalyst patent of relevant making ethylene from ethane oxidative dehydrogenation can be divided into two classes, and a class is a low-temp reaction catalyst, and another kind of is high temperature reaction catalyst.Be applicable to that low-temp reaction catalyst has the US4524236 and the US4596787 of the U.S., this patent is a Mo-V-Nb-Sb-X class catalyst, and best result is at 450 ℃ of ethane conversions 50%, ethylene selectivity 65%.Also has European patent EP 544372, be that Mo-P-X-Y-Z-Q-O class catalyst and Chinese patent CN1121844A are the X-Y-Z-O/ carried catalysts, it is the K-Mg-Zr-O system that the best catalyst that the latter provides is formed, at 620 ℃ of ethane conversions 58.45%, ethylene selectivity 71.7%.The patent of relevant high temperature making ethylene from ethane oxidative dehydrogenation has the CN1038461A patent of The British Petroleum Co.,P.L.C in China's application, and at 845 ℃ of Pt/ cordierite catalyst ethane conversions 70%, ethylene selectivity is 72.3%.Also have two catalyst patents that are the inventor at first, the ethane mixed material oxidation system ethene of China's application, number of patent application is [97115730.8] and [99112827.3], and the former is MnO x/ CaTi 0.9Li 0.1O 3Catalyst is at 850 ℃ of ethane conversions 75.3%, methane conversion 1.4%, ethylene selectivity 83.4%; Latter Li/MnO xCatalyst is at 800 ℃ of ethane conversions 76.2%, methane conversion 2.5%, ethylene selectivity 82.9%.
Summary of the invention
The purpose of this invention is to provide a kind of low-temp reaction catalyst that is used for first, ethane mixed material gas Selective Oxidation ethene, it can be used for oil refinery dry gas (or dried gas in oil field) methane, ethane low temperature Selective Oxidation ethene, has high activity, high selectivity.
The invention provides a kind of low-temp reaction catalyst that is used for first, ethane mixed material gas Selective Oxidation ethene, it is characterized in that: this catalyst is to add the MnO of binding agent xBeing carrier, is auxiliary agent with the alkali metal, and its general formula can be used AB MnO xExpression, wherein A is additive alkali metal Li; B is a binding agent, and X equals 1.5; The weight percent content of each component is, with MnO xBe 100% calculating, A:0.6～2.4%; B:10%.
The size shape of catalyst can change by the form of reactor, and catalyst can be any suitable shape and comprises spherical, column, bulk etc.
The Preparation of catalysts process is as follows:
Controlling catalyst carrier at first is with MnCO 3Sieve with mixed grindings such as binding agent red cement, white cement or Suzhou soil, health in the spin, water, conditioned time at least 1 hour be best 1～48 hour, dry roasting then, sintering temperature is greater than 200 ℃, be preferably in 300～400 ℃, roasting time at least 1 hour, generally, form the MnO that adds binding agent after the roasting at 2～5 hours xCatalyst base is pulverized 20 order sieving for standby.
Sulfate or aqueous chloride solution with alkali metal Li flooded above-mentioned particle 1～24 hour, oven dry about 100 ℃, and roasting is 4～12 hours in 600～800 ℃ of air.
Catalyst performance evaluation is taken off oil refinery dry gas behind the ethene with what the Fushun second branch factory of oil provided, and it consists of H 220%, CH 436%, C 2H 617%, CO 1.0%, CO 22.0% and 24%N 2Add an amount of oxygen in the dry gas, control C generally speaking 2H 6/ O 2About=0.9, dry gas flow velocity 5ml/min～40ml/min, dry gas air speed 2400hr -1～20000hr -1Between, react 650～800 ℃, reaction pressure 1atm, catalyst amount 0.2g or 1g.Reaction can be carried out in any reactor that proper temperature can be provided, and catalytic bed adopts the fixed bed form.
The specific embodiment
Below by embodiment the present invention is given to illustrate in further detail.Embodiment only is used for illustrating the result who obtains under composition, preparation process, appreciation condition and the corresponding conditions of the present invention middle part divided catalyst, but do not limit the present invention by better catalyst form, preparation technology and appreciation condition.
The preparation of embodiment 1 catalyst base (I)
Get 10g MnCO 3Add the 0.7g red cement and grind the back spin of sieving, bulb diameter reaches and adds the water health behind the 2mm and dry after 2 days, makes the MnO of interpolation red cement again in 4 hours 350 ℃ of roastings xCatalyst base, it is standby to pulverize 20 mesh sieves.
The preparation of embodiment 2 catalyst bases (II)
Get 10g MnCO 3Add the 0.7g white cement, other step and embodiment 1 are identical, prepare the MnO that adds white cement xCatalyst base is standby.
The preparation of embodiment 3 catalyst bases (III)
Get 10g MnCO 3Add 0.7g Suzhou soil, other step and embodiment 1 are identical, prepare the MnO that adds Suzhou soil xCatalyst base is standby.
The preparation of embodiment 4 catalyst (IV)
Get 0.694g LiClH 2O adds the 2ml deionized water, treats that LiCl all dissolves the MnO that the back adds the interpolation red cement of 5.5g embodiment 1 preparation xCarrier (I) floods after 24 hours oven dry, and 800 ℃ of roastings are 4 hours in air, prepare catalyst (IV).
The preparation of embodiment 5 catalyst (V)
Get 1.508g LiClH 2O adds the 2ml deionized water, treats that LiCl all dissolves the MnO that the back adds the interpolation red cement of 5.98g examples of implementation preparation xCarrier (I), following steps and embodiment 4 are identical, prepare catalyst (V).
The preparation of embodiment 6 catalyst (VI)
Get 0.126g LiClH 2O adds the 0.42ml deionized water, treats to add after LiCl all dissolves the MnO of the interpolation white cement of 1g embodiment 2 preparations xCatalyst base (II), following steps and embodiment 4 are identical, prepare catalyst (VI).
The preparation of embodiment 7 catalyst (VII)
Get 1.0g LiClH 2O adds the 1.7ml deionized water, treats to add after LiCl all dissolves the MnO of the interpolation white cement of 4g embodiment 2 preparations xCatalyst base (II), following steps and embodiment 4 are identical, prepare catalyst (VII).
The preparation of embodiment 8 catalyst (VIII)
Get 1.051g LiClH 2O adds the 3.5ml deionized water, treats that LiCl all dissolves the MnO that the back adds the interpolation Suzhou soil of 10g embodiment 3 preparations xCatalyst base (III), following steps and embodiment 4 are identical, prepare catalyst (VIII).
The preparation of embodiment 9 catalyst (IX)
Get 0.615g Li 2SO 4H 2O is dissolved in the 1ml deionized water, treats Li 2SO 4All the dissolving back add 3g embodiment 1 preparation the MnO of interpolation red cement xCatalyst base, following steps and embodiment 4 are identical, prepare catalyst (IX).
Embodiment 10 is 750 ℃ of evaluate catalysts performances
Utilize fixed-bed micro-reactor that catalyst of the present invention is carried out performance evaluation.Reaction condition: catalyst amount 0.2g, the long 300mm of crystal reaction tube diameter 8mm, room temperature feeds dry gas and oxygen mixture, dry gas flow velocity 10ml/min, oxygen gas flow rate 2ml/min, the dry gas air speed is 4800h -1, ethane oxygen ratio is about 0.9,750 ℃ of reaction temperatures, and reaction result is listed in table 1.
Table 1 is in the performance of 750 ℃ of each catalyst
Catalyst methane conversion ratio ethane conversion ethylene selectivity yield of ethene
(％) (％) (％) (％)
Catalyst I V 5.8 70.6 76.6 58.5
Catalyst V 7.7 76.5 77.1 64.9
Catalyst V I 7.5 63.5 64.9 48.6
Catalyst V II 2.0 60.5 76.1 47.8
Catalyst V III 7.8 60.3 80.2 54.6
Catalyst I X 6.3 65.3 73.7 52.8
Comparative examples A 4.2 28.1 59.2 19.1
Comparative example B 7.8 49.1 72.4 41.2
Comparative examples A is not add the MnO of any auxiliary agent and binding agent xCarrier, comparative example B are only to add the LiCl auxiliary agent and the LiCl/MnO that do not add binding agent xCatalyst.
By the visible MnO of table 1 xAdd LiCl auxiliary agent and the catalyst (IV) of red cement binding agent and performance the best (V), the catalyst of wherein high LiCl content (V) is better than the catalyst (IV) of low LiCl content.
Embodiment 11 is in the performance (ethane oxygen is than=0.9) of 675 ℃ of catalyst (V)
Table 2 is in the performance of 675 ℃ of catalyst (V)
Dry gas air speed reaction time methane conversion ethane conversion ethylene selectivity
(h -1) (branch) (%) (%) (%)
4800 5 17.7 78.5 80.3
4800 80 14.0 74.5 75.2
4800 160 15.6 77.6 78.9
6000 5 12.9 75.3 73.9
6000 80 7.9 76.9 69.8
6000 160 10.0 80.0 71.0
The relatively more visible catalyst (V) of table 2 and table 1 second line data slightly is better than its performance at 750 ℃ 675 ℃ of performances.
Embodiment 12 is in the performance of 650 ℃ of catalyst (V)
Table 3 is at performance (the air speed 4800h of 650 ℃ of catalyst (V) -1)
Ethane: O 2Methane conversion ethane conversion ethylene selectivity yield of ethene
(％) (％) (％) (％)
0.6 9.7 76.8 60.7 52
0.9 7.6 76.1 74.8 62
1.1 3.7 64.2 76.5 52
1.5 2.3 50.6 80.6 42
Comparison sheet 2 and table 3 are at identical air speed 4800h -1With identical ethane oxygen than under 0.9 the condition, catalyst (V) is more or less the same in 650 ℃ reactivity worth and 675 ℃ reactivity worth.
Bigger to the catalytic performance influence from the variation of the visible ethane oxygen ratio of table 2 data, the optimal proportion of ethane and oxygen is about 0.9.
As can be seen from the above-described embodiment, the maximum characteristics that catalyst of the present invention has are under 650～675 ℃ of lower temperatures, can realize first, ethane mixed material gas Selective Oxidation ethene, and the control proper reaction conditions can obtain the yield of ethene greater than 60%.

Claims (2)

1, a kind of low-temp reaction catalyst that is used for first, ethane mixed material gas Selective Oxidation ethene is characterized in that: this catalyst is to add the MnO of binding agent xBeing carrier, is auxiliary agent with alkali metal Li element, its general formula AB MnO xExpression, wherein A is additive alkali metal Li; B is a binding agent, and X equals 1.5; The weight percent content of each component is, with MnO xBe 100% calculating, A:0.6～2.4%; B:10%.
2, by the described preparation method who is used for the low-temp reaction catalyst of first, ethane mixed material gas Selective Oxidation ethene of claim 1, it is characterized in that the Preparation of catalysts process is as follows:
Controlling catalyst carrier at first is with MnCO 3Sieve with binding agent red cement, white cement or Suzhou soil mixed grinding, health in the spin, water, conditioned time 1～48 hour, dry roasting then, 300～400 ℃ of sintering temperatures, roasting time 2～5 hours forms the MnO that adds binding agent after the roasting xCatalyst base is pulverized 20 order sieving for standby;
Sulfate or aqueous chloride solution with alkali metal Li flooded above-mentioned particle 1～24 hour, 100 ℃ of oven dry, and roasting is 4～12 hours in 600～800 ℃ of air.
CNB001102605A 2000-03-29 2000-03-29 Low-temp reaction catalyst for preparing ethylene by selectively oxidizing mixture of raw methane and ethane gases Expired - Fee Related CN1160150C (en)

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