CN103420769B - The method of dehydrogenating low-carbon alkane producing light olefins - Google Patents

The method of dehydrogenating low-carbon alkane producing light olefins Download PDF

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CN103420769B
CN103420769B CN201210150493.8A CN201210150493A CN103420769B CN 103420769 B CN103420769 B CN 103420769B CN 201210150493 A CN201210150493 A CN 201210150493A CN 103420769 B CN103420769 B CN 103420769B
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reaction
low
carbon
carrier
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CN103420769A (en
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吴文海
吴省
樊志贵
马春景
张磊
缪长喜
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The present invention relates to a kind of method preparing low-carbon alkene for dehydrogenating low-carbon alkane, mainly solve in prior art and there is catalyzer easy coking deactivation in applied at elevated temperature process, the problem of poor stability.The present invention passes through to adopt with propane/Trimethylmethane for raw material, in temperature of reaction 520 ~ 620 oc, reaction pressure 0 ~ 0.4MPa, alkane mass space velocity 0.1 ~ 8.0h -1, H 2/ C nh 2n+2volume ratio is under 0.2 ~ 1.6 condition, raw material and catalyst exposure, and reaction generates the technical scheme of propylene/iso-butylene, solves this problem preferably, can be used for the industrial production of dehydrogenating low-carbon alkane producing light olefins catalyzer.

Description

The method of dehydrogenating low-carbon alkane producing light olefins
Technical field
The present invention relates to a kind of method of dehydrogenating low-carbon alkane producing light olefins.
Background technology
Propylene/iso-butylene mainly from coproduction or the by-product of steam cracking and refinery factory fluid catalytic cracking process, can be widely used in synthetic polymer, gasoline dope, rubber and various chemical intermediate.Growing with low-carbon alkene demand, what traditional production process was difficult to meet the need of market increases rapidly.The a large amount of low-carbon alkanes obtained by refinery are main components of liquefied petroleum gas (LPG), are mainly used as domestic fuel.Develop and opened up new alkene by low-carbon alkanes preparing low-carbon olefins process originate significant for making full use of low-carbon alkanes.At present, propane catalytic dehydrogenation technology with the Catofin technique of the Oleflex technique of Uop Inc. and Lummus company for representative.The domestic production equipment still not having dehydrogenating low-carbon alkane producing light olefins.
Dehydrogenating low-carbon alkane catalyzed reaction is carried out under high temperature, lower pressure, and catalyst carbon deposit inactivation is serious, and the catalyzer of exploitation high reactivity, highly selective and high stability becomes the key of this technology.The disclosed catalyzer of Chinese patent (CN200710025372.X), be the preparation method of platinum-impregnated tin component on carrier at alumina modified mesoporous molecular sieve, conversion of propane is only 17%, Propylene Selectivity 93%; Chinese patent (CN200710023431.X) adopts the method for Hydrothermal Synthesis that tin is introduced ZSM-5 molecular sieve carrier, and by pickling process Supported Pt Nanoparticles component, after this catalyzer runs 100 hours, conversion of propane is higher than 30%, Propylene Selectivity 99%, but this patent does not provide the stability data of coke-burning regeneration process.Chinese patent (CN200710020064.8) and (CN200710133324.2) disclose a kind of platinum-tin catalyst and react for dehydrogenating propane, have employed the preparation method of tin component and platinum component total immersion stain, carrier is that Y type, ZSM-5 etc. are containing Na molecular sieve, after catalyzer runs 720 hours continuously, conversion of propane 30.5%, Propylene Selectivity 96.4%, but activity decrease half after twice coke-burning regeneration.
Above-mentioned catalyzer all have employed the active ingredient tin that aluminum oxide carrys out supported catalyst, the easy coking deactivation of catalyzer in applied at elevated temperature process, the poor stability of catalyzer.The Pt system dehydrogenation catalyst adopting the method for doped element periodictable II B compound and rare earth element to obtain also has no report for the document that low-carbon alkanes prepares low-carbon alkene.
Summary of the invention
Technical problem to be solved by this invention there is catalyzer easy coking deactivation in applied at elevated temperature process in existing technology of preparing, the problem of poor stability, a kind of method for dehydrogenating low-carbon alkane producing light olefins is newly provided, the method has when using under the high temperature conditions, catalyst carbon deposit deactivation rate is slow, the advantage that stability is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method preparing low-carbon alkene for dehydrogenating low-carbon alkane, with propane or/and Trimethylmethane is raw material, in temperature of reaction 520 ~ 650 oC, reaction pressure 0 ~ 0.4MPa, alkane mass space velocity 0.1 ~ 8.0h -1, H 2/ C nh 2n+2volume ratio is under 0.2 ~ 1.6 condition, raw material and catalyst exposure, reaction generation third rare/iso-butylene; Wherein catalyst comprises following component:
A) be selected from least one in ruthenium in platinum metals, rhodium, palladium, osmium, iridium or platinum, count 0.01 ~ 1.2% of catalyst weight with simple substance;
B) be selected from least one in the periodic table of elements II B compound, count 0.01 ~ 4.0% of catalyst weight with simple substance;
C) be selected from the catalyst aid (M) of rare earth element, at least one in La, Ce, Pr, Nd, Sm, Eu, Gd, Tb or Tm, counts 0.01 ~ 4.0% of catalyst weight with simple substance;
D) be selected from least one in the periodic table of elements I A or II A compound, count 0.01 ~ 1.0% of catalyst weight with simple substance;
E) carrier of 90 ~ 99.5%, carrier is selected from α-Al 2o 3, γ-Al 2o 3, δ-l 2o 3, θ-Al 2o 3or at least one of spinel.
In technique scheme, temperature of reaction preferable range is 540 ~ 600 oc; Reaction pressure preferable range is 0.05 ~ 0.35MPa; Starting alkane air speed preferable range is 0.5 ~ 5.6h -1; H 2/ C nh 2n+2the preferable range of volume ratio is 0.4 ~ 1.0; Reaction raw materials is propane, Trimethylmethane or the mixture of the two; Platinum metals is selected from Pt or Pd, and preferable range counts 0.1 ~ 1.0% of catalyst weight with simple substance.The periodic table of elements I A or II element A are selected from least one in Li, Na, K, Ca, Mg or Ba, and preferable range counts 0.05 ~ 0.6% of catalyst weight with simple substance.Composition metal auxiliary agent comprises at least one in the periodic table of elements II B compound, and preferable range is to count 1.0 ~ 2.0% of catalyst weight with simple substance; Be selected from the catalyst aid (M) of rare earth element, at least one in La, Ce, Pr, Nd, Sm, Eu, Gd, Tb or Tm, preferable range counts 0.1 ~ 2.0% of catalyst weight with simple substance.
The preparation method of used catalyst of the present invention comprises the following steps:
A) mixing solutions I is prepared, comprise the soluble salt aqueous solution of II B compound Zn of aequum, Cd, Hg, rare earth element auxiliary agent M and I A or II element A, its rare earth elements auxiliary agent M is selected from least one in La, Ce, Pr, Eu or Tm, and I A/ II element A is selected from least one in Li, Na, K, Ca, Mg or Ba;
B) extrusion moulding is adopted to obtain composite alumina support: in the kneading process of precursor carrier pseudo-boehmite, to add solution I, after mediating evenly also extrusion moulding, 60 ~ 120 oCdry, 650 ~ 1000 oCroasting 3 ~ 12 hours, obtains composite catalyst carrier;
C) the platinichloride aqueous solution II of aequum is prepared;
D) with pickling process by soluble salt load contained in solution II in composite catalyst carrier, flood after 12 ~ 48 hours, after drying, obtain catalyst precursor;
Catalyst precursor is 450 ~ 650 oc roasting 0.5 ~ 12 hour, and obtain dehydrogenating low-carbon alkane producing light olefins catalyzer with hydrogen reducing with steam dechlorination after 0.5 ~ 10 hour.
The introducing of metal promoter plays critical effect for platinum group dehydrogenation catalyst, find after a large amount of experiments, the composite assistant that II B race elementary composition and rare earth element component form can play good promoter action for the activity of catalyzer, this is likely metal promoter component can be made fully to contact with carrier in the process of mediating, and the pressure produced in extrusion process also can make auxiliary component and carrier interact, auxiliary component is distributed on carrier more even, be thus conducive to activity and the stability of catalyzer.
Dehydrogenating low-carbon alkane reaction is carried out on the miniature catalyst reaction device of continuous flow quartz tube reactor.Product analysis adopts HP-5890 gas chromatograph (HP-AL/S capillary column, 50m × 0.53mm × 15 μm; Fid detector) alkane in on-line analysis dehydrogenation product, olefin(e) centent calculate the transformation efficiency of reaction, selectivity and yield.The catalyzer that use present method obtains is in temperature 520 ~ 650 oC, pressure 0 ~ 0.4MPa, alkane mass space velocity 0.1 ~ 8.0h -1, H 2/ C nh 2n+2be use under 0.1 ~ 1.6 condition, Trimethylmethane transformation efficiency is higher than 45%, selective isobutene is higher than 88%, after reaction in 100 hours, transformation efficiency is higher than 34%, and selectivity is higher than 90%, through the stable performance of the regenerated catalyst of more than 20 times, transformation efficiency is higher than 43%, and selectivity, higher than 90%, achieves good technique effect.
Embodiment
Below by embodiment, the present invention is further elaborated.
[embodiment 1]
In the former powder major ingredient of 300.2g pseudo-boehmite, add 9.0g sesbania powder mix, then add the mixing solutions of 130ml containing catalyst activity component, comprising NaNO 3, 2.2g; La (NO 3) 36H 2o, 2.5g; Zn (NO 3) 26H 2o, 1.91g, 0.8g50% manganese nitrate aqueous solution, 10g4% cyclodextrin aqueous solution, mediate extrusion fully, ambient temperatare puts 12 hours, keep 3 hours with 90 DEG C, 120 DEG C of programs kept 10 hours are dried again, and pelletizing also processes the obtained complex carrier containing catalyst aid at 750 DEG C.
The composite alumina support obtained, adopts platinum component in dipping technique load, namely at room temperature with the Platinic chloride (H of the alumina supporter dipping aequum of gained 2ptCl 66H 2o, 2.23g) the aqueous solution 24 hours (metal platinum carrying capacity 0.3%), then 60 oCdry, in the air stream 530 oCroasting 3 hours, then uses water vapour 530 oClower process 4 hours, finally logical dry air 530 oCprocess and obtain catalyst sample in 1 hour, be designated as A.Sample uses hydrogen before dehydrogenation reaction, and 500 oCreduction activation 90 minutes, for propane/dehydrogenation of isobutane reaction.Reaction result is in table 2.
[embodiment 2]
By the method Kaolinite Preparation of Catalyst of embodiment 1, difference is; H 2ptCl 66H 2o, 5.3g; Zn (NO 3) 26H 2o, 13.6g; Ce (NO 3) 36H 2o, 7.0g; Mg (NO 3) 26H 2o, 10.7g.Gained catalyst weight composition is in table 1, and be designated as B, reaction result is in table 2.
[embodiment 3]
By the method Kaolinite Preparation of Catalyst of embodiment 1, difference is; (NH 4) 2pdCl 4, 3.4g; Zn (NO 3) 26H 2o, 7.3g; La (NO 3) 36H 2o, 14.0g; KNO 3, 4.5g.Gained catalyst weight composition is in table 1, and be designated as C, reaction result is in table 2.
[embodiment 4]
By the method Kaolinite Preparation of Catalyst of embodiment 1, difference is; H 2ptCl 66H 2o, 0.7g; Cd (NO 3) 24H 2o, 4.1g; Nd (NO 3) 36H 2o, 3.0g; Ca (NO 3) 24H 2o, 0.1g.Gained catalyst weight composition is in table 1, and be designated as D, reaction result is in table 2.
[embodiment 5]
By the method Kaolinite Preparation of Catalyst of embodiment 1, difference is; Rh (NO 3) 32H 2o, 3.2g; Zn (NO 3) 26H 2o, 5.2g; Ce (NO 3) 36H 2o, 0.6g; NaNO 3, 4.6g.Gained catalyst weight composition is in table 1, and be designated as E, reaction result is in table 2.
[comparative example 1]
By the method Kaolinite Preparation of Catalyst of embodiment 1, difference is with the former powder 321.4g of pseudo-boehmite; SnCl 45H 2o, 5.9g; NaNO 3, 2.5g; H 2ptCl 66H 2o, 2.9g; Do not add Zn (NO 3) 26H 2o and La (NO 3) 36H 2o.Gained catalyst weight composition is in table 1, and be designated as F, reaction result is in table 2, and reaction conditions is with embodiment 1.
[comparative example 2]
By the method Kaolinite Preparation of Catalyst of comparative example 1, difference is with the former powder 312.3g of pseudo-boehmite; SnCl 45H 2o, 4.5g; NaNO 3, 2.8g; H 2ptCl 66H 2o, 2.3g; Wherein SnCl 45H 2o adopts impregnation method to introduce catalyzer after obtained carrier.Gained catalyst weight composition is in table 1, and be designated as G, reaction result is in table 2, and reaction conditions is with embodiment 1.
Table 1
Embodiment 1 ~ 5, comparative example 1 ~ 2 at normal pressure, temperature 550 oC; C nh 2n+2/ H 2=5/2 (vol/vol); Alkane air speed (WHSV) is 4.6h -1carry out activity rating under condition, test result lists in table 2.
Table 2*
* the data in bracket are for adopting same catalyst, and raw material changes the dehydrogenation data of propane into.
[comparative example 3]
The comparative example 1 gained catalyzer F (adopting traditional Sn auxiliary agent) and comparative example 2 catalyzer G that do not contain composition metal auxiliary agent are carried out the experiment of stability, and contrast with embodiment 1, experimental result is in A, F, the G in table 2.Reaction conditions is with embodiment 1.The catalyzer F transformation efficiency of containing metal auxiliary agent does not drop to 21.8% from 41.6% after 100 hours, and lowering speed is far above catalyst A (only dropping to 34.6% from 45.8%).Comparative example 2 gained catalyzer G, also has similar result.
[comparative example 4]
Embodiment 1 gained catalyzer is carried out coke-burning regeneration performance evaluation, and reaction conditions is with embodiment 1, and the reaction result of catalyzer after 6 hours is in table 3, and raw material is Trimethylmethane.
Table 3
[embodiment 6 ~ 12]
Embodiment 2 is carried out performance evaluation under differential responses processing condition, the results are shown in Table 4.
Table 4

Claims (2)

1. a method for low-carbon alkene is prepared for dehydrogenating low-carbon alkane, with propane or/and Trimethylmethane is raw material, temperature of reaction 540 ~ 600 DEG C, reaction pressure 0.05 ~ 0.35MPa, alkane mass space velocity 0.5 ~ 5.6h -1, H 2/ C nh 2n+2volume ratio is under 0.2 ~ 1.6 condition, raw material and catalyst exposure, and reaction generates propylene/iso-butylene; Wherein catalyst is composed of the following components:
A) be selected from least one in ruthenium in platinum metals, rhodium, palladium, osmium, iridium or platinum, count 0.01 ~ 1.2% of catalyst weight with simple substance;
B) be selected from least one in the periodic table of elements II B compound, count 0.01 ~ 4.0% of catalyst weight with simple substance;
C) be selected from the catalyst aid (M) of rare earth element, the one in La, Ce, Pr, Nd, Sm, Eu, Gd, Tb or Tm, counts 0.01 ~ 4.0% of catalyst weight with simple substance;
D) be selected from least one in the periodic table of elements II A compound, count 0.01 ~ 1.0% of catalyst weight with simple substance;
E) carrier of 90 ~ 99.5%, carrier is selected from α-Al 2o 3, γ-Al 2o 3, δ-l 2o 3, θ-Al 2o 3or at least one of spinel;
The preparation method of described catalyzer comprises the following steps:
A) mixing solutions I is prepared, comprise the soluble salt aqueous solution of II B compound Zn of aequum, Cd, Hg, rare earth element auxiliary agent M and II element A, its rare earth elements auxiliary agent M is selected from the one in La, Ce, Pr, Eu or Tm, and II element A is selected from least one in Ca, Mg or Ba;
B) extrusion moulding is adopted to obtain composite alumina support: in the kneading process of precursor carrier pseudo-boehmite, add solution I, after mediating evenly also extrusion moulding, 60 ~ 120 DEG C of oven dry, 650 ~ 1000 DEG C of roastings 3 ~ 12 hours, obtain composite catalyst carrier;
C) the platinichloride aqueous solution II of aequum is prepared;
D) with pickling process by soluble salt load contained in solution II in composite catalyst carrier, flood after 12 ~ 48 hours, after drying, obtain catalyst precursor;
Catalyst precursor 450 ~ 650 DEG C of roastings 0.5 ~ 12 hour, and obtains dehydrogenating low-carbon alkane producing light olefins catalyzer with hydrogen reducing with steam dechlorination after 0.5 ~ 10 hour.
2. prepare the method for low-carbon alkene according to claim 1 for dehydrogenating low-carbon alkane, it is characterized in that reaction raw materials is at least one in propane or Trimethylmethane.
CN201210150493.8A 2012-05-16 2012-05-16 The method of dehydrogenating low-carbon alkane producing light olefins Active CN103420769B (en)

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CN106607025B (en) * 2015-10-22 2020-01-03 中国石油化工股份有限公司 Isobutane dehydrogenation catalyst and preparation method thereof
CN105688891B (en) * 2016-03-02 2018-09-28 天津科技大学 A kind of high initial activity catalyst and preparation method thereof for preparing propylene by dehydrogenating propane
CN107537485B (en) * 2016-06-29 2020-08-07 中国石油化工股份有限公司 Catalyst for preparing isoamylene by dehydrogenating isopentane and preparation method thereof
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CN110496631B (en) * 2018-05-17 2021-09-21 中国石油化工股份有限公司 Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation
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CN110496632B (en) * 2018-05-17 2021-12-21 中国石油化工股份有限公司 Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation

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