CN102463152A - Method for processing dehydrogenation catalyst before application - Google Patents
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- CN102463152A CN102463152A CN2010105359012A CN201010535901A CN102463152A CN 102463152 A CN102463152 A CN 102463152A CN 2010105359012 A CN2010105359012 A CN 2010105359012A CN 201010535901 A CN201010535901 A CN 201010535901A CN 102463152 A CN102463152 A CN 102463152A
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Abstract
The invention discloses a method for processing a dehydrogenation catalyst before application, which comprises the following steps: employing a platinum group loaded type dehydrogenation catalyst, taking alumina as a carrier of the catalyst, taking one or more of platinum, palladium, iridium, rhodium or osmium in the platinum group as an active component, wherein the active component in the form of single substance accounts for 0.01%-2% of the carrier weight, carrying out sulfuration treatment on the dehydrogenation catalyst, wherein the sulfuration processing method comprises that the dehydrogenation catalyst is dipped by a vulcanizing agent-containing solution, and dried under the inert atmosphere to obtain the final dehydrogenation catalyst. The application of the dehydrogenation catalyst has the advantages of high target product selectivity and good stability.
Description
Technical field
The present invention relates to the method before a kind of processing method, particularly C3～C7 dehydrating alkanes system alkene catalyst that is used for before saturated alkane dehydrogenation catalyst carries out dehydrogenation reaction used.
Background technology
Got into since the new century; 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 propylene, and traditional conventional method can not satisfy the demand of quick growth, it is global in short supply that its market has been occurred.And deficient day by day along with petroleum resources, the production of propylene has been that raw material changes to the diversified technology path of raw material from simple dependence oil, particularly is the technology path that raw material is produced propylene with the low-carbon alkanes.In recent years, it is very fast in the area development that resources advantage is arranged with the low-carbon alkanes to be that raw material is produced the technology of propylene, becomes the third-largest propylene production.
The propane catalytic dehydrogenating reaction receives thermodynamics equilibrium limit, must under the harsh conditions of high temperature, low pressure, carry out.Too high reaction temperature makes propane cracking reaction and degree of depth dehydrogenation aggravation, and selectivity descends; Accelerate the catalyst surface carbon deposit simultaneously, make rapid catalyst deactivation.Because the shortening of catalyst life is restricted the PDH method under lower conversion of propane and the harsh reaction condition when commercial Application.Therefore, exploitation has the catalyst for preparing propylene with propane dehydrogenation of high selectivity and high stability and the key that supporting technology becomes this technology.The dehydrogenating propane technology is representative with the Oleflex technology of Uop Inc. and the Catafin technology of U.S. Air Product company.Oleflex technology is mainly catalyst based with Pt to be main, and Catafin technology is mainly with Cr
2O
3/ Al
2O
3Be main.
The platinum family loaded catalyst is in the alkane dehydrogenating catalyst important one type, and the production method of such catalyst is also open in the art.USP4914075, USP4353815, USP4420649, USP4506032, USP4595673, EP562906, EP98622 etc. have reported that to be used for propane and other dehydrogenating low-carbon alkane Pt catalyst based, have high alkane conversion and olefine selective.Although alkane conversion and the olefine selective of these catalyst under some reaction condition is high, because catalyst is prone to coking deactivation under hot conditions, cause catalytic reaction to get poor stability, the service life of catalyst is shorter.
In order to improve the anti-carbon deposition ability of catalyst; Prolong the service life of catalyst; It is the stability that carrier improves dehydrogenating propane that CN200710025372 has adopted alumina modified mesoporous molecular sieve, and CN200710133324 adds inorganic oxide binder and does the stability that carrier improves catalyst in refractory oxides.Except the moulding of the selection of carrier and catalyst very key, also be one of good measure to presulfiding of catalyst.The effect and the catalyst stability of presulfurization are closely related.Presulfurization in the main collector of dehydrogenation method for pre-sulphuration in the prior art; Catalyst is loaded into reactor, introduce vulcanizing agent then and vulcanize, CNg7101513A discloses and a kind ofly before reduction, has introduced the sulphur component with wet method sulfuration; Promoted the method for activity of such catalysts with stability; The sulphur component is inorganic sulphides such as ammonium sulfide, potassium sulfide, vulcanized sodium in this method, and experiment shows that the selectivity of sulfuration rear catalyst is not enough with stability.Before catalyst reduction, introduce vulcanizing agent, can save on-stream time, make to go into operation easylier, poisonous sulfide has been avoided using in the scene of going into operation, nor needs to install special-purpose vulcanizing deice.Therefore, the serviceability of catalyst is not influenced can further improve if introduce the sulphur component before the catalyst reduction, then significant to commercial Application.
Summary of the invention
To the deficiency of prior art, the present invention provides the processing method before a kind of dehydrogenation is used, and goes into operation on the basis of process simplifying dehydrogenation, and the serviceability, particularly purpose product selectivity and activity of such catalysts that improve catalyst are stable.
Processing method before dehydrogenation of the present invention is used comprises following process: adopt platinum family support type dehydrogenation; Catalyst generally is carrier with the aluminium oxide; With in the platinum in the platinum family, palladium, iridium, rhodium or the osmium one or more is active component, is 0.01%～2% of vehicle weight in the simple substance active component.Dehydrogenation carries out vulcanizing treatment, and the sulfurizing treatment method process is for using the solution impregnation dehydrogenation that contains vulcanizing agent, and drying obtains final dehydrogenation under inert atmosphere at last.
In the inventive method; The solution that contains vulcanizing agent is inorganic polymeric form sulfide solution; Be that elemental sulfur is dissolved in the solution such as ammonium sulfide, vulcanized sodium, potassium sulfide and forms, the addition of elemental sulfur is theoretical 20%～90%, preferred 40%～70% of the sulfur content that needs of dehydrogenation in the vulcanizing agent.
In the inventive method, with after containing the solution impregnation dehydrogenation of vulcanizing agent, baking temperature is generally 80～200 ℃, is generally drying time 1～10 hour.Solution impregnation dehydrogenation and subsequent dry run with the Containing Sulfur agent can be carried out 1～4 time, are preferably 2～3 times, and last drying is carried out under nitrogen atmosphere.
Can contain suitable auxiliary agent in the described dehydrogenation, like Sn, K, rare earth metal etc., the content of Sn is counted 0.1%～10% of vehicle weight with simple substance, and the content of K is counted 0.1%～10% of vehicle weight with element.Dehydrogenation can adopt the conventional method preparation in this area, and as adopting infusion process load dehydrogenation active component, auxiliary agent can and/or adopt infusion process to introduce in the preparing carriers process.
One of reason that life of dehydrogenation catalysts is short is a catalyst surface carbon deposit under reaction condition; For improving the stability of catalyst; Usually the sulfuration of catalyst is after reduction, to carry out vulcanizing treatment with hydrogen sulfide and hydrogen mixed gas, and the initial stage cracking performance that its purpose is to suppress catalyst is in order to long-term stability.Introducing the sulphur component through the outer pre-curing technology of device also is one of approach that improves the dehydrogenation serviceability; But the outer method for pre-sulphuration of different devices has different influences to the serviceability of catalyst, and the outer method for pre-sulphuration of existing device is limited to the serviceability that improves catalyst.Through discovering in a large number, in the outer pre-vulcanization process of device, use different vulcanizing agent or sulfidation, the performance of catalyst there is different influences.Experiment shows; Adopt the vulcanizing agent and the sulfurizing treatment method of the inventive method; Particularly adopt repeatedly the sulfuration dipping to adopt different atmosphere to carry out dried with the dipping back; Can effectively improve the selectivity and the activity stability of dehydrogenation, obtain the beyond thought technique effect of technical staff.
The specific embodiment
Processing method before dehydrogenation of the present invention is used has promoted the active and stable of Pt based dehydrogenation catalyst, and the process of sulfuration in the reactors has been eliminated the influence of hydrogen sulfide to reaction unit simultaneously.Dehydrogenation is an active component with Pt preferably, is auxiliary agent with Sn, and auxiliary agent can also comprise K, rare earth metal etc. simultaneously.
Dehydrogenation can adopt conventional preparation method, and as adopting infusion process load dehydrogenation activity metal, auxiliary agent can prepare in the process and/or the introducing of employing dipping method at alumina support.
Catalyst of the present invention is a carrier to contain the Sn aluminium oxide, 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.
The present invention is to contain in the dehydrogenation that the Sn aluminium oxide is a carrier, and Sn introduces the material that contains Sn when aluminium oxide becomes glue, process carrier then.
The present invention is to contain in the dehydrogenation that the Sn aluminium oxide is a carrier, and the dehydrogenation activity metal component can be evenly distributed in the catalyst, and preferred dehydrogenation activity metal component is concentrated and is distributed in the catalyst outer layer, forms hud typed catalyst.
The present invention can contain suitable auxiliary agent, like alkali metal, alkaline-earth metal, rare earth metal and sulphur etc. simultaneously to contain in the dehydrogenation that the Sn aluminium oxide is a carrier.
Introduce a kind of typical dehydrogenation Preparation of Catalyst below and use the detailed process and the condition of pre-treatment:
(1) preparation contains the alumina globule of Sn, and wherein content can need to confirm by use, preferably counts 0.1%～5% of alumina weight with simple substance;
(2) contain 800 ℃ of roastings of alumina globule of Sn after, adopt the supersaturation infusion process to introduce dehydrogenation active component; Can make the dehydrogenation active component basic load in the skin of carrier through the conditions such as pH value and dip time of control dipping solution, keep certain thickness;
(3) catalyst intermediate after the heat treatment is carried out the steam dechlorination in the step (2);
(4) add the required a certain amount of alkali metal promoter of catalyst in the catalyst that step (3) obtains;
(5) catalyst that obtains of step (4) vulcanizes with wet method, and vulcanizing agent is elemental sulfur and (NH
4)
2The inorganic polymeric form sulfide that S, vulcanized sodium, potassium sulfide etc. form adopts above-mentioned inorganic polymeric form sulfide solution dipping dehydrogenation, dry then getting final product.
(6) dehydrogenation reaction is carried out under suitable condition, preferably carries out under as the atmosphere of diluent at hydrogen.
The alumina support that contains Sn in the step (1) is introduced Sn when aluminium oxide becomes glue, preparation contains the alumina support of Sn then.The described Sn of containing alumina support prepares with cogelled mode;, introduces in aluminium oxide the material that contains Sn when becoming glue; The material that contains Sn is generally soluble-salt, like nitrate, chloride etc., then by the existing method moulding in this area; As dripping ball forming, extrusion modling etc., aluminium oxide becomes glue to be known by the technical staff.The preparation method of above-mentioned carrier is the method that the technical staff knew.
Wherein 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 confirm, generally count 0.1%～2% of vehicle weight with simple substance by use.
The described steam dechlorination of step (3) is to handle 1～20 hour down at 300～700 ℃, and the atmosphere of dechlorination is the air that contains 10v%～30v% water vapour, and chlorinity is less than 0.15wt%.
The described vulcanizing agent consumption of step (5) is that the total dehydrogenation activity theoretical metal of dehydrogenation needs 80%～120% of sulfur content, and wherein the addition of elemental sulfur is theoretical 20%～90%, preferred 40%～70% of the sulfur content that needs of dehydrogenation in the vulcanizing agent.Dehydrogenation is theoretical need sulfur content to be the amount that needs sulphur when contained dehydrogenation activity metal component is converted into sulfide (like platinic sulfide) on the catalyst.Divide double-steeping, adopt conventional atmosphere (air) dry down after the preferred drying for the first time, the second time, drying was carried out in inert atmosphere.
The described catalyst of step (5) adopts the mode of temperature programming to reduce.
The described dehydrogenation reaction conditions of step (7) is: 450～650 ℃ of reaction temperatures, volume space velocity 1000～3000h
-1, absolute pressure 0.1～0.3MPa, hydrogen: the ratio of alkane was at 1: 1 :～6: between 1 (mol ratio).Alkane can be the alkane of C2～C5.
Find after deliberation, in the Preparation of catalysts process, be incorporated into Sn in the alumina support with cogelled method, flood active component then, can make that Sn disperses more evenly, strengthen the active force of Sn and aluminium oxide, inhibition Sn
4+Be reduced to zeroth order Sn
0, stop the gathering of dehydrogenation activity metal in the pyroreaction environment.
Enforcement through dehydrogenation of isobutane further specifies technology of the present invention below.
Instance 1
Preparation contains the alumina support of Sn.Behind the aluminum trichloride solution and the mixing of 0.01M butter of tin solution with a certain amount of 0.98M, add a certain amount of 8% ammoniacal liquor, under 60～80 ℃, in neutralizing tank, mix; Control pH value 7.0～9.0; After filtration, washing, the acidifying, the balling-up of pressurizeing in the oil ammonia column is through super-dry, aging; 650 ℃ of roastings 4 hours, promptly get the alumina globule that contains Sn 0.3wt%.
The alumina globule carrier that will contain 0.3wt%Sn floods 6h with the carrier after the roasting and the aqueous solution that contains chloroplatinic acid down at 70 ℃, at 120 ℃ of oven dry 2h, 500 ℃ of following roasting 4h at 800 ℃ of roasting 3h.Dechlorination 4h in 450 ℃ of air that contain water vapour 20v%.Descend and contain KNO at 70 ℃ then
3Aqueous solution dipping 2h, dry, roasting under the same condition.Process catalyst P DH-FY, what account for vehicle weight consists of Pt 0.5wt%, Sn 0.3wt%, K0.5wt%.
Be that theoretical 120% the inorganic polymeric form sulfide solution of sulfur content that needs of dehydrogenation reactive metal divides the double-steeping catalyst with the vulcanizing agent consumption then; For the first time the dipping back was 120 ℃ of dryings (air atmosphere) 2 hours; For the second time dipping back 120 ℃ of dryings 4 hours under the condition that inert gas exists obtain the dehydrogenation A that presulfurization is handled.Elemental sulfur accounts for theoretical 70% of the sulfur content that needs of dehydrogenation in the inorganic polymeric form sulfide, and all the other are ammonium sulfide.
Reducing condition: adopt the mode of temperature programming to reduce, volume space velocity is 900h
-1, 480 ℃ of reduction 1 hour, hydrogen was High Purity Hydrogen.
Appreciation condition: catalyst volume 3.0ml, volume space velocity 3000h
-1, reaction pressure 0.1MPa, reaction temperature is 520 ℃, hydrogen: the mol ratio of iso-butane is 1: 1.
Evaluation result: this catalyst is after estimating 60h continuously, and the iso-butane conversion ratio is 34.2%, and selective isobutene is 98.0%; Conversion ratio decline (than initial reaction stage) 1.2 percentage points; Selectivity is constant basically, and coke content is merely 0.13%, and yield maintains more than 34%; Demonstrate good catalytic activity and stability (percentage is mass percent, down together).
Comparative example
Process catalyst P DH-FY according to embodiment 1 identical method.Vulcanizing agent is merely ammonium sulfide, dipping twice, and each dipping back was 120 ℃ of dryings 4 hours.
Reducing condition: adopt the mode of temperature programming to reduce, volume space velocity is 900h
-1, 480 ℃ of reduction 1 hour, hydrogen was High Purity Hydrogen.
Appreciation condition: catalyst volume 3.0ml, volume space velocity 3000h
-1, reaction pressure 0.1MPa, reaction temperature is 520 ℃, hydrogen: the mol ratio of iso-butane is 1: 1.
Evaluation result: this catalyst is after continuously estimating 60h, and the iso-butane conversion ratio is 30.5%, and selective isobutene is 96.1%, and conversion ratio descends 5.8 percentage points, and the selectivity of isobutene also has obvious decline, and coke content is 0.45%.
Instance 2
Process catalyst P DH-FY according to embodiment 1 identical method.The vulcanizing agent consumption is theoretical 105% of the sulfur content that needs of dehydrogenation reactive metal; Flood twice; For the first time the dipping back is 120 ℃ of dryings 2 hours, and dipping back 120 ℃ of dryings 4 hours under the condition that inert gas exists obtain the dehydrogenation B that presulfurization is handled for the second time.Elemental sulfur accounts for theoretical 40% of the sulfur content that needs of dehydrogenation in the inorganic polymeric form sulfide, and all the other are ammonium sulfide.
Reducing condition: adopt the mode of temperature programming to reduce, volume space velocity is 900h
-1, 480 ℃ of reduction 1 hour, hydrogen was High Purity Hydrogen.
Appreciation condition: catalyst volume 3.0ml, volume space velocity 3000h
-1, reaction pressure 0.1MPa, reaction temperature is 520 ℃, hydrogen: the mol ratio of iso-butane is 1: 1.
Evaluation result: this catalyst is being estimated 60h continuously, and the iso-butane conversion ratio is 33.8%, and selective isobutene is 97.9%, and conversion ratio descends 2.0 percentage points, and selectivity is constant basically, and coke content is merely 0.19%, demonstrates good catalytic activity and stability.
Instance 3
Process catalyst P DH-FY according to embodiment 1 identical method.The vulcanizing agent consumption is theoretical 95% of the sulfur content that needs of dehydrogenation reactive metal; Flood twice; For the first time the dipping back is 120 ℃ of dryings 2 hours, and dipping back 120 ℃ of dryings 4 hours under the condition that inert gas exists obtain the dehydrogenation C that presulfurization is handled for the second time.Elemental sulfur accounts for theoretical 40% of the sulfur content that needs of dehydrogenation in the inorganic polymeric form sulfide, and all the other are vulcanized sodium.
Reducing condition: adopt the mode of temperature programming to reduce, volume space velocity is 900h
-1, 480 ℃ of reduction 1 hour, hydrogen was High Purity Hydrogen.
Appreciation condition: catalyst volume 3.0ml, volume space velocity 3000h
-1, reaction pressure 0.1MPa, reaction temperature is 520 ℃, hydrogen: the mol ratio of iso-butane is 1: 1.
Evaluation result: this catalyst is after estimating 60h continuously, and the iso-butane conversion ratio is 33.7%, and selective isobutene is 97.7%, and conversion ratio descends 2.2 percentage points, and selectivity is constant basically, and coke content is 0.21%, demonstrates good catalytic activity and stability.
Table one dehydrogenation reactivity worth
| Catalyst | Initial stage conversion ratio % | Initial stage selectivity % | Latter stage conversion ratio % | Latter stage selectivity % |
| Comparative example | 36.3 | 97.2 | 30.5 | 96.1 |
| A | 35.4 | 98.3 | 34.2 | 98.0 |
| B | 35.8 | 97.9 | 33.8 | 97.9 |
| C | 35.9 | 97.8 | 33.7 | 97.7 |
Initial stage: 4 hours reaction time
Latter stage: 60 hours reaction time
Evaluation result by catalyst can find out that the dehydrogenation that the inventive method is handled has the selectivity and the stability of obvious raising.
Claims (7)
1. the processing method before a dehydrogenation is used; Comprise following process: adopt platinum family support type dehydrogenation; Catalyst is carrier with the aluminium oxide; With in the platinum in the platinum family, palladium, iridium, rhodium or the osmium one or more is active component, is 0.01%～2% of vehicle weight in the simple substance active component, and dehydrogenation carries out vulcanizing treatment; The sulfurizing treatment method process is for using the solution impregnation dehydrogenation that contains vulcanizing agent, and drying obtains final dehydrogenation under inert atmosphere at last.
2. according to the described method of claim 1; It is characterized in that: the solution that contains vulcanizing agent is inorganic polymeric form sulfide solution; Elemental sulfur is dissolved in ammonium sulfide, vulcanized sodium or the potassium sulfide solution and forms, and the addition of elemental sulfur is theoretical 20%～90% of the sulfur content that needs of dehydrogenation in the vulcanizing agent.
3. according to the described method of claim 2, it is characterized in that: the addition of elemental sulfur is theoretical 40%～70% of the sulfur content that needs of dehydrogenation in the vulcanizing agent.
4. according to the described method of claim 1, it is characterized in that: with after containing the solution impregnation dehydrogenation of vulcanizing agent, baking temperature is 80～200 ℃, is generally drying time 1～10 hour.
5. according to the described method of claim 1, it is characterized in that: solution impregnation dehydrogenation and subsequent dry run with the Containing Sulfur agent are carried out 1～4 time, and last drying is carried out under nitrogen atmosphere.
6. according to the described method of claim 1, it is characterized in that: contain auxiliary agent in the dehydrogenation, auxiliary agent is Sn, K or rare earth metal.
7. according to the described method of claim 6, it is characterized in that: the content of Sn is counted 0.1%～10% of vehicle weight with simple substance in the dehydrogenation, and the content of K is counted 0.1%～10% of vehicle weight with element.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588002A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司大连石油化工研究院 | Sulfuration mode palladium/alumina catalyst, and preparation method and application thereof |
| CN112237929A (en) * | 2019-07-19 | 2021-01-19 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by dehydrogenating light alkane and method for preparing olefin |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1256171A (en) * | 1998-10-12 | 2000-06-14 | 欧洲催化剂加工公司 | Off-site presulphidation in the presence of hydrocarbon molecular |
| JP2001162165A (en) * | 1999-12-09 | 2001-06-19 | Sumitomo Metal Mining Co Ltd | Dehydrogenation catalyst for paraffin and method of dehydrogenating paraffin by using the catalyst |
| CN1861257A (en) * | 2005-05-12 | 2006-11-15 | 中国石油化工股份有限公司 | Treatment method before application of hydrogenation catalyst |
| CN101125298A (en) * | 2007-07-26 | 2008-02-20 | 南京大学 | Catalyst propane using aluminium oxide modified mesonore molecular sieve as carrier for dehydrogenation producing propylene |
-
2010
- 2010-11-04 CN CN201010535901.2A patent/CN102463152B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1256171A (en) * | 1998-10-12 | 2000-06-14 | 欧洲催化剂加工公司 | Off-site presulphidation in the presence of hydrocarbon molecular |
| JP2001162165A (en) * | 1999-12-09 | 2001-06-19 | Sumitomo Metal Mining Co Ltd | Dehydrogenation catalyst for paraffin and method of dehydrogenating paraffin by using the catalyst |
| CN1861257A (en) * | 2005-05-12 | 2006-11-15 | 中国石油化工股份有限公司 | Treatment method before application of hydrogenation catalyst |
| CN101125298A (en) * | 2007-07-26 | 2008-02-20 | 南京大学 | Catalyst propane using aluminium oxide modified mesonore molecular sieve as carrier for dehydrogenation producing propylene |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104588002A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司大连石油化工研究院 | Sulfuration mode palladium/alumina catalyst, and preparation method and application thereof |
| CN112237929A (en) * | 2019-07-19 | 2021-01-19 | 中国石油化工股份有限公司 | Catalyst for preparing olefin by dehydrogenating light alkane and method for preparing olefin |
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