CN103420769A - Method for preparing low-carbon olefin from low-carbon alkane through dehydrogenation - Google Patents
Method for preparing low-carbon olefin from low-carbon alkane through dehydrogenation Download PDFInfo
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- CN103420769A CN103420769A CN2012101504938A CN201210150493A CN103420769A CN 103420769 A CN103420769 A CN 103420769A CN 2012101504938 A CN2012101504938 A CN 2012101504938A CN 201210150493 A CN201210150493 A CN 201210150493A CN 103420769 A CN103420769 A CN 103420769A
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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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- 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
Abstract
The invention relates to a method for preparing low-carbon olefin from low-carbon alkane through dehydrogenation, and mainly solves the problems of poor stability and high tendency to carbon deposition inactivation of a catalyst in a high temperature use process in the prior art. The technical scheme is as follows: propane/isobutane are used as raw materials, the raw materials are contacted and reacted with the catalyst under conditions of a reaction temperature of 520-620 DEG C, a reaction pressure of 0-0.4 MPa, a quality airspeed of the alkane of 0.1-8.0 h<-1> and the volume ratio of H2/CnH2n+2 for 0.2-1.6, and then propylene/isobutylene can be generated. According to the technical scheme, the problems of poor stability and high tendency to carbon deposition inactivation of the catalyst in the high temperature use process are well solved. The method can be used for industrial production of the catalyst for preparing the low-carbon olefin from the low-carbon alkane through dehydrogenation.
Description
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 the 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 that obtained by refinery are main components of liquefied petroleum gas (LPG), mainly as domestic fuel.By low-carbon alkanes preparing low-carbon olefins process, for taking full advantage of low-carbon alkanes, to open up new alkene source significant in exploitation.At present, to take the Oleflex technique of Uop Inc. and the Catofin technique of Lummus company be representative to propane catalytic dehydrogenation technology.The domestic production equipment that still there is no the dehydrogenating low-carbon alkane producing light olefins.
The dehydrogenating low-carbon alkane catalyzed reaction is carried out under high temperature, low pressure condition, and the 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), the preparation method who is 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 to the ZSM-5 molecular sieve carrier, and by pickling process Supported Pt Nanoparticles component, this catalyzer operation is after 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, adopted the preparation method of tin component and platinum component total immersion stain, carrier is that Y type, ZSM-5 etc. are containing the Na molecular sieve, after catalyzer moves 720 hours continuously, conversion of propane 30.5%, Propylene Selectivity 96.4%, but active drop by half after twice coke-burning regeneration.
Above-mentioned catalyzer has all adopted aluminum oxide to come the active ingredient tin of supported catalyst, the easy coking deactivation of catalyzer in the applied at elevated temperature process, the poor stability of catalyzer.To adopt Pt that the method for doped element periodictable II B compound and rare earth element obtains be dehydrogenation catalyst and have 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 is to have catalyzer easy coking deactivation in the applied at elevated temperature process in existing technology of preparing, the problem of poor stability, a kind of new method for the dehydrogenating low-carbon alkane producing light olefins is provided, the method has while using under hot conditions, the 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 for preparing low-carbon alkene for dehydrogenating low-carbon alkane, take 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, and raw material contacts with catalyzer, reaction generates third rare/iso-butylene; Wherein used catalyst comprises following component by weight percentage:
A) be selected from least one in ruthenium in platinum metals, rhodium, palladium, osmium, iridium or platinum, with simple substance, count 0.01～1.2% of catalyst weight;
B) be selected from least one in periodic table of elements II B compound, with simple substance, count 0.01～4.0% of catalyst weight;
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, count 0.01～4.0% of catalyst weight with simple substance;
D) be selected from least one in periodic table of elements I A or II A compound, with simple substance, count 0.01～1.0% of catalyst weight;
E) 90～99.5% carrier, 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, the temperature of reaction preferable range is 540～600
oC; The reaction pressure preferable range is 0.05～0.35MPa; Raw material alkane air speed preferable range is 0.5～5.6h
-1H
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 is counted 0.1～1.0% of catalyst weight with simple substance.Periodic table of elements I A or II A element are selected from least one in Li, Na, K, Ca, Mg or Ba, and preferable range is counted 0.05～0.6% of catalyst weight with simple substance.The composition metal auxiliary agent comprises at least one in 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 is counted 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) preparation mixing solutions I, the soluble salt aqueous solution that comprises II B compound Zn, Cd, Hg, rare earth element auxiliary agent M and I A or the II A element of aequum, its rare earth elements auxiliary agent M is selected from least one in La, Ce, Pr, Eu or Tm, and I A/ II A element is selected from least one in Li, Na, K, Ca, Mg or Ba;
B) adopt extrusion moulding to obtain composite alumina support: in the kneading process of precursor carrier pseudo-boehmite, to add the solution I, after mediating evenly also extrusion moulding, 60～120
OCDry 650～1000
OCRoasting 3～12 hours, obtain the composite catalyzing agent carrier;
C) the platinichloride aqueous solution II of preparation aequum;
D) by pickling process, contained soluble salt in the solution II is loaded on the composite catalyzing agent carrier, after flooding 12～48 hours, obtain catalyst precursor after drying;
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 the platinum group dehydrogenation catalyst, after a large amount of experiments, find, the composite assistant that the elementary composition of II B family and rare earth element component form can play good promoter action for the activity of catalyzer, this is likely can make the metal promoter component fully contact with carrier in the process of mediating, and the pressure produced in extrusion process also can make auxiliary component and carrier interact, make auxiliary component distribute on carrier more even, thereby be conducive to activity and the stability of catalyzer.
The 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 μ m; Fid detector) transformation efficiency, selectivity and the yield of the alkane in the on-line analysis dehydrogenation product, olefin(e) centent calculating reaction.The catalyzer that uses present method to obtain 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 to use under 0.1～1.6 condition, the 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%, stable performance through the regeneration rear catalyst more than 20 times, transformation efficiency is higher than 43%, and selectivity, higher than 90%, has obtained technique effect preferably.
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 to mix, then add the mixing solutions of 130 ml containing the catalyst activity component, comprising NaNO
3, 2.2g; La (NO
3)
36H
2O, 2.5g; Zn (NO
3)
26H
2O, 1.91g, 0.8g 50% manganese nitrate aqueous solution, 10g 4% cyclodextrin aqueous solution, mediate fully rear extrusion, under room temperature, places 12 hours, with 90 ℃, keep 3 hours, 120 ℃ of programs that keep 10 hours are dried again, and pelletizing is also processed and made the complex carrier containing catalyst aid under 750 ℃.
The composite alumina support obtained, adopt platinum component in the dipping technique load, at room temperature with the alumina supporter of gained, floods the Platinic chloride (H of aequum
2PtCl
66H
2O, 2.23g) the aqueous solution 24 hours (metal platinum carrying capacity 0.3%), then 60
OCDry, in airflow 530
OCRoasting 3 hours, then use water vapour 530
OCLower processing 4 hours, finally logical dry air 530
OCProcess and obtain catalyst sample in 1 hour, be designated as A.Sample is used hydrogen, 500 before dehydrogenation reaction
OCReduction activation 90 minutes, for propane/dehydrogenation of isobutane reaction.Reaction result is in Table 2.
[embodiment 2]
Press 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.The gained catalyst weight forms in Table 1, is designated as B, and reaction result is in Table 2.
[embodiment 3]
Press 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.The gained catalyst weight forms in Table 1, is designated as C, and reaction result is in Table 2.
[embodiment 4]
Press 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.The gained catalyst weight forms in Table 1, is designated as D, and reaction result is in Table 2.
[embodiment 5]
Press 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.The gained catalyst weight forms in Table 1, is designated as E, and reaction result is in Table 2.
[Comparative Examples 1]
Press 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.The gained catalyst weight forms in Table 1, is designated as F, and reaction result is in Table 2, and reaction conditions is with embodiment 1.
[Comparative Examples 2]
By the method Kaolinite Preparation of Catalyst of Comparative Examples 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; SnCl wherein
45H
2O adopts impregnation method to introduce catalyzer after making carrier.The gained catalyst weight forms in Table 1, is designated as G, and reaction result is in Table 2, and reaction conditions is with embodiment 1.
Table 1
Embodiment 1～5, and Comparative Examples 1～2 is at normal pressure, temperature 550
OCC
nH
2n+2/ H
2=5/2 (vol/vol); Alkane air speed (WHSV) is 4.6h
-1Carry out activity rating under condition, test result is listed 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 Examples 3]
To containing Comparative Examples 1 gained catalyzer F (adopting traditional Sn auxiliary agent) and the Comparative Examples 2 catalyzer G of composition metal auxiliary agent, not carry out the experiment of stability, and contrasted with embodiment 1, experimental result is in Table A, F, G in 2.Reaction conditions is with embodiment 1.The catalyzer F transformation efficiency of containing metal auxiliary agent did 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 Examples 2 gained catalyzer G, also have similar result.
[Comparative Examples 4]
Embodiment 1 gained catalyzer is carried out to the 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 under the differential responses processing condition to performance evaluation, the results are shown in Table 4.
Table 4
Claims (6)
1. a method for preparing low-carbon alkene for dehydrogenating low-carbon alkane, take 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, and raw material contacts with catalyzer, reaction generates third rare/iso-butylene; Wherein used catalyst comprises following component by weight percentage:
A) be selected from least one in ruthenium in platinum metals, rhodium, palladium, osmium, iridium or platinum, with simple substance, count 0.01～1.2% of catalyst weight;
B) be selected from least one in periodic table of elements II B compound, with simple substance, count 0.01～4.0% of catalyst weight;
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, count 0.01～4.0% of catalyst weight with simple substance;
D) be selected from least one in periodic table of elements I A or II A compound, with simple substance, count 0.01～1.0% of catalyst weight;
E) 90～99.5% carrier, 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.
2. prepare according to claim 1 the method for low-carbon alkene for dehydrogenating low-carbon alkane, it is characterized in that temperature of reaction is 540～600
oC.
3. prepare according to claim 1 the method for low-carbon alkene for dehydrogenating low-carbon alkane, it is characterized in that reaction pressure is 0.05～0.35MPa.
4. prepare according to claim 1 the method for low-carbon alkene for dehydrogenating low-carbon alkane, it is characterized in that the alkane mass space velocity is 0.5～5.6h
-1.
5. prepare according to claim 1 the method for low-carbon alkene for dehydrogenating low-carbon alkane, it is characterized in that H
2/ C
nH
2n+2Volume ratio is 0.2～1.6.
6. prepare according to claim 1 the method for low-carbon alkene for dehydrogenating low-carbon alkane, it is characterized in that reaction raw materials is at least one in propane or Trimethylmethane.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105688891A (en) * | 2016-03-02 | 2016-06-22 | 天津科技大学 | High-initial-activity catalyst for propane dehydrogenation to prepare propylene and preparing method thereof |
| CN106311311A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst for preparing propylene through propane dehydrogenation, preparation method of catalyst, and method for propylene through propane dehydrogenation |
| CN106607025A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst and preparation method thereof |
| CN107428711A (en) * | 2015-01-14 | 2017-12-01 | 赢创德固赛有限公司 | Prepare the integrated approach of propylene oxide and alkyl-tert-butyl ether |
| CN107537485A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Catalyst of isopentane dehydrogenation iso-amylene and preparation method thereof |
| CN107899619A (en) * | 2017-10-31 | 2018-04-13 | 西南化工研究设计院有限公司 | A kind of preparing propylene by dehydrogenating propane composite alumina support catalyst and preparation method thereof |
| CN110496631A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| CN110496632A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| CN110496633A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
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| CN107428711A (en) * | 2015-01-14 | 2017-12-01 | 赢创德固赛有限公司 | Prepare the integrated approach of propylene oxide and alkyl-tert-butyl ether |
| CN106311311A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst for preparing propylene through propane dehydrogenation, preparation method of catalyst, and method for propylene through propane dehydrogenation |
| CN106607025A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst and preparation method thereof |
| 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 |
| CN105688891A (en) * | 2016-03-02 | 2016-06-22 | 天津科技大学 | High-initial-activity catalyst for propane dehydrogenation to prepare propylene and preparing method thereof |
| 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 |
| CN107537485A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | Catalyst of isopentane dehydrogenation iso-amylene and preparation method thereof |
| CN107899619B (en) * | 2017-10-31 | 2019-07-30 | 西南化工研究设计院有限公司 | A kind of preparing propylene by dehydrogenating propane composite alumina support catalyst and preparation method thereof |
| CN107899619A (en) * | 2017-10-31 | 2018-04-13 | 西南化工研究设计院有限公司 | A kind of preparing propylene by dehydrogenating propane composite alumina support catalyst and preparation method thereof |
| CN110496631A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| CN110496632A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| CN110496633A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| 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 |
| CN110496633B (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 |
| 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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