CN102910997B - 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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- CN102910997B CN102910997B CN201110217383.4A CN201110217383A CN102910997B CN 102910997 B CN102910997 B CN 102910997B CN 201110217383 A CN201110217383 A CN 201110217383A CN 102910997 B CN102910997 B CN 102910997B
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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
Since entering the new millennium, the mankind will sustainable growth to the demand of world's petrochemical material and petroleum chemicals, as petrochemical industry basic material alkene, will continue to increase as the demand of propylene, and traditional ordinary method can not meet the demand of rapid growth, its market occurred global in short supply.And day by day deficient along with petroleum resources, from simple dependence oil, to be raw material 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 that the low-carbon alkanes of take is waste propylene, there being the regional development of resources advantage very fast, becomes the third-largest propylene production.
Propane catalytic dehydrogenating reaction is subject to thermodynamics equilibrium limit, must under the severe condition of high temperature, low pressure, carry out.Too high temperature of reaction, makes Deposition During Propane Pyrolysis reaction and degree of depth dehydrogenation aggravation, and selectivity declines; Accelerated catalyst surface carbon deposit simultaneously, made rapid catalyst deactivation.Due to the shortening of catalyst life under lower conversion of propane and harsh reaction conditions, dehydrogenating propane (PDH) method is restricted 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.It is representative that dehydrogenating propane technology be take the Oleflex technique of Uop Inc. and the Catafin technique of U.S. Air Product company.It is catalyst based as main that Oleflex technique mainly be take Pt, and Catafin technique is mainly with Cr
2o
3/ Al
2o
3be main.
Platinum family loaded catalyst is an important class in 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 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 active metal.During above-mentioned this class catalyst activation, need first under hydrogen, to reduce, then with the mixed air of S-contained substance and hydrogen, vulcanize, to improve Activity and stabill.But along with the development of dehydrogenating technology technology, its stability can not meet the requirement of high conversion dehydrogenation novel process.CN87101513A discloses and a kind ofly before reduction, with wet method sulfuration, has introduced sulphur component, has promoted the activity of catalyzer and the method for stability.But there is the problem that cannot control as required case depth.In order to improve the economy of dehydrating alkanes technique, need do further improvement to the reduction of catalyzer and sulfidation.
Summary of the invention
For deficiency of the prior art, the invention provides a kind of method that improves catalyst stability and active manufacturing olefin by low-carbon alkane dehydrogenation, improved economic benefit.
The method of Oxidative Dehydrogenation alkene of adding the low-carbon alkanes of S-contained substance in raw material of the present invention comprises following content: dehydrogenation catalyst is 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 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 during dehydrogenation reaction in dehydrogenation feed, also can carry out dehydrogenation reaction after 2～12 hours with the dehydrogenation material that contains S-contained substance, preferably, after 4～8 hours, in raw material, no longer add S-contained substance to proceed dehydrogenation reaction.
In the inventive method, dehydrogenation feed is hydrogen and C
3～C
5the alkane mol ratio mixture that is 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 platinum family loaded catalyst, catalyzer generally take aluminum oxide or slightly acidic molecular sieve as: ZSM-5, spinel etc. is carrier, one or more in platinum, palladium, iridium, rhodium or the osmium of take in platinum family are active ingredient, and the simple substance active ingredient of take is vehicle weight 0.01%～2%.In dehydrogenation catalyst, can contain suitable auxiliary agent, as Sn, K, Na, rare earth metal etc., the content of Sn is counted 0.1%～10% of vehicle weight with simple substance simultaneously, 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 adopted pickling process load dehydrogenation active component, auxiliary agent can and/or adopt pickling process to introduce in carrier preparation process.
Conventionally the sulfuration of catalyzer is that hydrogen sulfide mixes with hydrogen and carries out sulfidizing after reduction, and its object is that the initial stage cracking performance that suppresses catalyzer is in order to long-term stability.Existing dehydrogenation catalyst, when activation, first reduces, and then carries out sulfidizing, although this activation method has advantages of dehydrogenation activity metallic reducing fully and initial action is active high, but stability is relatively poor, along with the carrying out of reaction, active decline comparatively fast.The present invention adopts ordinary method to prepare after platinum based catalyst, do not carry out conventional reduction, vulcanisation operation, directly carry out dehydrogenation, under existing, a small amount of S-contained substance carries 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 object product and the stability of long-time reaction have particularly been improved, simultaneously, reduced Star-up, saved on-stream time, improved economic benefit.
Embodiment
Dehydrogenation catalyst activation method of the present invention must process before having eliminated Pt based dehydrogenation catalyst and using reduction, vulcanisation step, directly reduce, sulfuration, dehydrogenation reaction mode.Dehydrogenation catalyst preferably be take Pt as active ingredient, take Sn as auxiliary agent, and auxiliary agent can also comprise K, Na, rare earth metal etc. simultaneously.
Dehydrogenation catalyst can adopt conventional preparation method, and as adopted 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.
It is carrier that catalyzer of the present invention be take aluminum oxide or slightly acidic molecular sieve, and dehydrogenation activity metal component is generally selected from one or more in platinum, palladium, iridium, rhodium or the osmium in 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.
The present invention be take in the dehydrogenation catalyst that aluminum oxide or slightly acidic molecular sieve be carrier, and dehydrogenation activity metal component can be evenly distributed in catalyzer, and preferably dehydrogenation activity metal component is concentrated and is distributed in catalyst outer layer, forms hud typed catalyzer.
The present invention be take in the dehydrogenation catalyst that aluminum oxide or slightly acidic molecular sieve be carrier, can contain suitable auxiliary agent, as basic metal, alkaline-earth metal, rare earth metal and sulphur etc. simultaneously.
Introduce detailed process and the condition of a kind of typical dehydrogenation method for preparing catalyst and sulfuration method of dehydrogenating below:
(1) take alumina globule or slightly acidic molecular sieve as carrier impregnation SnCl
4solution, wherein content can need to determine by using, and preferably with simple substance, counts 0.1%～5% of aluminum oxide or slightly acidic molecular sieve weight;
(2), containing after 800 ℃ of roastings of carrier of Sn, adopt supersaturation pickling process to introduce dehydrogenation active component; Can make dehydrogenation active component basic load in the skin of carrier by controlling the conditions such as the pH value of dipping solution and dipping time, keep certain thickness;
(3) in step (2), the catalyst intermediate after thermal treatment is carried out water vapour dechlorination;
(4) in the catalyzer that step (3) obtains, add the required a certain amount of alkali metal promoter of catalyzer;
(5) catalyzer that step (4) obtains directly heats up and reacts;
(6) dehydrogenation reaction is carried out under suitable condition, preferably at hydrogen, carries out under as the atmosphere of thinner.
The described dehydrogenation activity metal of step (2) is generally selected from one or more elements in platinum, palladium, iridium, rhodium or the osmium in platinum family, and content can need to determine by using, generally with simple substance, count 0.1%～2% of vehicle weight.
Water vapour dechlorination described in step (3) for to process 1～20 hour at 300～700 ℃, and the atmosphere of dechlorination is the air containing 10v%～30v% water vapor, and cl content is less than 0.15wt%.
The described reductive condition of step (5) is: high-purity hydrogen, temperature is 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 quality percentage composition.
Example 1
On Spinel carrier, flood tin tetrachloride ethanolic soln, through super-dry, 600 ℃ of roastings 4 hours, obtain the Spinel containing Sn0.3wt%.The Spinel that contains 0.3wt%Sn, at 800 ℃ of roasting 3h, is flooded to 6h by the carrier after roasting and the aqueous solution that contains Platinic chloride at 70 ℃, at 120 ℃, dry 2h, roasting 4h at 500 ℃.Dechlorination 4h in 450 ℃ of air that contain water vapor 20v%.Then at 70 ℃ with contain KNO
3aqueous solution dipping 2h, dry, roasting under same condition.In catalyzer, the charge capacity of each component is: Pt0.5wt%, Sn0.3wt%, K0.5wt%.
Appreciation condition: volume space velocity 2000h
-1, temperature of reaction is 600 ℃, dehydrogenation feed is hydrogen: the mixing raw material of Trimethylmethane mol ratio 2:1, in dehydrogenation feed, the content of thiomethyl alcohol is 10 μ mol/mol.
Evaluation result: this catalyzer is being evaluated after 40h continuously, and Trimethylmethane transformation efficiency is 48.5%, and selective isobutene is 98.6%, transformation efficiency declines 2.4 percentage points, and selectivity is substantially constant, and coke content is only 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 2000h
-1, temperature of reaction is 600 ℃, dehydrogenation feed is hydrogen: the mixture that Trimethylmethane mol ratio is 2:1.
Evaluation result: this catalyzer is being evaluated 40h continuously, Trimethylmethane transformation efficiency is 44.6%, selective isobutene is 97.1%, transformation efficiency declines 6.5 percentage points, selectivity slightly declines, and coke content is 0.76%, and the activity data of contrast can obviously be found out, compared with the conventional method, activity stability obviously improves the method for dehydrogenating of dehydrogenation catalyst of the present invention.
Example 2
According to the method that embodiment 1 is identical, prepare dehydrogenation catalyst.
Appreciation condition: volume space velocity 2000h
-1, temperature of reaction is 600 ℃, dehydrogenation feed is hydrogen: the mixture that the mol ratio of Trimethylmethane is 2:1, in dehydrogenation feed, thiomethyl alcohol content is 5 μ mol/mol.
Evaluation result: this catalyzer is being evaluated 40h continuously, and Trimethylmethane transformation efficiency is 46.8%, and selective isobutene is 98.1%, and transformation efficiency declines 2.8 percentage points, and selectivity is substantially constant, and coke content is only 0.39%, demonstrates good catalytic activity and stability.
Example 3
According to the method that embodiment 1 is identical, prepare dehydrogenation catalyst.
Appreciation condition: volume space velocity 2000h
-1, temperature of reaction is 550 ℃, dehydrogenation feed is hydrogen: the mixture that the mol ratio of Trimethylmethane is 2:1, in dehydrogenation feed, thiomethyl alcohol content is 20 μ mol/mol.
Evaluation result: this catalyzer is being evaluated after 40h continuously, and Trimethylmethane transformation efficiency is 49.4%, and selective isobutene is 98.9%, transformation efficiency declines 1.5 percentage points, selectivity is substantially constant, and coke content is only 0.20%, demonstrates good catalytic activity and stability.
Example 4
According to the method that embodiment 1 is identical, prepare dehydrogenation catalyst.
Appreciation condition: volume space velocity 2000h
-1, temperature of reaction is 500 ℃, dehydrogenation feed is hydrogen: the mixture that the mol ratio of Trimethylmethane is 2:1, in dehydrogenation feed, thiomethyl alcohol, sulfur alcohol and hydrogen sulfide mixture content are 20 μ mol/mol.
Evaluation result: this catalyzer is being evaluated after 40h continuously, and Trimethylmethane transformation efficiency is 47.8, and selective isobutene is 98.2%, and transformation efficiency declines 2.3 percentage points, and selectivity is substantially constant, and coke content is only 0.28%, demonstrates good catalytic activity and stability.
Example 5
Take aluminum oxide as carrier.0.01M tin tetrachloride ethanolic soln is impregnated on carrier, through super-dry, aging, 650 ℃ of roastings 4 hours, obtains the alumina globule containing Sn0.3wt%.
The alumina globule that contains 0.3wt%Sn, at 800 ℃ of roasting 3h, is flooded to 6h by the carrier after roasting and the aqueous solution that contains Platinic chloride at 70 ℃, at 120 ℃, dry 2h, roasting 4h at 500 ℃.Dechlorination 4h in 450 ℃ of air that contain water vapor 20v%.Then at 70 ℃ with contain KNO
3aqueous solution dipping 2h, under same condition, dry, roasting, do not reduce.In catalyzer, the charge capacity of each component is: Pt0.5wt%, Sn0.3wt%, K0.5wt%.
Appreciation condition: volume space velocity 2000h
-1, temperature of reaction is 600 ℃, dehydrogenation feed is hydrogen: the mixture that the mol ratio of Trimethylmethane is 2:1, in dehydrogenation feed, dithiocarbonic anhydride content is 10 μ mol/mol.
Evaluation result: this catalyzer is being evaluated after 40h continuously, and Trimethylmethane transformation efficiency is 46.4%, and selective isobutene is 97.6%, transformation efficiency declines 2.0 percentage points, selectivity is substantially constant, and coke content is only 0.25%, demonstrates good catalytic activity and stability.
Claims (10)
1. in a raw material, add the C of S-contained substance
3～C
5the method of manufacturing olefin by low-carbon alkane dehydrogenation, comprise following content: dehydrogenation catalyst is platinum family loaded catalyst, dehydrogenation catalyst does not carry out conventional reduction and sulfuration before use, in dehydrogenation feed, add a small amount of S-contained substance directly to carry out dehydrogenation reaction, S-contained substance is 5～100 μ mol/mol in the concentration of dehydrogenation feed, and dehydrogenation feed is hydrogen and C
3～C
5the alkane mol ratio mixture that is 1:1～6:1.
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. in accordance with the method for claim 1, it is characterized in that: 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, sulfur alcohol.
5. in accordance with the method for claim 1, it is characterized in that: dehydrogenation catalyst is platinum family loaded catalyst, catalyzer take aluminum oxide or slightly acidic molecular sieve as: ZSM-5, spinel etc. is carrier, one or more in platinum, palladium, iridium, rhodium or the osmium of take in platinum family are active ingredient, and the simple substance active ingredient of take is vehicle weight 0.01%～2%.
6. in accordance with the method for claim 5, it is characterized in that: in dehydrogenation catalyst, also contain Sn, the content of Sn is counted 0.1%～10% of vehicle weight with simple substance.
7. according to the method described in claim 5 or 6, it is characterized in that: in dehydrogenation catalyst, also contain K, 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: during dehydrogenation reaction, all in dehydrogenation feed, adding S-contained substance.
9. in accordance with the method for claim 1, it is characterized in that: with the dehydrogenation material that contains S-contained substance, carry out dehydrogenation reaction after 2～12 hours, in raw material, no longer add S-contained substance to proceed dehydrogenation reaction.
10. in accordance with the method for claim 1, it is characterized in that: with the dehydrogenation material that contains S-contained substance, carry out dehydrogenation reaction after 4～8 hours, in raw material, no longer add S-contained substance to proceed dehydrogenation reaction.
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| 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 |
| 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 |
| BR112016013610B1 (en) * | 2013-12-20 | 2021-01-26 | Dow Global Technologies Llc | method for reducing sulfur present as sulfur or sulfur compounds in a hydrocarbon feed stream |
| CN104525195B (en) * | 2014-12-30 | 2018-01-05 | 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 |
| 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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| US4353815A (en) * | 1979-06-08 | 1982-10-12 | Uop Inc. | Hydrocarbon dehydrogenation with an attenuated superactive multimetallic catalytic composite for use therein |
| CN1081435A (en) * | 1992-03-26 | 1994-02-02 | 法国石油公司 | The method of continous dehydrogenation of paraffin hydrocarbon to producing olefin hydrocarbon |
| 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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2011
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4353815A (en) * | 1979-06-08 | 1982-10-12 | Uop Inc. | Hydrocarbon dehydrogenation with an attenuated superactive multimetallic catalytic composite for use therein |
| CN1081435A (en) * | 1992-03-26 | 1994-02-02 | 法国石油公司 | The method of continous dehydrogenation of paraffin hydrocarbon to producing olefin hydrocarbon |
| 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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