CN1768936A - Method for preparing platinum sulfide dehydrogenation catalyst - Google Patents

Method for preparing platinum sulfide dehydrogenation catalyst Download PDF

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Publication number
CN1768936A
CN1768936A CN 200410086385 CN200410086385A CN1768936A CN 1768936 A CN1768936 A CN 1768936A CN 200410086385 CN200410086385 CN 200410086385 CN 200410086385 A CN200410086385 A CN 200410086385A CN 1768936 A CN1768936 A CN 1768936A
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catalyst
preparation
platinum
reduction
carrier
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CN1327955C (en
Inventor
吕顺丰
吴秀香
张秀英
秦燕璜
周维先
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention discloses a method for preparing the sulfonated platinum de-oxidation catalyst. The method comprises: preparing platinum Pt catalyst, reduction sulfonated, and blowing cooling, to attain the PtSx catalyst whose platinum content is 0.01-0.5% (wt) and the mol rate x of S/Pt is 0.1-50 With said inventive method, the sulfonated platinum de-oxidation catalyst can be directly prepared, and the sulfidization can be directly processed on the Pt/Al2O3 catalyst used in present producing device, to improve the service life, de-oxidation activity and antitoxin of de-oxidation catalyst.

Description

The preparation method of platinum sulfide dehydrogenation catalyst
Technical field
The present invention relates to a kind of platinum sulfide (PtS that is used to remove micro amount of oxygen in the various sulfurous gas, particularly synthesis gas x) preparation method of dehydrogenation catalyst.
Background technology
The micro amount of oxygen that contains in the unstrpped gas can make the active decline of synthetic reaction expensive catalysts even lose activity, for example, and at material synthesis gas (CO and the H of the synthetic preparation of low pressure carbonyl fourth octanol 2Mist) in, the existence of micro amount of oxygen can reduce the Noble Metal Rhodium activity of such catalysts.Use precious metals pt or Pd/Al 2O 3Catalyst utilizes H 2-O 2Water generation reaction can be removed micro amount of oxygen.But the Pd catalyst is very easily because of ubiquitous Determination of Trace Sulfur poisoning and deactivation in the unstrpped gas; The CO disproportionated reaction can take place and tie charcoal, thereby reduce the service life and the deoxy activity of catalyst in the Pt catalyst in the CO of high concentration gas.
CN85102710A discloses a kind of platinum, Pd/TiO 2 deoxygenationcatalyst, and this catalyst is used for general hydrogen, ultra-pure hydrogen, nitrogen are produced in the nitrogen deoxidation, and catalytic activity is good.CN1175478 discloses a kind of high strength, highly heat-resistant catalyst, and adopting titanium dioxide to add aluminium oxide is carrier, and active component is palladium and/or platinum, and this catalyst is used for the quantitative deoxidization by adding hydrogen reaction of thick hydrogen deoxygenation, nitrogen and inert gas, anti-H 2S, SO 2Poisoning capability strong; The embodiment of this patent is for being the bicomponent catalyst of active component with palladium and platinum, and bullion content is higher in the catalyst, is 0.5%.
In sum, join the hydrogen dehydrogenation catalyst in the prior art and exist impurity poisoning capability such as resisting sulfide and CO poor, active low, shortcomings such as life-span weak point.Chinese patent application 200310121870.6 (it is for referencial use that the full content of this application is all introduced the present invention) discloses a kind of PtS xDehydrogenation catalyst is by carrier and the active component platinum sulfide PtS that loads on the carrier xForm, wherein in vehicle weight, platinum content is 0.01～0.5% (wt); S/Pt mol ratio x is 0.1～50.This catalyst has overcome the problem of sulfur poisoning and CO disproportionation knot carbon, can be used for the removing of synthesis gas micro amount of oxygen of sulfur-bearing.This catalyst adopts spraying or dipping method with PtS xLoad to Al 2O 3Above.
Summary of the invention
The purpose of this invention is to provide a kind of new PtS xThe preparation method of dehydrogenation catalyst.
The invention discloses a kind of preparation PtS xThe new method of dehydrogenation catalyst uses the method for the present invention can be by the Pt/Al to using in the process units 2O 3Deoxidier carries out vulcanizing treatment, obtains sulfur-tolerance deoxidation catalyst, thereby improves the service life and the deoxy activity of raw catalyst.
Concrete, PtS of the present invention xThe preparation method of dehydrogenation catalyst may further comprise the steps:
(1) platinum Pt Preparation of catalysts: use platiniferous solution, adopt spraying process or infusion process that platinum is carried on the carrier, obtain platinum catalyst, wherein platinum content is 0.01～0.5% (wt), with the total restatement of catalyst;
(2) reduction-sulfurization: the Pt catalyzer temperature-elevating that step (1) is obtained, logical H 2Reduction, subsequently, to H 2The middle vulcanizing agent that feeds vulcanizes, and after sulfuration finished, the mol ratio x that makes S/Pt in the catalyst was 0.1～50, and preferred 1～20;
(3) purge cooling: the H that continues logical hydrogen purge catalyst surface physical absorption 2S is until tail gas H 2Middle H 2S content cools the temperature to room temperature less than 0.1ppm in nitrogen atmosphere, logical nitrogen displacement H 2After, obtain described PtS xDehydrogenation catalyst.
Wherein said carrier is selected from a kind of in alundum (Al, silica, titanium dioxide, active carbon, diatomite and the molecular sieve, preferred alundum (Al; The shape of carrier can be shapes such as bar shaped, sphere.
Preferred platiniferous solution is selected from H 2PtCl 6, K 2PtCl 6And PtCl 4One of the aqueous solution, with carrier the solution of absorbent maximum flood, and the consumption of platiniferous solution should to make the platinum content in the platinum catalyst of (350～450 ℃) after the last roasting be 0.01～0.5% (wt), preferred 0.05～0.3% (wt).
After with platiniferous solution impregnation or spraying carrier, 100～150 ℃ of dryings 3～8 hours, 300～500 ℃ of roastings 2～8 hours.
In the preferred described reduction-sulfurization step, platinum catalyst is warming up to 250～450 ℃, at hydrogen gas space velocity 5～100hr -1Condition under, logical hydrogen 2～5 hours.Described vulcanizing agent can be H 2S, or can produce H after other hydrogenolysis 2The reagent of S is as (CH 3) 2S 2, cure time is 0.5～10 hour; The preferred H that uses 2S gas is as vulcanizing agent, and H 2S is at H 2In concentration be 0.1%～10% (v/v).
Method of the present invention uses fixed bed reactors as the reversion tower, at first platinum catalyst being put into the reversion tower heats up, reducing gas hydrogen and vulcanizing agent feed through metering then, after reduction-sulfurization, purging cooling, and the emptying after alkali lye absorbs of sulfur-bearing tail gas.
Utilize the PtS of method preparation of the present invention xDehydrogenation catalyst goes for general hydrogen and general nitrogen, alkane etc. are joined the hydrogen deoxidation, or the synthesis gas of sulfur-bearing (CO and H 2Gaseous mixture) waits the purification of other gas micro amount of oxygen.
Beneficial effect of the present invention is as follows:
1,,, is specially adapted to removing of micro amount of oxygen in the sulfurous gas so have very strong anti-sulfur poisoning performance because catalyst activity sexual element of the present invention is the sulfide of Pt.
2, catalyst of the present invention does not need preliminary treatment promptly can be directly used in the deoxidation of hydrogen-containing gas.
3, method of the present invention both can be used for the direct preparation of platinum sulfide dehydrogenation catalyst, also was applicable to directly the deoxidier that uses on the existing process units is carried out vulcanizing treatment, can improve existing Pt/Al 2O 3The service life of catalyst, deoxy activity and anti-poisoning capability.
The specific embodiment
Illustrate content of the present invention below, but protection scope of the present invention is not limited to following examples.
Embodiment 1 Preparation of catalysts
By dipping 15Kg γ-Al 2O 3And Pt content in catalyst is that 0.076% (wt) calculates, and takes by weighing 125 gram H 2PtCl 6Solution (Pt content 9.12%).According to γ-Al 2O 3The water absorption rate adding distil water with H 2PtCl 6Solution is diluted to about 8000ml.With 15Kg γ-Al 2O 3Pour in the titanium material coating pan, get under the rotating speed at 24 rev/mins, the control spray time was sprayed on carrier surface equably with the Pt solution for preparing between 10～15 minutes.After having sprayed, 120 ℃ of dryings 6 hours.450 ℃ of roastings are 4 hours then, are prepared into Pt/Al 2O 3Catalyst.
With the Pt/Al after the roasting 2O 3Catalyst pack into the reduction and vulcanization plant in, at 400 ℃, H 2Air speed 10hr -1Reduction is 3 hours under the condition; In hydrogen stream, allocate H into 2S gas makes H 2The concentration of S in hydrogen is 3.2% (v/v), sulfuration 5hr.After sulfuration finishes, continue logical H 2Purging is removed unreacted H 2S, H in tail gas hydrogen 2S content during less than 0.1ppm, is reduced to room temperature before alkali lye absorbs, lead to N 2Displacement back discharging.The PtS of preparation x/ Al 2O 3It is 2.1 that catalyst is analyzed the S/Pt mol ratio with inductively coupled plasma method (ICP).
Embodiment 2 catalyst performance evaluation
The employed synthesis gas of catalyst performance evaluation of the present invention consists of: H 249.6%, CO 48.6%, N 21.0%, O 20.05%, CO 20.1%, COS 0.01%, H 2S 0.05%, and other is 0.6% years old.Detect micro-oxygen content in the gas with Teledyne UltraTrace 3000 trace oxygen analyzers.
Get the deoxidier of 50ml embodiment 1 preparation, use above-mentioned sulfur-bearing synthesis gas, at 180 ℃, 2.2Mpa, 2000hr -1Carry out catalyst activity and stability test under the condition.Analyze the syngas outlet oxygen content every day once, in the process of the test of 1000hr, micro amount of oxygen in the synthesis gas can be purified extremely≤1ppm all the time, do not see active decline.This catalyst of this presentation of results has very high activity and anti-S poisoning capability.After catalyst drawn off, utilize electron microscope not observe catalyst surface knot carbon.Simultaneously, the weight of catalyst is not seen obvious increase yet before and after estimating.
Embodiment 3
Prepare Pt/Al according to embodiment 1 method 2O 3Catalyst 15Kg, the reduction-sulfurization device of packing into.At 300 ℃, H 2Air speed 15hr -1Reduction is 4 hours under the condition.In 5 hours, in hydrogen stream, inject the DMDS (CH after heating is vaporized continuously 3) 2S 245 grams.DMDS is at H 2H behind the pyrolytic in the gas 2The concentration of S is 1.24% (v/v).After sulfuration finishes, continue logical H 2H to the tail gas 2S concentration before alkali lye absorbs＜0.1ppm.Cooling, logical N 2Displacement H 2Back discharging.It is 1.9 that this catalyst is analyzed the S/Pt mol ratio with inductively coupled plasma method (ICP).
Getting the dehydrogenation catalyst of 50ml present embodiment preparation, is 3000hr in the air speed of synthesis gas -1The time, other condition is carried out deoxy performance evaluation, syngas outlet O according to embodiment 2 2Can purify to＜1.0ppm.
Embodiment 4
Method according to embodiment 1 prepares dehydrogenation catalyst.Change Pt/Al 2O 3Sintering temperature is 400 ℃, and the reduction-sulfurization temperature is 350 ℃, and the concentration of hydrogen sulfide in hydrogen is 5.0% (v/v), and other conditions are constant.Finished product PtS xDeoxidier is 2.3 through icp analysis S/Pt mol ratio.According to the condition evaluating catalyst performance of embodiment 2, at air speed 3000hr -1The time, oxygen in the synthesis gas can be purified extremely＜1.0ppm from 500ppm.
Embodiment 5
Change Pt/Al 2O 3The content of middle Pt is 0.2% (wt), and all the other carry out roasting, reduction, sulfuration and purging according to the condition of embodiment 4.The PtS for preparing x/ Al 2O 3Catalyst is 2.4 through icp analysis S/Pt mol ratio.Press the condition evaluating catalyst performance of embodiment 2.At air speed 3000hr -1The time, oxygen in the synthesis gas can be purified extremely＜1ppm from 500ppm.

Claims (9)

1, a kind of active component is platinum sulfide PtS xThe preparation method of support type dehydrogenation catalyst, may further comprise the steps:
(1) platinum Pt Preparation of catalysts: use platiniferous solution, adopt spraying process or infusion process that platinum is carried on the carrier, obtain platinum catalyst, wherein platinum content is 0.01～0.5% (wt), with the total restatement of catalyst;
(2) reduction-sulfurization: the Pt catalyzer temperature-elevating that step (1) is obtained, logical H 2The reduction, to H 2The middle vulcanizing agent that adds vulcanizes, and after sulfuration finished, the mol ratio x that makes S/Pt in the catalyst was 0.1～50;
(3) purge cooling: continue logical hydrogen until tail gas H 2Middle H 2S content cools the temperature to room temperature less than 0.1ppm in nitrogen atmosphere, obtain described PtS xDehydrogenation catalyst.
2, preparation method as claimed in claim 1 is characterized in that described carrier is selected from a kind of in alundum (Al, silica, titanium dioxide, active carbon, diatomite and the molecular sieve; Its shape can be bar shaped or sphere.
3, preparation method as claimed in claim 2 is characterized in that described carrier is an alundum (Al.
4, preparation method as claimed in claim 1 is characterized in that described platiniferous solution is selected from H 2PtCl 6, K 2PtCl 6And PtCl 4One of the aqueous solution, and the consumption of platiniferous solution should to make the platinum content in the platinum catalyst be 0.05～0.3% (wt).
5, preparation method as claimed in claim 1 is characterized in that with behind the platiniferous solution impregnating carrier, 100～150 ℃ of dryings 3～8 hours, and 300～500 ℃ of roastings 2～8 hours.
6, preparation method as claimed in claim 1 is characterized in that platinum catalyst being warming up to 250～450 ℃, at hydrogen gas space velocity 5～100hr in the described reduction-sulfurization step -1Condition under, logical hydrogen 2～5 hours.
7, preparation method as claimed in claim 1 is characterized in that described vulcanizing agent can be H 2S, or can produce H after other hydrogenolysis 2The reagent of S, cure time are 0.5～10 hour.
8, preparation method as claimed in claim 7 is characterized in that described vulcanizing agent is H 2S, and H 2S is at H 2In concentration be 0.1%～10% (v/v).
9, preparation method as claimed in claim 1, the mol ratio x that it is characterized in that S/Pt in the described catalyst is 1～20.
CNB2004100863854A 2004-10-27 2004-10-27 Method for preparing platinum sulfide dehydrogenation catalyst Active CN1327955C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102429312A (en) * 2011-10-31 2012-05-02 华南理工大学 Quick deoxidizer for in-situ generation of primary battery and preparation method thereof
CN103372369A (en) * 2012-04-13 2013-10-30 中国石油化工股份有限公司 Method for removing trace impurities from synthesis gas and application of synthesis gas
CN105854900A (en) * 2016-04-27 2016-08-17 厦门大学 Catalytic wet oxidation catalyst applied to harmless treatment of ammonia-nitrogen wastewater and preparation method thereof
CN106140322A (en) * 2015-04-15 2016-11-23 中国石油化工股份有限公司 A kind of hydrogenation catalyst activation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3275567A (en) * 1963-06-27 1966-09-27 Engelhard Ind Inc Method of preparing a sulfided platinum on carbon catalyst
TW322432B (en) * 1993-06-14 1997-12-11 Degussa

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102429312A (en) * 2011-10-31 2012-05-02 华南理工大学 Quick deoxidizer for in-situ generation of primary battery and preparation method thereof
CN103372369A (en) * 2012-04-13 2013-10-30 中国石油化工股份有限公司 Method for removing trace impurities from synthesis gas and application of synthesis gas
CN106140322A (en) * 2015-04-15 2016-11-23 中国石油化工股份有限公司 A kind of hydrogenation catalyst activation method and application thereof
CN106140322B (en) * 2015-04-15 2019-04-16 中国石油化工股份有限公司 A kind of hydrogenation catalyst activation method and its application
CN105854900A (en) * 2016-04-27 2016-08-17 厦门大学 Catalytic wet oxidation catalyst applied to harmless treatment of ammonia-nitrogen wastewater and preparation method thereof

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