CN102531817B - Method for preparing olefin by dehydrogenating low-carbon alkane - Google Patents
Method for preparing olefin by dehydrogenating low-carbon alkane Download PDFInfo
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- CN102531817B CN102531817B CN201010610690.4A CN201010610690A CN102531817B CN 102531817 B CN102531817 B CN 102531817B CN 201010610690 A CN201010610690 A CN 201010610690A CN 102531817 B CN102531817 B CN 102531817B
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- catalyzer
- reaction
- carbon monoxide
- alkane
- unstripped gas
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
Abstract
The invention discloses a method for preparing olefin by dehydrogenating low-carbon hydrocarbons. A hydrogen product is consumed by using reaction of hydrogen and carbon monoxide to break through the balance of the reaction, and the reaction tends to the dehydrogenation direction, so that the balance conversion rate of the low-carbon hydrocarbons and the selectivity of the corresponding olefin are improved.
Description
Technical field
The present invention relates to a kind of hydro carbons in carbon monoxide atmosphere, carry out the novel method of dehydrogenation of hydrocarbons alkene processed.
Background technology
Ethene is the most important a kind of basic raw material of petrochemical complex, mainly for the production of Organic Chemicals such as the polymkeric substance such as polyethylene, polyvinyl chloride and oxyethane, ethylene glycol, approximately has 75% petrochemicals to be produced by ethene at present.Current industrial ethylene production mainly adopts the preparation of hydrocarbon vapours cracking process, the method severe reaction conditions, and investment is large, generates coke and be deposited in furnace wall in reaction process, and reaction preference is poor, regularly coke cleaning.
In order to utilize more fully ethane resource, the novel process of Recent study making ethylene from ethane oxidative dehydrogenation has obtained certain progress.In ethane, add oxygen, but due to the hyperoxia voltinism of oxygen, can make the ethene generating further be oxidized generation carbonic acid gas, a lot of scholars are by adding weak oxidant carbonic acid gas to prevent the further oxidation of ethene.Xu Long childs etc. (Xu Longya et al.Appl.Catal.A:193 (2000) 95-101) prepare 5%K-0.5%Ni-9%Mn-7%Cr/Si-2 catalyzer, its ethane conversion and carbon dioxide conversion are respectively 66.9% and 19.2%, and the selectivity of ethane brings up to 85.3%.
In addition, propylene, as important petrochemical complex intermediate, is a kind of important petrochemical complex basic raw material, can be used for manufacturing the important Chemicals such as vinyl cyanide, phenol, fourth/octanol, propylene oxide and vinylformic acid, can also be as the raw material of producing stop bracket gasoline.The supply of propylene is mainly derived from the by product of naphtha steam cracking ethene processed and catalytic cracking.But in order to meet the demand of petrochemical industry to propylene, dehydrogenating propane technique receives increasing concern.Relatively abundant at natural gas source, be that the research of propylene has important theory and practical significance to the petrochemical industry development of China and carry out transformation of propane under the weary background of petroleum resources plaque.
The method of current industrial employing high temperature By Direct Pyrolysis low-carbon alkanes is produced alkene, as the Oleflex technique of the Catofin technique of ABBLummus company and Uop Inc..But cracking temperature is high, process energy consumption is large, cracking product composition complexity, and separation and purification difficulty, therefore adopts oxidative dehydrogenation process more to be paid close attention to.Loaded catalyst take chromium as main active component has good catalytic activity to oxidative dehydrogenation of propane.Piotr (Piotr Michorczyk, Jan Ogonowski, MartaNiemczyk.Appl.Catal.A:Gen.374 (2010) 142-149) etc. the Cr catalyzer on the mesoporous SBA-1 with rule space structure of loading on of preparation for propane, dehydrogenation under the condition of carbonic acid gas generates propylene and has good effect.Shen Jianyi (CN 1472005A) adopts the chromium potassium catalyzer of superfine silicon dioxide load, and propane and carbon dioxide reaction can selectively be converted into propylene by height, and invert point reduces.High specific surface area chromium Si catalyst has been invented by Rhom and Hass (CN 101481290A), and the maximum yield of its propylene in the time of reaction 10min reaches 49%.
In sum, in reaction, add the weak carbonic acid gas of relative dioxygen oxidation, thus both can prevent product further oxidation improve selectivity, carry out to object product direction thereby can also eliminate the hydrogen driving a reaction that reaction generates.Obviously, hydro carbons and carbon dioxide reaction system tool have great advantage, but due to CO
2the gas of very difficult activation, and and H
2it is more difficult to react, and therefore still needs to find out the reaction system of being prepared alkene by hydro carbons high yield, and this reaction system can better driving a reaction be carried out and the consumption of postreaction energy.
Summary of the invention
One object of the present invention is to provide a kind of method that contains manufacturing olefin by low-carbon alkane dehydrogenation, utilize hydrogen and reaction of carbon monoxide, cause the consumption of product hydrogen, break molecular balance, impel reaction to carry out towards dehydrogenation direction, thereby improve equilibrium conversion and the corresponding olefine selective of alkane.; a kind of mode of new dehydrating alkanes is provided on the basis of alkane dehydrogenating catalyst system; it is characterized in that; contain and under carbon monoxide atmosphere, pass into the reactor that contains catalyzer at alkane; generate methane and water by hydrogen and reaction of carbon monoxide; consume the hydrogen in product, impel reaction to carry out to dehydrogenation direction, thereby effectively improve transformation efficiency and the selectivity of hydro carbons.
In the present invention, described alkane carries out dehydrogenation reaction under the existence of carbon monoxide, generates described alkene, and wherein said alkane contains 2 to 10 carbon atoms.
In the present invention, described reaction is that the unstripped gas that comprises described alkane and described carbon monoxide is fed in reactor.
In the present invention, described alkane is any one or any several mixture in ethane, propane, butane and Trimethylmethane.
In the present invention, described unstripped gas also contains other gas.
In the present invention, described other gas is N
2, He, Ar, O
2and CO
2in any one or any several mixture.
In the present invention, in described unstripped gas, the molar content of carbon monoxide is 0.5%-90%.
In the present invention, in described unstripped gas, the molar content of carbon monoxide is 10%-80%.
In the present invention, in described unstripped gas, the molar content of carbon monoxide is 20%-80%.
In the present invention, described catalysts is dehydrogenation catalyst.
In the present invention, described catalyst activity component is selected from one or more in VIB, VIIB and group VIII metal, as be selected from Cr, V, Mo, Ga, Mn, Fe, Ru, Rh, Ni, Pd, Pt and Ni any one or several combination arbitrarily, be preferably Cr and/or Ga.In the present invention, described catalyst adjuvant is selected from any one or arbitrarily several combination of basic metal, alkaline-earth metal, IIIA, IV and IIB family metal, and preferred auxiliary agent is potassium.
In the present invention, described support of the catalyst is SiO
2, Al
2o
3, SBA-15.
In the present invention, after described metal/modification, metal catalyst is take matrix weight as benchmark, take its content of metal as 0.3%-15%.
In the present invention, described catalyst adjuvant, take matrix weight as benchmark, is no more than 10% in its content of metal.
In the present invention, described low-carbon alkanes is 400-800 ℃ with the temperature of reaction of the unstripped gas that contains carbon monoxide in reactor.
The outstanding advantage of the present invention is, by adding of carbon monoxide, consumes the hydrogen producing, and effectively improves transformation efficiency and the selectivity of hydro carbons.
Embodiment
In the present invention, product adopts Agilent (Agilent) 7890 type chromatograms to analyze product, and concrete analysis condition is:
FID chromatographic column: HP-PLOT-Q 19091P-Q04,30m × 0.32mm (internal diameter), 20 μ m thickness
Carrier gas: helium, 1.5ml/min
Post case temperature: 40 ℃ keep 1min; 40-180 ℃, 10 ℃/min of temperature rise rate; 180 ℃ keep 10min.
Injection port: shunting (100: 1) temperature is 170 ℃.
Detector temperature: 250 ℃
TCD chromatographic column: carbonaceous molecular sieve post, TDX-01 2m × 2mm (internal diameter)
Carrier gas: helium, 20ml/min
Post case temperature: 40 ℃ keep 1min; 40-180 ℃, 10 ℃/min; 180 ℃ keep 10min
Injection port: temperature: 170 ℃
Detector temperature: 200 ℃
Be that middle tie is normalized and calculates each material amount of substance percentage composition by the amount of methane in chromatogram FID and TCD detected result, transformation efficiency and selectivity are specifically calculated as follows formula:
N
cO2/ n
cH4/ n
c2H4/ n
c2H6/ n
c3H6/ n
c3H8: the amount of substance percentage ratio of carbonic acid gas/methane/ethylene/ethane/propylene/propane in product
Below by embodiment in detail the present invention is described in detail, but the present invention is not limited to these embodiment.
Embodiment mono-
In embodiment, table 1 is listed in raw materials used character and source
The preparation of catalyzer
3%Cr/SiO
2the preparation of catalyzer
By 0.71 gram of Cr (NO
3)
39H
2o adds water 2.25 milliliters and dissolves, and adding 3 grams of specific surface areas is 640m
2the silicon-dioxide dipping of/g, the room temperature that stirs is placed 24 hours, then at 120 ℃, is dried 2 hours.
In static retort furnace, by the 600 ℃ of roastings 4 hours in air of the silicon-dioxide of dry load chromium nitrate precursor, make 3%Cr/SiO
2catalyzer.
3%Cr/SiO
2the preparation of-1 catalyzer
By 0.71 gram of Cr (NO
3)
39H
2o adds water 2.25 milliliters and dissolves, and adds 3 grams of silicon-dioxide dippings, and the room temperature that stirs is placed 24 hours, then at 120 ℃, is dried 2 hours.
In static retort furnace, by the multistage intensification roasting in air of the silicon-dioxide of dry load chromium nitrate precursor, 250 ℃ of roasting 30min, 350 ℃ of roasting 30min, 450 ℃ of roasting 30min, 600 ℃ of roasting 4h, prepare 3%Cr/SiO
2-1 catalyzer.
6%Cr/Si0
2the preparation of catalyzer
By 1.47 grams of Cr (NO
3)
39H
2o adds water 2.25 milliliters and dissolves, and adding 3 grams of specific surface areas is 640m
2the silicon-dioxide dipping of/g, the room temperature that stirs is placed 24 hours, then at 120 ℃, is dried 2 hours.
In static retort furnace, by the 600 ℃ of roastings 4 hours in air of the silicon-dioxide of dry load chromium nitrate precursor, make 6%Cr/SiO
2catalyzer.
10%Cr/SiO
2the preparation of catalyzer
By 2.57 grams of Cr (NO
3)
39H
2o adds water 2.25 milliliters and dissolves, and adding 3 grams of specific surface areas is 640m
2the silicon-dioxide dipping of/g, the room temperature that stirs is placed 24 hours, then at 120 ℃, is dried 2 hours.
In static retort furnace, by the 600 ℃ of roastings 4 hours in air of the silicon-dioxide of dry load chromium nitrate precursor, make 6%Cr/SiO
2catalyzer.
Cr/K/SiO
2the preparation of catalyzer
By 0.71 gram of Cr (NO
3)
39H
2o and 0.039g saltpetre add water 2.25 milliliters and dissolve, and adding 3 grams of specific surface areas is 640m
2the silicon-dioxide dipping of/g, the room temperature that stirs is placed 24 hours, then at 120 ℃, is dried 2 hours.
In static retort furnace, by the 600 ℃ of roastings 4 hours in air of the silicon-dioxide of dry load chromium nitrate precursor and saltpetre precursor, make 3%Cr/0.5%K/SiO
2catalyzer.
3%Ga/SiO
2the preparation of catalyzer
By 0.34 gram of Ga (NO
3)
3dissolve with adding water 2.25 milliliters, adding 3 grams of specific surface areas is 640m
2the silicon-dioxide dipping of/g, the room temperature that stirs is placed 24 hours, then at 120 ℃, is dried 2 hours.
In static retort furnace, by the 600 ℃ of roastings 4 hours in air of the silicon-dioxide of dry load chromium nitrate precursor, make 3%Ga/SiO
2catalyzer.
3%Cr/Al
2o
3the preparation of catalyzer
By 0.71 gram of Cr (NO
3)
39H
2o dissolves with adding water 1.14 milliliters, adds 3 grams of γ-Al
2o
3dipping, the room temperature that stirs is placed 24 hours, then at 120 ℃, is dried 2 hours.
In static retort furnace, by the 600 ℃ of roastings 4 hours in air of the silicon-dioxide of dry load chromium nitrate precursor, make 3%Cr/Al
2o
3catalyzer.
The preparation of 3%Cr/SBA-15 catalyzer
By 0.71 gram of Cr (NO
3)
39H
2o dissolves with adding water 3.78 milliliters, adds 3 grams of SBA-15 dippings, and the room temperature that stirs is placed 24 hours, then at 120 ℃, is dried 2 hours.
In static retort furnace, by the 600 ℃ of roastings 4 hours in air of the silicon-dioxide of dry load chromium nitrate precursor, make 3%Cr/SBA-15 catalyzer.
Embodiment bis-
In stainless steel reactor (internal diameter 6mm), pack 0.3g catalyzer into, catalyzer is at N
2under purging, be warming up to 600 ℃, then switch to reaction gas, it specifically consists of 20%C
3h
8, 80%CO or CO
2or N
2, above-mentioned percentage composition is molar content, and feed stream air speed is 1750h
-1, reacted product enters chromatogram analysis, under normal pressure, reacts after 6 minutes, records the fresh productive rate of propylene.Analytical results lists in table 2.
Table 2C
3h
8respectively with CO, CO
2, N
2reaction result on different Cr charge capacity catalyzer
Propane reacts in different atmospheres as can be seen from Table 2, and carbon monoxide is greater than carbonic acid gas and nitrogen to the promoter action of dehydrogenating propane reaction; Cr charge capacity is that 6% catalyst effect is better, obtains higher conversion of propane and Propylene Selectivity.
The reaction result of multistage intensification calcined catalyst in embodiment tri-air atmosphere
Except changing catalyzer into 3%Cr/SiO
2outside-1 catalyzer, react to carry out dehydrogenating propane with the same way of embodiment 2.The results are shown in table 3.
Table 3C
3h
8respectively with CO, CO
2, N
2at catalyzer 3%Cr/SiO
2reaction result on-1
Can be found out by the contrast of table 3 and table 2, the multistage catalyzer making that heats up is better than catalyzer in embodiment 1 on conversion of propane and Propylene Selectivity.
Under embodiment tetra-differing tempss at catalyzer 3%Cr/SiO
2on reaction result
Except changing temperature of reaction, react to carry out dehydrogenating propane with the same way of embodiment 2.The results are shown in table 4.
Under table 4 differing temps at catalyzer 3%Cr/SiO
2on reaction result
As can be seen from Table 4 along with the rising conversion of propane of temperature increases, but Propylene Selectivity reduces along with temperature raises simultaneously.
Embodiment five differential responses materials are at catalyzer 3%Cr/SiO
2reaction result on-1
Except changing reaction mass, react to carry out dehydrogenating propane with the same way of embodiment 2.The results are shown in table 5.
Table 5 differential responses material is at catalyzer 3%Cr/SiO
2reaction result on-1
The changing effect of differential responses material on catalyzer is different as can be seen from Table 5, and the participation of oxygen can improve conversion of propane, but easily makes product further be oxidized to carbonic acid gas, thereby causes the selectivity of low propylene.
The different CO of embodiment six and C
3h
8molar ratio is at catalyzer 3%Cr/SiO
2reaction result on-1
Except changing CO and C
3h
8outside molar ratio, react to carry out dehydrogenating propane with the same way of embodiment 2.The results are shown in table 5.
The different CO of table 6 and C
3h
8molar ratio is at 3%Cr/SiO
2reaction result on-1
Along with the increase of carbon monoxide and propane ratio, the transformation efficiency of propane and the selectivity of propylene all increase as can be seen from Table 6.
Embodiment seven different catalysts result contrast: Cr/K/SiO
2, 3%Ga/SiO
2, 3%Cr/Al
2o
3, 3%Cr/SBA-15
Except changing catalyzer, react to carry out dehydrogenating propane with the same way of embodiment 2.The results are shown in table 7.
Table 7C
3h
8reaction result with CO in different catalysts
Different catalyzer is different to the catalytic performance of dehydrogenating propane as can be seen from Table 7, adds the Cr catalyst catalytic performance after auxiliary agent to improve, and the 3%Cr/SBA-15 catalyzer with ordered structure has good catalytic performance.
Embodiment eight ethane dehydrogenations
In stainless steel reactor (internal diameter 6mm), pack 0.3g 6%Cr/SiO into
2catalyzer, catalyzer is at N
2under purging, be warming up to 600 ℃, then switch to reaction gas, it specifically consists of 20%C
3h
8, 50%C
2h
6, 50%CO
2, above-mentioned percentage composition is molar content, and feed stream air speed is 1750h
-1, reacted product enters chromatogram analysis, reacts after 6 minutes under normal pressure, and ethane conversion is 14.67%, and selectivity is 97.44%.
Claims (8)
1. a method for dehydrating alkanes alkene processed, said method comprising the steps of:
Described alkane carries out dehydrogenation reaction under the existence of carbon monoxide and dehydrogenation catalyst, generates described alkene, and wherein said alkane contains 2 to 10 carbon atoms,
The active ingredient of wherein said dehydrogenation catalyst is selected one or more in white VIB, VIIB and group VIII metal, and the carrier of described catalyzer is SiO
2, Al
2o
3or SBA-15; And
The temperature of reaction of described dehydrogenation reaction is 400-800 ℃.
2. method according to claim 1, is wherein fed to the unstripped gas that comprises described alkane and carbon monoxide in reactor.
3. method according to claim 1, wherein said alkane is any one or any several mixture in ethane, propane, butane and Trimethylmethane.
4. method according to claim 2, wherein said unstripped gas is made up of described alkane and carbon monoxide.
5. method according to claim 2, wherein said unstripped gas also contains N
2, He, Ar, O
2and CO
2in any one or any several mixture.
6. method according to claim 2, wherein, in described unstripped gas, the molar content of carbon monoxide is 0.5%-90%.
7. method according to claim 6, wherein, in described unstripped gas, the molar content of carbon monoxide is 10%-80%.
8. method according to claim 6, in wherein said unstripped gas, the molar content of carbon monoxide is 20%-80%.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010610690.4A CN102531817B (en) | 2010-12-29 | 2010-12-29 | Method for preparing olefin by dehydrogenating low-carbon alkane |
| PCT/CN2011/076410 WO2012088859A1 (en) | 2010-12-29 | 2011-06-27 | Process for preparing alkene by dehydrogenation of low carbon alkane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010610690.4A CN102531817B (en) | 2010-12-29 | 2010-12-29 | Method for preparing olefin by dehydrogenating low-carbon alkane |
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| Publication Number | Publication Date |
|---|---|
| CN102531817A CN102531817A (en) | 2012-07-04 |
| CN102531817B true CN102531817B (en) | 2014-05-14 |
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| WO (1) | WO2012088859A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104177705A (en) * | 2014-08-22 | 2014-12-03 | 华东理工大学 | Method for preparing halogen-free flame retardant polyolefin material by utilizing multi-metal composite catalyst |
| EP3224227A1 (en) * | 2014-11-26 | 2017-10-04 | SABIC Global Technologies B.V. | Concurrent reduction for improving the performance of the dehydrogenation of alkanes |
| CN105289699B (en) * | 2015-09-18 | 2018-04-20 | 宁波海越新材料有限公司 | A kind of hydrogen selective oxidation catalyst and preparation method thereof |
| EP3668827B1 (en) * | 2017-08-16 | 2021-06-23 | Shell Internationale Research Maatschappij B.V. | Ethane oxidative dehydrogenation |
| CN110614116A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Non-noble metal low-carbon alkane dehydrogenation catalyst, preparation method thereof and method for preparing low-carbon olefin by low-carbon alkane dehydrogenation |
| CN113019357A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Catalyst for preparing propylene by direct dehydrogenation of propane, preparation method and application thereof |
| CN114573413B (en) * | 2020-11-18 | 2023-06-06 | 中国科学院大连化学物理研究所 | Method for generating aromatic hydrocarbon by coupling alkane and carbon monoxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1339336A (en) * | 2000-08-23 | 2002-03-13 | 中国科学院大连化学物理研究所 | Catalyst for producing ethylene by carbon dioxide oxidation and dehydrogenation of ethane under low temperature |
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|---|---|---|---|---|
| US20050124840A1 (en) * | 2003-12-05 | 2005-06-09 | Conocophillips Company | Process for the production of olefins from alkanes with carbon monoxide co-feed and/or recycle |
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|---|---|---|---|---|
| CN1339336A (en) * | 2000-08-23 | 2002-03-13 | 中国科学院大连化学物理研究所 | Catalyst for producing ethylene by carbon dioxide oxidation and dehydrogenation of ethane under low temperature |
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| CN102531817A (en) | 2012-07-04 |
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