CN102794173A - Selective hydrogenation catalyst for removing alkynes and preparation methods thereof - Google Patents
Selective hydrogenation catalyst for removing alkynes and preparation methods thereof Download PDFInfo
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- CN102794173A CN102794173A CN2011101398563A CN201110139856A CN102794173A CN 102794173 A CN102794173 A CN 102794173A CN 2011101398563 A CN2011101398563 A CN 2011101398563A CN 201110139856 A CN201110139856 A CN 201110139856A CN 102794173 A CN102794173 A CN 102794173A
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Abstract
The invention discloses a multi-metal selective hydrogenation catalyst for removing alkynes and preparation methods thereof. The invention aims to solve the problem of poor selectivity in the existing selective hydrogenation catalyst containing Pd and Pb. The catalyst disclosed by the invention uses aluminum oxide as a supporter. On the basis of the total weight of the catalyst as 100%, the catalyst comprises the following elemental ingredients in percentage by weight: (1) 0.01-1% of main active element Pd, (2) 0.01-5% of auxiliary active element Pb, (3) 0.01-10% of more than one of rare-earth elements La, Pr and Nd, and 0.01-5% of more than one of Si, B, F, S and P. The invention also provides two preparation methods. The catalyst disclosed by the invention is used for selectively removing alkynes from the raw material containing rich dialkenes, has the advantages of high air speed and high selectivity, and can be repeatedly used after multiple regeneration.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst, more particularly, the present invention relates to a kind of in being rich in the raw material of alkadienes the alternative hydrogenation catalyst of alkynes and preparation method thereof of removing.
Background technology
Contain the 1,3-butadiene about 50% in the cracking mixed c 4, also contain simultaneously have an appointment 1% carbon three, carbon four alkynes,, must alkynes be removed for obtaining highly purified 1,3-butadiene.Select hydrogenation catalyst can the alkynes in the mixed c 4 be removed to less than 15ppm, butadiene has small loss simultaneously.
Cu is catalyst based to be the catalyst that is used to select acetylene hydrogenation the earliest, and DOW company and Uop Inc. be with its commercial Application, at present, is 1,000,000 tons/year based on the butadiene treating capacity of this catalyst, about 10 covering devices.From the patent of DOW company, like U.S. Pat 3912789, US4101451, US4493906 etc., Cu selection of catalysts property is fine; Do not remaining under the condition of alkynes; The butadiene loss is merely about 1%, but its reaction velocity is very low, and the liquid air speed of mixed c 4 is less than 2h
-1, the cycle of operation is short.
What bibliographical information was more in the recent period is Pd Quito metallic catalyst.Is active component like U.S. Pat 4547600 with Pd and Ag; U.S. Pat 7288686 is an active component with Pd and Ag, Zn, Bi etc.; Japan Patent WO2010035325 is an active component with Pd and Bi, Te, document (Zhao Yinong etc., petrochemical industry; 1997, be active component 26:505-508) with Pd and Pb.The modification of many metal pairs Pd catalyst has not only prevented the loss of Pd in course of reaction, has improved hydrogenation selectivity simultaneously.
Though the Pd catalyst of the additive modification of report is all to have had than much progress in selectivity or aspect stable in the recent period; But the subject matter of restriction Pd catalyst commercial Application is that still its selectivity is good inadequately, promptly the degree of depth remove butadiene in the process of alkynes loss much larger than the Cu catalyst.Through discovering that one or more among elements Si, B, F, S, the P are to Pb-Pd/ rare earth-Al
2O
3The acetylene hydrogenation selectivity of catalyst is improved obviously; Can reach residue alkynes less than 15ppm, butadiene loses the technical indicator less than 1%, and this has reached the level of the Cu catalyst of Uop Inc.; And air speed, running time etc., index was much better than the Cu catalyst, showed better industrial application prospect.
Summary of the invention
The present invention is primarily aimed at the problem of the poor selectivity that has the selection hydrogenation catalyst that contains Pd and Pb now, and purpose provides a kind of hydrogenation catalyst of high selectivity, and this catalyst is particularly suitable for the acetylene hydrogenation technology of cracking mixed c 4 cut.The present invention provides this Preparation of catalysts method simultaneously.
It is carrier with the aluminium oxide that carbon four of the present invention is selected the acetylene hydrogenation catalyst, is 100% in total catalyst weight, comprises each elemental constituent of following percetage by weight:
(1) main active element Pd, 0.01～1%;
(2) help active element Pb, 0.01～5%;
(3) more than one among rare-earth elements La, Pr and the Nd, total content is 0.01～10%; With
(4) more than one among elements Si, B, F, S and the P, total content is 0.01～5%.
Preferably, be 100% in the gross weight of catalyst, the percentage by weight of component (1) is 0.1～0.5%.
Preferably, be 100% in the gross weight of catalyst, the percentage by weight of component (2) is 0.05～2%.
Preferably, be 100% in the gross weight of catalyst, the total weight percent of component (3) is 0.1～5%.
Preferably, be 100% in the gross weight of catalyst, the total weight percent of component (4) is 0.05～2%.
Preferably, said carrier be shaped as sphere, bar shaped, sheet, cloverleaf pattern or tooth is spherical.
Preferably, the specific area of said catalyst is 40～200m
2/ g, pore volume are 0.3～0.9cm
3/ g.
Catalyst of the present invention is a Pd-Pb bimetallic hydrogenation catalyst, and the adding of Pb can improve the electronic environment of Pd, makes its adsorptive selectivity to carbon four alkynes and butadiene better, thereby improves the hydrogenation selectivity of Pd catalyst; The another one effect of Pb is stable metal Pd, and it is not run off in the process of reaction, and this is confirmed in our experiment.
Catalyst of the present invention contains rare-earth elements La, Pr and/or Nd; They are most important to the structure of stablizing Pd and Pb and in the preparation process, forming, if because there is not this type component, catalyst is behind long-time reaction inactivation; In case through regeneration, selectivity will decline to a great extent.
The another kind of important component of catalyst of the present invention is elements Si, B, F, S and/or P, and they can suitably improve the acidity of carrier, and this has influenced the electronic state of Pd, thereby has significantly improved selection of catalysts property.
The present invention also provides two kinds to prepare Preparation of catalysts method of the present invention.
Wherein a kind of preparation method may further comprise the steps: with component (3) and component (4) and aluminium hydrate powder mediate, moulding, after oven dry, roasting, substep or dip composition (1) and component (2) more synchronously, process is dried at last, roasting makes said catalyst.
Another kind of preparation method may further comprise the steps: with component (3) and aluminium hydrate powder kneading, moulding; Through oven dry, after the roasting, dip composition (4) again is after oven dry, roasting; Last substep or synchronous dip composition (1) and component (2) make said catalyst through oven dry, roasting at last.
More particularly, first kind of preparation method's preparation process is:
(1) the inorganic acid acid solution of the salting liquid of La, Pr and/or Nd and Si, B, F, S, P or its sour ammonium salt solution and aluminium hydrate powder are mediated; Moulding; 100～200 ℃ of oven dry 10～20 hours, at last according to the required specific area of experiment with sample temperature required calcining 4～10 hours.The precursor salt of this step rare-earth elements La, Pr and/or Nd is preferably nitrate.
Above-mentioned carrier can be different shapes such as sphere, bar shaped, sheet, cloverleaf pattern, tooth sphere, and its specific surface can be 40～200m
2/ g.The preparation approach of used aluminium hydroxide does not have any influence to the character of catalyst of the present invention, all can like nitrate method, carbonizatin method.
(2) load of Pd and Pb can be carried out simultaneously, also can carry out step by step.All need 100～200 ℃ of oven dry 10～20 hours, then 400～600 ℃ of roastings 4～10 hours behind each step dipping.The precursor of Pd and Pb selects corresponding nitrate, chloride or acetate all can.
More particularly, second kind of preparation method's preparation process is:
(1) with the salting liquid of La, Pr and/or Nd and aluminium hydrate powder mediate, moulding, 100～200 ℃ of oven dry 10～20 hours, at last according to the required specific area of experiment with sample temperature required calcining 4～10 hours.The precursor salt of this step rare-earth elements La, Pr and/or Nd is preferably nitrate.
Above-mentioned carrier can be different shapes such as sphere, bar shaped, sheet, cloverleaf pattern, tooth sphere, and its specific surface can be 40～200m
2/ g.The preparation approach of used aluminium hydroxide does not have any influence to the character of catalyst of the present invention, all can like nitrate method, carbonizatin method.
(2) load Si, B, F, S, P use the inorganic acid solution of these elements or the carrier of its sour ammonium salt solution impregnation steps (1) equally, behind the dipping, need 100～200 ℃ of oven dry 10～20 hours, then 400～600 ℃ of roastings 4～10 hours.
(3) final load Pd and Pb, the load of Pd and Pb can be carried out simultaneously, also can carry out step by step.All need 100～200 ℃ of oven dry 10～20 hours, then 400～600 ℃ of roastings 4～10 hours behind each step dipping.The precursor of Pd and Pb selects corresponding nitrate, chloride or acetate all can.
Catalyst of the present invention needs Pd is reduced to metallic forms before use, can adopt wet reducing (as using the mixture of formaldehyde and KOH) or use H at a certain temperature
2Directly reduction.
Catalyst provided by the invention can be removed the alkynes in the C-4-fraction (allylene, ethyl acetylene and vinylacetylene) under the condition of liquid phase through selective hydrogenation, butadiene loss simultaneously seldom.
Can make the stable rare-earth elements La of Pb, Pr and/or Nd owing to having added in the catalyst of the present invention; But high temperature regeneration after the use; Thereby prolonged the service life of catalyst, the more important thing is, owing to added elements Si, B, F, S and/or the P that can improve acidity of catalyst; Selection of catalysts property significantly improves, thereby has improved the economy of selecting hydrogenation technique.
The specific embodiment
Embodiment 1
Accurately take by weighing the aluminium hydrate powder that the 1Kg nitrate method is produced, accurately take by weighing lanthanum nitrate, its consumption makes the catalyst that finally makes contain lanthanum 1.5% (weight), is dissolved in water.Accurately take by weighing Ludox, its consumption makes the catalyst that finally makes contain Si1.5% (weight).Alumina powder, lanthanum nitrate hexahydrate, Ludox and nitric acid, water mixed pinch, extrusion is processed gear shape, and through 120 ℃ of oven dry 10 hours, 850 ℃ of roastings 4 hours made and contain lanthanum aluminum oxide carrier La-Si-Al
2O
3
Measure an amount of palladium nitrate solution so that the catalyst that finally makes contains palladium 0.3% (weight), with its thin up to La-Si-Al
2O
3The saturated water adsorptive value of carrier, with gained palladium solution spraying in La-Si-Al
2O
3On the carrier, through 120 ℃ of dryings 10 hours, 450 ℃ of roastings 4 hours made Pd/La-Si-Al
2O
3
Accurately take by weighing plumbi nitras, its consumption makes leaded 0.3% (weight) of the catalyst that finally makes, and is dissolved in water, and amount of water equals La-Al
2O
3The saturated water adsorptive value of carrier is sprayed at Pd/La-Si-Al with the lead nitrate solution of gained
2O
3On, through 120 ℃ of dryings 10 hours, 450 ℃ of roastings 4 hours made Pb/Pd/La-Si-Al
2O
3
Contain Pb 0.3% (weight) in the catalyst that finally makes, contain Pd 0.3% (weight), contain La 1.5% (weight), contain Si 1.5% (weight).
Comparative Examples 1
The preparation method is with embodiment 1, but in the process that aluminium hydrate powder is mediated, do not add lanthanum nitrate and Ludox, processes Pb/Pd/Al
2O
3
Contain Pb 0.3% (weight) in the catalyst of gained, contain Pd 0.3% (weight).
Comparative Examples 2
The preparation method is with embodiment 1, but in the process that aluminium hydrate powder is mediated, do not add Ludox, processes Pb/Pd/La-Al
2O
3
Contain Pb0.3% (weight) in the catalyst of gained, contain Pd0.3% (weight), contain La1.5% (weight).
Embodiment 2
The preparation method is with embodiment 1, and different is in the process that alumina powder is mediated, to add lanthanum nitrate and phosphoric acid, processes Pb/Pd/La-P-Al
2O
3
Contain Pb0.3% (weight) in the catalyst of gained, contain Pd0.3% (weight), contain La1.5% (weight), contain P1.5% (weight).
Embodiment 3
Accurately take by weighing the aluminium hydrate powder that the 1Kg nitrate method is produced, accurately take by weighing lanthanum nitrate, its consumption makes the catalyst that finally makes contain lanthanum 1.5% (weight), is dissolved in water.Alumina powder, lanthanum nitrate hexahydrate and nitric acid, water mixed pinch, extrusion is processed gear shape, and through 120 ℃ of oven dry 10 hours, 850 ℃ of roastings 4 hours made and contain lanthanum aluminum oxide carrier La-Al
2O
3
Accurately take by weighing boric acid, its consumption makes the catalyst that finally makes contain B0.5% (weight), is dissolved in water, and the water yield of using is La-Al
2O
3The saturated water adsorptive value of carrier is sprayed at La-Al with the BAS of gained
2O
3On the carrier, through 120 ℃ of dryings 10 hours, 450 ℃ of roastings 4 hours made B/La-Al
2O
3
Measure an amount of palladium nitrate solution so that the catalyst that finally makes contains palladium 0.3% (weight), with its thin up to B/La-Al
2O
3Saturated water adsorptive value, with gained palladium solution spraying in B/La-Al
2O
3On, through 120 ℃ of dryings 10 hours, 450 ℃ of roastings 4 hours made Pd/B/La-Al
2O
3
Accurately take by weighing plumbi nitras, its consumption makes leaded 0.3% (weight) of the catalyst that finally makes, and is dissolved in water, and amount of water equals B/La-Al
2O
3Saturated water adsorptive value, the lead nitrate solution of gained is sprayed at Pd/B/La-Al
2O
3On, through 120 ℃ of dryings 10 hours, 450 ℃ of roastings 4 hours made Pb/Pd/B/La-Al
2O
3
Contain Pb0.3% (weight) in the catalyst that finally makes, contain Pd0.3% (weight), contain La1.5% (weight), contain B0.5% (weight).
Embodiment 4
The preparation method uses ammonium fluoride to substitute boric acid dipping La-Al with embodiment 3
2O
3Carrier is processed Pb/Pd/F/La-Al
2O
3
Contain Pb0.3% (weight) in the catalyst of gained, contain Pd0.3% (weight), contain La1.5% (weight), contain F0.5% (weight).
Embodiment 5
The preparation method uses ammonium sulfate to substitute boric acid dipping La-Al with embodiment 3
2O
3Carrier is processed Pb/Pd/S/La-Al
2O
3
Contain Pb0.3% (weight) in the catalyst of gained, contain Pd0.3% (weight), contain La1.5% (weight), contain S0.5% (weight).
Embodiment 6
Present embodiment is estimated catalyst of the present invention, and test condition is following:
Catalyst test carries out in fixed bed reactors; Loaded catalyst is 200mL, before the reaction must with nitrogen replacement, again 150 ℃ down with hydrogen reducing 4 hours, mixed c 4 raw material composition is listed in table 1; Mixed c 4 from bottom to top flows through reactor after joining hydrogen; The beds inlet temperature is 45 ℃, and reaction pressure is 1.0MPa, and the liquid air speed of C-4-fraction is 20h
-1, the mol ratio of hydrogen and alkynes (often being called for short hydrogen alkynes ratio) is 2～10.
Table 1 mixed c 4 raw material is formed
| Component | Content (weight %) |
| Iso-butane | 2.35 |
| Normal butane | 4.73 |
| Instead-the 2-butylene | 4.49 |
| The 1-butylene | 13.90 |
| Isobutene | 21.31 |
| Suitable-the 2-butylene | 3.36 |
| 1, the 2-butadiene | 0.17 |
| 1,3-butadiene | 48.56 |
| Propine | 0.08 |
| Vinylacetylene | 0.73 |
| Ethyl acetylene | 0.14 |
The reaction result of catalyst of the present invention is listed in table 2.
The average result of estimating in 1000 hours of table 2 embodiment and Comparative Examples catalyst
Can find out that from the data of table 2 the selection of catalysts property of embodiment 1～5 all can reach residue alkynes total amount less than 15ppm, the butadiene loss is less than the index of 1% (weight), and their selectivity obviously is superior to the catalyst of Comparative Examples 1 and Comparative Examples 2.
Claims (9)
1. the catalyst of alkynes is removed in a raw material selective hydrogenation that is used for being rich in alkadienes, it is characterized in that said catalyst is carrier with the aluminium oxide, is 100% in total catalyst weight, comprises each elemental constituent of following percetage by weight:
(1) main active element Pd, 0.01～1%;
(2) help active element Pb, 0.01～5%;
(3) more than one among rare-earth elements La, Pr and the Nd, total content is 0.01～10%; With
(4) more than one among elements Si, B, F, S and the P, total content is 0.01～5%.
2. catalyst as claimed in claim 1 is characterized in that: the gross weight in catalyst is 100%, and the percentage by weight of component (1) is 0.1～0.5%.
3. catalyst as claimed in claim 1 is characterized in that: the gross weight in catalyst is 100%, and the percentage by weight of component (2) is 0.05～2%.
4. catalyst as claimed in claim 1 is characterized in that: the gross weight in catalyst is 100%, and the total weight percent of component (3) is 0.1～5%.
5. catalyst as claimed in claim 1 is characterized in that: the gross weight in catalyst is 100%, and the total weight percent of component (4) is 0.05～2%.
6. catalyst as claimed in claim 1 is characterized in that: said carrier be shaped as sphere, bar shaped, sheet, cloverleaf pattern or tooth is spherical.
7. catalyst as claimed in claim 1 is characterized in that: the specific area of said catalyst is 40～200m
2/ g, pore volume are 0.3～0.9cm
3/ g.
8. like each said Preparation of catalysts method in the claim 1～7; It is characterized in that; Said preparation method may further comprise the steps: with component (3) and component (4) and aluminium hydrate powder kneading, moulding; After oven dry, roasting, substep or dip composition (1) and component (2) more synchronously make said catalyst through oven dry, roasting at last.
9. like each said Preparation of catalysts method in the claim 1～7; It is characterized in that said preparation method may further comprise the steps: with component (3) and aluminium hydrate powder kneading, moulding, after oven dry, roasting; Dip composition (4) again; After oven dry, roasting, last substep or synchronous dip composition (1) and component (2) make said catalyst through oven dry, roasting at last.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104707622B (en) * | 2013-12-11 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of preparation method of selective acetylene hydrocarbon hydrogenation catalyst |
| CN112657512A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Silver-fluorine supported catalyst, preparation method and application |
| CN112657511A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | C4Distillate selective hydrogenation acetylene removal catalyst, preparation method and application |
| CN112717925A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation catalyst, preparation method and application thereof |
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| CN1236333A (en) * | 1996-11-07 | 1999-11-24 | 法国石油公司 | Selective hydrogenation catalysts containing palladium and at least one element selected among tin and lead |
| CN101862653A (en) * | 2009-04-17 | 2010-10-20 | 中国石油化工股份有限公司 | Acetylene selective hydrogenation catalyst and preparation method and application thereof |
| CN102049255A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Palladium-based catalyst for selective hydrogenation of cracked C4 fractions and preparation method thereof |
-
2011
- 2011-05-27 CN CN2011101398563A patent/CN102794173A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1236333A (en) * | 1996-11-07 | 1999-11-24 | 法国石油公司 | Selective hydrogenation catalysts containing palladium and at least one element selected among tin and lead |
| CN101862653A (en) * | 2009-04-17 | 2010-10-20 | 中国石油化工股份有限公司 | Acetylene selective hydrogenation catalyst and preparation method and application thereof |
| CN102049255A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Palladium-based catalyst for selective hydrogenation of cracked C4 fractions and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104707622B (en) * | 2013-12-11 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of preparation method of selective acetylene hydrocarbon hydrogenation catalyst |
| CN112657512A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | Silver-fluorine supported catalyst, preparation method and application |
| CN112657511A (en) * | 2019-10-15 | 2021-04-16 | 中国石油化工股份有限公司 | C4Distillate selective hydrogenation acetylene removal catalyst, preparation method and application |
| CN112717925A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Anthraquinone hydrogenation catalyst, preparation method and application thereof |
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Application publication date: 20121128 |