CN102910997A - Method for preparing olefins by using dehydrogenation of light alkanes with sulfur-containing substances added in raw materials - Google Patents
Method for preparing olefins by using dehydrogenation of light alkanes with sulfur-containing substances added in raw materials Download PDFInfo
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Abstract
The present invention discloses a method for preparing olefins by using dehydrogenation of light alkanes with sulfur-containing substances added in raw materials, comprising: the dehydrogenation catalyst, which is a platinum group metal-supported catalyst, is not subjected to a reduction and sulfurization before use; and a small amount of sulfur-containing materials are added in the dehydrogenation raw materials for a dehydrogenation reaction directly, wherein the concentration of the sulfur-containing materials in the dehydrogenation raw materials is 5-100 [mu]mol/mol. Compared with the prior art, the method of the present invention improves the stability of the dehydrogenation catalyst, and can effectively prolong the service life of the dehydrogenation catalyst and reduce the carbon deposition rate of the catalyst, thereby improving the economic benefits of preparing corresponding olefins by using light hydrocarbon dehydrogenation.
Description
Technical field
The present invention relates to the method for manufacturing olefin by low-carbon alkane dehydrogenation, particularly the processing method of the corresponding alkene of C3 ~ C5 dehydrating alkanes system.
Background technology
Entered since the new millennium, human demand to world's petrochemical material and petroleum chemicals will sustainable growth, to continue to increase as the demand of petrochemical industry basic material alkene such as propylene, and traditional ordinary method can not satisfy the demand of rapid growth, it is global in short supply that its market has been occurred.And day by day deficient along with petroleum resources, to be raw material from simple dependence oil change to the technological line of diversification of feedstock in the production of propylene, particularly take the technological line of low-carbon alkanes as waste alkene.In recent years, the technology take low-carbon alkanes as the waste propylene is very fast at the regional development that resources advantage is arranged, and becomes the third-largest propylene production.
The propane catalytic dehydrogenating reaction is subjected to thermodynamics equilibrium limit, must carry out under the severe condition of high temperature, low pressure.Too high temperature of reaction makes Deposition During Propane Pyrolysis reaction and degree of depth dehydrogenation aggravation, and selectivity descends; Accelerated simultaneously the catalyst surface carbon deposit, made rapid catalyst deactivation.Because the shortening of catalyst life is restricted dehydrogenating propane (PDH) method under lower conversion of propane and the harsh reaction conditions when industrial application.Therefore, exploitation has the catalyst for preparing propylene with propane dehydrogenation of highly selective and high stability and the key that supporting technique becomes this technology.The dehydrogenating propane technology is take the Catafin technique of the Oleflex technique of Uop Inc. and U.S. Air Product company as representative.Oleflex technique is mainly catalyst based as main take Pt, and Catafin technique is mainly with Cr
2O
3/ Al
2O
3Be main.
The platinum family loaded catalyst is an important class in the alkane dehydrogenating catalyst, and the production method of such catalyzer is also open in the art.USP4914075, USP4353815, USP4420649, USP4506032, USP4595673, EP562906, EP98622 etc. have reported for propane and other dehydrogenating low-carbon alkane Pt catalyst based, have high alkane conversion and olefine selective.CN200710133324.2 discloses a kind of method that improves the catalyst for preparing propylene with propane dehydrogenation reactive behavior.USP3897368 and CN87108352 disclose a kind of method of producing hud typed catalyzer, and Pt optionally concentrates and is deposited on the outside surface of support of the catalyst, and the inner Pt content of support of the catalyst is lower, can improve the utilization ratio of reactive metal.During above-mentioned this class catalyst activation, need to reduce under hydrogen first, then the mixed air with S-contained substance and hydrogen vulcanizes, to improve Activity and stabill.But along with the development of dehydrogenating technology technology, its stability can not satisfy the requirement of high conversion dehydrogenation novel process.CN87101513A discloses and has a kind ofly introduced the sulphur component with wet method sulfuration before reduction, has promoted the activity of catalyzer and the method for stability.But there is the problem that to control as required case depth.In order to improve the economy of dehydrating alkanes technique, need reduction and the sulfidation of catalyzer are done further improvement.
Summary of the invention
For deficiency of the prior art, the invention provides a kind of method that improves the manufacturing olefin by low-carbon alkane dehydrogenation of catalyst stability and activity, improved economic benefit.
The method of the Oxidative Dehydrogenation alkene of the low-carbon alkanes of interpolation S-contained substance comprises following content in the raw material of the present invention: dehydrogenation catalyst is the platinum family loaded catalyst, and dehydrogenation catalyst does not reduce before use, vulcanizes.In dehydrogenation feed, add a small amount of S-contained substance, the lower boiling vulcanizing agents such as preferred dithiocarbonic anhydride, hydrogen sulfide, thiomethyl alcohol, sulfur alcohol, can be that dehydrogenation reaction is directly carried out in one or more mixing in the S-contained substance, S-contained substance is 5 ~ 100 μ mol/mol in the concentration of dehydrogenation feed, is preferably 10 ~ 50 μ mol/mol.
In the inventive method, S-contained substance can all added in dehydrogenation feed during the dehydrogenation reaction, also can carry out dehydrogenation reaction after 2 ~ 12 hours with the dehydrogenation material that contains S-contained substance, after preferred 4 ~ 8 hours, no longer add S-contained substance in the raw material and proceed dehydrogenation reaction.
In the inventive method, dehydrogenation feed is C
3~ C
5Alkane and hydrogen mol ratio be the mixture of 1:1 ~ 6:1.The condition of dehydrogenation reaction is: 400 ~ 650 ℃ of temperature of reaction, volume space velocity 500 ~ 5000h
-1, absolute pressure 0.01 ~ 0.5MPa.
Dehydrogenation catalyst of the present invention is the platinum family loaded catalyst, catalyzer generally take aluminum oxide or slightly acidic molecular sieve as: ZSM-5, spinel etc. are as carrier, in platinum, palladium, iridium, rhodium or the osmium in the platinum family one or more are as active ingredient, take the simple substance active ingredient as vehicle weight 0.01% ~ 2%.Simultaneously can contain suitable auxiliary agent in the dehydrogenation catalyst, such as Sn, K, Na, rare earth metal etc., the content of Sn is counted 0.1% ~ 10% of vehicle weight with simple substance, and the content of K, Na, rare earth metal is counted 0.1% ~ 10% of vehicle weight with element.Dehydrogenation catalyst can adopt the method preparation of this area routine, and as adopting pickling process load dehydrogenation active component, auxiliary agent can and/or adopt pickling process to introduce in the carrier preparation process.
Usually the sulfuration of catalyzer is to mix with hydrogen at the later hydrogen sulfide of reduction to carry out sulfidizing, and its purpose is to suppress the initial stage cracking performance of catalyzer in order to long-term stability.Existing dehydrogenation catalyst at first reduces when activation, then carries out sulfidizing, although this activation method has the dehydrogenation activity metallic reducing fully and the active high advantage of initial action, but stability is relatively relatively poor, along with the carrying out of reaction, and active decline comparatively fast.After the present invention adopts ordinary method to prepare platinum based catalyst, do not carry out conventional reduction, vulcanisation operation, directly carry out dehydrogenation, namely in the presence of a small amount of S-contained substance, carry out the dehydrogenation reaction of alkane, when carrying out dehydrogenation reaction, reduce and vulcanize, the too fast phenomenon of catalyst activity inactivation not high or that case depth causes not of having avoided the sulfuration of dehydrogenation activity metal depth to cause, and then improved the use properties of catalyzer, the selectivity of purpose product and the stability of long-time reaction have particularly been improved, simultaneously, reduce Star-up, saved on-stream time, improved economic benefit.
Embodiment
Reduction, vulcanisation step that must process before dehydrogenation catalyst activation method of the present invention has been eliminated the Pt based dehydrogenation catalyst and used be directly reduced, sulfuration, dehydrogenation reaction mode.Dehydrogenation catalyst is preferably take Pt as active ingredient, and take Sn as auxiliary agent, auxiliary agent can also comprise K, Na, rare earth metal etc. simultaneously.
Dehydrogenation catalyst can adopt conventional preparation method, and as adopting pickling process load dehydrogenation activity metal, auxiliary agent can and/or adopt dipping method to introduce in aluminum oxide or slightly acidic molecular sieve carrier preparation process.
Catalyzer of the present invention is take aluminum oxide or slightly acidic molecular sieve as carrier, and the dehydrogenation activity metal component generally is selected from one or more in platinum, palladium, iridium, rhodium or the osmium in the platinum family, and consumption is counted 0.01% ~ 2% of vehicle weight with simple substance.The content of Sn is counted 0.1% ~ 10% of vehicle weight with simple substance.
In the dehydrogenation catalyst of carrier, the dehydrogenation activity metal component can be evenly distributed in the catalyzer take aluminum oxide or slightly acidic molecular sieve in the present invention, and preferred dehydrogenation activity metal component is concentrated and is distributed in the catalyst outer layer, forms hud typed catalyzer.
The present invention in the dehydrogenation catalyst of carrier, can contain suitable auxiliary agent, such as basic metal, alkaline-earth metal, rare earth metal and sulphur etc. take aluminum oxide or slightly acidic molecular sieve simultaneously.
The below introduces detailed process and the condition of a kind of typical dehydrogenation method for preparing catalyst and sulfuration method of dehydrogenating:
(1) take alumina globule or slightly acidic molecular sieve as carrier impregnation SnCl
4Solution, wherein content can need to determine by using, and preferably counts 0.1% ~ 5% of aluminum oxide or slightly acidic molecular sieve weight with simple substance;
(2) contain 800 ℃ of roastings of carrier of Sn after, adopt the supersaturation pickling process to introduce dehydrogenation active component; Can make the dehydrogenation active component basic load in the skin of carrier by conditions such as the control pH value of dipping solution and dipping time, keep certain thickness;
(3) catalyst intermediate after the thermal treatment is carried out the water vapour dechlorination in the step (2);
(4) add the required a certain amount of alkali metal promoter of catalyzer in the catalyzer that step (3) obtains;
(5) catalyzer that obtains of step (4) directly heats up and reacts;
(6) dehydrogenation reaction is carried out under suitable condition, preferably carries out under as the atmosphere of thinner at hydrogen.
The described dehydrogenation activity metal of step (2) generally is selected from one or more elements in platinum, palladium, iridium, rhodium or the osmium in the platinum family, and content can need to determine by using, generally count 0.1% ~ 2% of vehicle weight with simple substance.
The described water vapour dechlorination of step (3) is that the atmosphere of dechlorination is for containing the air of 10v% ~ 30v% water vapor 300 ~ 700 ℃ of lower processing 1 ~ 20 hour, and cl content is less than 0.15wt%.
The described reductive condition of step (5) is: high-purity hydrogen, temperature are 400 ~ 600 ℃, 0.5 ~ 5 hour time.
The described dehydrogenation reaction conditions of step (6) is: 400 ~ 650 ℃ of temperature of reaction, volume space velocity 500 ~ 5000h
-1, absolute pressure 0.01 ~ 0.5MPa, hydrogen: the mol ratio of alkane is between 1:1 ~ 6:1.
Enforcement below by dehydrogenation of isobutane is described further technology of the present invention.The percentage composition that does not indicate benchmark is the quality percentage composition.
Example 1
At Spinel carrier dipping tin tetrachloride ethanolic soln, through super-dry, 600 ℃ of roastings 4 hours, namely get the Spinel that contains Sn 0.3wt%.To contain the Spinel of 0.3wt% Sn at 800 ℃ of roasting 3h, with the carrier after the roasting and the aqueous solution that contains Platinic chloride dipping 6h under 70 ℃, at 120 ℃ of oven dry 2h, 500 ℃ of lower roasting 4h.Dechlorination 4h in 450 ℃ of air that contain water vapor 20v%.Then descend and contain KNO at 70 ℃
3Aqueous solution dipping 2h, dry, roasting under the same condition.The charge capacity of each component is in the catalyzer: Pt 0.5wt%, Sn 0.3wt%, K0.5wt%.
Appreciation condition: volume space velocity 2000 h
-1, temperature of reaction is 600 ℃, dehydrogenation feed is hydrogen: the mixing raw material of Trimethylmethane mol ratio 2:1, the content of thiomethyl alcohol is 10 μ mol/mol in the dehydrogenation feed.
Evaluation result: this catalyzer is after estimating 40h continuously, and the Trimethylmethane transformation efficiency is 48.5%, and selective isobutene is 98.6%, transformation efficiency descends 2.4 percentage points, and selectivity is substantially constant, and coke content only is 0.25%, yield maintains more than 48%, demonstrates good catalytic activity and stability.
Comparative example
The preparation of catalyzer is with example 1, and different is to obtain catalyzer through 450 ℃ of hydrogen reducings, then activates.
Activation condition: the volume space velocity of the mixed gas of hydrogen sulfide, hydrogen and nitrogen is 900h
-1, molar ratio is 1:9:5,450 ℃ of temperature, soak time 1h.
Appreciation condition: volume space velocity 2000 h
-1, temperature of reaction is 600 ℃, dehydrogenation feed is hydrogen: the Trimethylmethane mol ratio is the mixture of 2:1.
Evaluation result: this catalyzer is being estimated 40h continuously, the Trimethylmethane transformation efficiency is 44.6%, selective isobutene is 97.1%, transformation efficiency descends 6.5 percentage points, selectivity slightly descends, and coke content is 0.76%, and the activity data of contrast can obviously be found out, the method of dehydrogenating of dehydrogenation catalyst of the present invention is compared with existing method, and activity stability obviously improves.
Example 2
Prepare dehydrogenation catalyst according to embodiment 1 identical method.
Appreciation condition: volume space velocity 2000 h
-1, temperature of reaction is 600 ℃, and dehydrogenation feed is hydrogen: the mol ratio of Trimethylmethane is the mixture of 2:1, and thiomethyl alcohol content is 5 μ mol/mol in the dehydrogenation feed.
Evaluation result: this catalyzer is being estimated 40h continuously, and the Trimethylmethane transformation efficiency is 46.8%, and selective isobutene is 98.1%, and transformation efficiency descends 2.8 percentage points, and selectivity is substantially constant, and coke content is 0.39% only, demonstrates good catalytic activity and stability.
Example 3
Prepare dehydrogenation catalyst according to embodiment 1 identical method.
Appreciation condition: volume space velocity 2000 h
-1, temperature of reaction is 550 ℃, and dehydrogenation feed is hydrogen: the mol ratio of Trimethylmethane is the mixture of 2:1, and thiomethyl alcohol content is 20 μ mol/mol in the dehydrogenation feed.
Evaluation result: this catalyzer is after estimating 40h continuously, and the Trimethylmethane transformation efficiency is 49.4%, and selective isobutene is 98.9%, and transformation efficiency descends 1.5 percentage points, and selectivity is substantially constant, and coke content is 0.20% only, demonstrates good catalytic activity and stability.
Example 4
Prepare dehydrogenation catalyst according to embodiment 1 identical method.
Appreciation condition: volume space velocity 2000 h
-1, temperature of reaction is 500 ℃, and dehydrogenation feed is hydrogen: the mol ratio of Trimethylmethane is the mixture of 2:1, and thiomethyl alcohol, sulfur alcohol and hydrogen sulfide mixture content are 20 μ mol/mol in the dehydrogenation feed.
Evaluation result: this catalyzer is after estimating 40h continuously, and the Trimethylmethane transformation efficiency is 47.8, and selective isobutene is 98.2%, and transformation efficiency descends 2.3 percentage points, and selectivity is substantially constant, and coke content is 0.28% only, demonstrates good catalytic activity and stability.
Example 5
Take aluminum oxide as carrier.0.01M tin tetrachloride ethanolic soln is impregnated on the carrier, through super-dry, aging, 650 ℃ of roastings 4 hours, namely gets the alumina globule that contains Sn 0.3wt%.
To contain the alumina globule of 0.3wt% Sn at 800 ℃ of roasting 3h, with the carrier after the roasting and the aqueous solution that contains Platinic chloride dipping 6h under 70 ℃, at 120 ℃ of oven dry 2h, 500 ℃ of lower roasting 4h.Dechlorination 4h in 450 ℃ of air that contain water vapor 20v%.Then descend and contain KNO at 70 ℃
3Aqueous solution dipping 2h, dry, roasting are not reduced under the same condition.The charge capacity of each component is in the catalyzer: Pt 0.5wt%, Sn 0.3wt%, K0.5wt%.
Appreciation condition: volume space velocity 2000 h
-1, temperature of reaction is 600 ℃, and dehydrogenation feed is hydrogen: the mol ratio of Trimethylmethane is the mixture of 2:1, and dithiocarbonic anhydride content is 10 μ mol/mol in the dehydrogenation feed.
Evaluation result: this catalyzer is after estimating 40h continuously, and the Trimethylmethane transformation efficiency is 46.4%, and selective isobutene is 97.6%, and transformation efficiency descends 2.0 percentage points, and selectivity is substantially constant, and coke content is 0.25% only, demonstrates good catalytic activity and stability.
Claims (10)
1. add the method for the manufacturing olefin by low-carbon alkane dehydrogenation of S-contained substance in the raw material, comprise following content: dehydrogenation catalyst is the platinum family loaded catalyst, dehydrogenation catalyst does not carry out conventional reduction and sulfuration before use, add a small amount of S-contained substance and directly carry out dehydrogenation reaction in dehydrogenation feed, S-contained substance is 5 ~ 100 μ mol/mol in the concentration of dehydrogenation feed.
2. it is characterized in that in accordance with the method for claim 1: S-contained substance is 10 ~ 50 μ mol/mol in the concentration of dehydrogenation feed.
3. it is characterized in that in accordance with the method for claim 1: dehydrogenation feed is C
3~ C
5Alkane and hydrogen mol ratio be the mixture of 1:1 ~ 6:1, the temperature of reaction of dehydrogenation reaction is 400 ~ 650 ℃, volume space velocity is 500 ~ 5000h
-1, absolute pressure is 0.01 ~ 0.5MPa.
4. it is characterized in that in accordance with the method for claim 1: S-contained substance is selected from one or more in dithiocarbonic anhydride, hydrogen sulfide, thiomethyl alcohol, the sulfur alcohol.
5. in accordance with the method for claim 1, it is characterized in that: dehydrogenation catalyst is the platinum family loaded catalyst, catalyzer take aluminum oxide or slightly acidic molecular sieve as: ZSM-5, spinel etc. are as carrier, in platinum, palladium, iridium, rhodium or the osmium in the platinum family one or more are as active ingredient, take the simple substance active ingredient as vehicle weight 0.01% ~ 2%.
6. in accordance with the method for claim 5, it is characterized in that: also contain Sn in the dehydrogenation catalyst, the content of Sn is counted 0.1% ~ 10% of vehicle weight with simple substance.
7. according to claim 5 or 6 described methods, it is characterized in that: also contain K in the dehydrogenation catalyst, the content of K is counted 0.1% ~ 10% of vehicle weight with element.
8. it is characterized in that in accordance with the method for claim 1: all in dehydrogenation feed, adding S-contained substance during the dehydrogenation reaction.
9. in accordance with the method for claim 1, it is characterized in that: carry out dehydrogenation reaction after 2 ~ 12 hours with the dehydrogenation material that contains S-contained substance, no longer add S-contained substance in the raw material and proceed dehydrogenation reaction.
10. in accordance with the method for claim 1, it is characterized in that: carry out dehydrogenation reaction after 4 ~ 8 hours with the dehydrogenation material that contains S-contained substance, no longer add S-contained substance in the raw material and proceed dehydrogenation reaction.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104107712A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Mixed C3/C4 alkane dehydrogenation catalyst and preparation method thereof |
| CN104525195A (en) * | 2014-12-30 | 2015-04-22 | 中国石油天然气股份有限公司 | Catalyst for preparing isobutene through isobutane dehydrogenation and preparation method and application thereof |
| CN104588008A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司 | Saturated alkane dehydrogenation catalyst and preparation method thereof |
| CN105233818A (en) * | 2015-11-05 | 2016-01-13 | 中国海洋石油总公司 | Method for improving stability of low-carbon alkane dehydrogenation catalyst through acidity and alkalinity adjustment |
| CN105814174A (en) * | 2013-12-20 | 2016-07-27 | 陶氏环球技术有限责任公司 | Propane dehydrogenation sulfur management |
| WO2019123121A1 (en) * | 2017-12-18 | 2019-06-27 | Sabic Global Technologies B.V. | Sulfur injection in fluidization bed dehydrogenation on chromium catalyst for dehydrogenation process improvement and process scheme optimization |
| CN110614120A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Non-noble metal isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation |
| CN115138360A (en) * | 2022-09-05 | 2022-10-04 | 烟台百川汇通科技有限公司 | Catalyst for preparing propylene by propane dehydrogenation under sulfur-containing condition, preparation method and application thereof |
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| CN101898138A (en) * | 2009-05-25 | 2010-12-01 | 中国石油化工股份有限公司 | Method for preparing vulcanized dehydrogenation catalyst |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104107712A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Mixed C3/C4 alkane dehydrogenation catalyst and preparation method thereof |
| CN104107712B (en) * | 2013-04-16 | 2018-02-13 | 中国石油化工股份有限公司 | Mix C3/C4 alkane dehydrogenating catalysts and preparation method thereof |
| CN104588008A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司 | Saturated alkane dehydrogenation catalyst and preparation method thereof |
| CN104588008B (en) * | 2013-11-01 | 2017-03-01 | 中国石油化工股份有限公司 | Saturated alkane dehydrogenation catalyst and preparation method thereof |
| CN105814174A (en) * | 2013-12-20 | 2016-07-27 | 陶氏环球技术有限责任公司 | Propane dehydrogenation sulfur management |
| CN104525195A (en) * | 2014-12-30 | 2015-04-22 | 中国石油天然气股份有限公司 | Catalyst for preparing isobutene through isobutane dehydrogenation and preparation method and application thereof |
| CN105233818A (en) * | 2015-11-05 | 2016-01-13 | 中国海洋石油总公司 | Method for improving stability of low-carbon alkane dehydrogenation catalyst through acidity and alkalinity adjustment |
| WO2019123121A1 (en) * | 2017-12-18 | 2019-06-27 | Sabic Global Technologies B.V. | Sulfur injection in fluidization bed dehydrogenation on chromium catalyst for dehydrogenation process improvement and process scheme optimization |
| US11358917B2 (en) | 2017-12-18 | 2022-06-14 | Sabic Global Technologies B.V. | Sulfur injection in fluidization bed dehydrogenation on chromium catalyst for dehydrogenation process improvement and process scheme optimization |
| CN110614120A (en) * | 2018-06-20 | 2019-12-27 | 中国石油化工股份有限公司 | Non-noble metal isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation |
| CN115138360A (en) * | 2022-09-05 | 2022-10-04 | 烟台百川汇通科技有限公司 | Catalyst for preparing propylene by propane dehydrogenation under sulfur-containing condition, preparation method and application thereof |
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