CN1325160C - Palladium-carrying catalyst using titanium dioxide as carrier for acetylene hydrocarbon selective hydrogenation - Google Patents
Palladium-carrying catalyst using titanium dioxide as carrier for acetylene hydrocarbon selective hydrogenation Download PDFInfo
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- CN1325160C CN1325160C CNB2004100216515A CN200410021651A CN1325160C CN 1325160 C CN1325160 C CN 1325160C CN B2004100216515 A CNB2004100216515 A CN B2004100216515A CN 200410021651 A CN200410021651 A CN 200410021651A CN 1325160 C CN1325160 C CN 1325160C
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Abstract
The present invention provides a preparation method of a catalyst for the catalytic selective hydrogenation of acetylene to prepare ethene by adopting titanium dioxide from various sources as a carrier; good reaction effect can be obtained, and the yield of the ethene can reach 95%. The present invention is characterized in that the catalyst contains 0.01 to 5 wt% of palladium as a main active component, and at least one of alkali metals, alkaline earth metals or transitional metals of the eighth family as a cocatalyst component. The finished product of the titanium dioxide carrier is soaked with a solution containing one or some of the required metallic elements in a stepwise mode or for one time, or the active component and the cocatalyst component are added during the formation process of the titanium dioxide carrier, and then, the mixture is dried, roasted and reduced to obtain the catalyst.
Description
The present invention is a kind of selective catalytic hydrogenation catalyst for reaction that is used for alkynes, belong to the catalysis material technical field, it is characterized in that containing 0.01 to 5wt% active component palladium and I main group, the auxiliary agent of at least a metal in II main group and the group VIII, wherein said auxiliary agent is a metal Na, K, Mg, Ca, Sr, Ba, Fe, Co, among the Ni one or more, contain the solution substep of one or more required metallic elements or flood the finished product titania support jointly by employing, or in the titania support forming process, add active component and auxiliary agent, then dry, roasting and reduction, can obtain remarkable reaction effect, yield of ethene can reach more than 95%.
As everyone knows, the large basic Organic Chemicals of preparation in petrochemical industry--in the production of alkene, always being accompanied by classes such as alkynes or alkadienes influences the generation of the poison control centre of the further deep processing of alkene, and to remove the research of unwanted impurity be carbon two (C always so develop new selection hydrogenation catalyst
2) cut fraction hydrogenation removes the focus of attention of process of alkyne.
Present industrial most group VIII elements that adopt are as the reactive activity component, as palladium, platinum, rhodium, nickel etc., wherein palladium catalyst with its good reaction activity and ethylene selectivity by numerous scholars and researcher's extensive concern.Auxiliary agent research aspect such as patent EP0689872 adopt Ag as the selectivity of co-catalyst with the raising palladium catalyst; US4533779 mentions at Pd/Al
2O
3The middle Au element that adds is united and is adopted ammoniacal liquor to improve the sulfur resistance of catalyst; US5889187 then uses alkali or alkaline-earth metal comes the conditioned reaction performance; Added rare earth element among the Chinese patent CN1296880; Dai Wei etc. (CN1279126A) have then prepared palladium/bismuth bimetallic catalyst.The study on the carrier aspect as: the complex carrier that proposes to prepare with chemical method aluminium oxide and titanium dioxide among the patent CN1361231 comes loaded palladium, thereby improves selectivity and life cycle; It is carrier that Tao Jialin etc. (CN1317367) propose with the ZnO that contains auxiliary component; Carrier among the US6388150 is the fiber with tridimensional network; Other relates to employing cordierite, sepiolite or SiO in addition
2, diatomite, ceramic honey comb etc. research.To these aspects, comprise that the research of the processing of catalyst also has a considerable amount of reports on documents and materials.
Purpose of the present invention is exactly at the discussion focus of hydrogenation catalyst research field now, further optimizes the loaded catalyst design and improves its catalytic perfomance, obtains good reaction effect.Consider that the interaction partners reactivity worth between carrier and active component and auxiliary agent works the key effect of being played on the loaded catalyst, the inventor has adopted the titania support that is prone to strong interaction between carrier and metallic element, when improving catalyst low-temp reaction effect, improved the yield of target product ethene, reached more than 95%.
The invention provides a kind of is the novel supported hydrogenization catalyst preparation method of carrier with titanium dioxide, it is characterized in that: based on catalyst, titanium dioxide with various sources is carrier, support the auxiliary agent of at least a element in 0.01 to 5wt.% main active component palladium and I main group, II main group and the group VIII, wherein said auxiliary agent is one or more among element Na, K, Mg, Ca, Sr, Ba, Fe, Co, the Ni.Preparation process comprises that employing contains the salting liquid substep of one or more required metals or floods finished product titanium dioxide jointly, or can add active component and auxiliary agent in the titania support forming process, drying, roasting and reduction.Carrier adopts the titanium dioxide of anatase, rutile and the brookite type in various sources, and the preparation method comprises co-precipitation, sol-gel method.
Acetylene hydrogenation is reflected in the atmospheric fixed bed flow reactor that has temperature regulating device and carries out among the present invention, load type palladium is a catalyst, product is detected by gas-chromatography (hydrogen flames F exiting ID), and detector temperature is that 110 ℃, vaporizer are 90 ℃, and data are by chromatographic work station N2000 record.
Feature of the present invention also is: unstripped gas is the mist of acetylene, hydrogen and nitrogen, and its reaction temperature is room temperature～200 ℃, is preferably 30～120 ℃; Yield of ethene reaches more than 95%.
The present invention is further illustrated below in conjunction with embodiment:
Reference example:
Take by weighing an amount of 20～40 purpose activated aluminas (1050 ℃ of following roastings) and be catalyst carrier, add the certain density palladium chloride solution that measures in the carrier and add an amount of distilled water and take wet dip method dipping 1h, behind 100 ℃～150 ℃ dry 5h in Muffle furnace 500 ℃ of roasting 5h, before using in following 300 ℃～500 ℃ reduction of hydrogen atmosphere.The activity rating device as mentioned above, question response is at the stable back of institute's controlling temperature point sample analysis.The light-off temperature of this catalyst is about 70 ℃, works stable corresponding conversion of alkyne in back of the afterreaction of living and ethylene selectivity and is respectively 97.02%, 91.06%, and the C 2 hydrocarbon in the product is 1798 with the methane ratio.
Embodiment one:
Adopting butyl titanate is the titanium source, regulate suitable pH value with NaOH solution and make the abundant hydrolysis of butyl titanate, ageing, afterwards by filter, wash, the titania powder of drying and roasting acquisition Detitanium-ore-type.Anatase titanium dioxide with the preparation of commodity titanium dioxide and above-mentioned coprecipitation method is a carrier respectively, and adopting the conventional preparation method's preparation of the employed palladium catalyst of reference example to contain palladium is 0.15% catalyst, and its reactivity worth sees Table 1.
The performance of catalyst on the titania support of two kinds of sources of table 1
Table 1 Influerence of preparation method of TiO
2 support
| TiO 2 | 40℃ | 80℃ | ||||
| conv.％ | sele.％ | yield％ | conv.％ | sele.％ | yield％ | |
| purchase coprecipitation | 0.07 0.71 | 97.12 94.17 | 0.70 0.67 | 86.20 86.17 | 98.06 95.51 | 84.52 82.30 |
catalyst＝0.15wt％Pd/TiO
2，m＝80mg.
No matter the result shows that the hydrogenation catalyst that adopts behind the titania support is at conversion of alkyne or all than the conventional oxidation alumina supporter bigger improvement is being arranged aspect the ethylene selectivity, observing during reaction is investigated with the titanium dioxide among the present invention is that the light-off temperature of the catalyst of equal active component palladium content behind the carrier has reduced by 10～15 ℃ than alumina support, rise live before and after a target product selectivity all remain on more than 95%.C 2 hydrocarbon and methane ratio is all greater than 4500, promptly adopts effective carrying out that has suppressed cracking reaction behind the titania support.
Embodiment two:
Adopt reference example and embodiment one made loaded catalyst, the activity rating device as mentioned above, change reaction process condition, under the serious excessive situation of hydrogen, investigate its catalytic performance, found that the palladium catalyst that the self-control aluminium oxide supports under 120 ℃ reaction temperature can only reach 21% yield of ethene, and under the uniform temp on the same content load type palladium catalyst that with titanium dioxide is carrier conversion of alkyne near 100%, its target product selectivity has reached 88%, along with its selectivity of carrying out of reacting can reach 91%.This shows, under harsh reaction condition, be that the reactivity worth of the load type palladium catalyst of carrier is far superior to conventional alumina support sample with titanium dioxide.
Embodiment three:
Adopt the conventional preparation method of the employed palladium catalyst of reference example, prepare active component palladium content (wt.%) in the catalyst overall weight respectively and be seven kinds of titania supported type metallic catalysts of 0.02%, 0.05%, 0.08%, 0.15%, 1.0%, 2.0%, 3.0%.The same reference example of activity rating device, 80 ℃ of reaction temperatures.Concrete reaction result is shown in Table 2.
Palladium content is to the influence of reactivity worth on table 2 titania support
Table 2 Influence of palladium content on TiO
2
| Pd content wt％ | conv.％ | sele.％ | yield％ |
| 0.02 0.05 0.08 0.15 1.00 2.00 3.00 | 0.07 23.10 77.97 86.20 99.05 98.92 99.60 | 100.0 78.74 97.09 98.06 96.78 94.21 83.03 | 0.07 18.19 75.70 84.52 95.86 93.20 82.70 |
T＝80℃，catalyst＝Pd/TiO
2，m＝80mg.
The result shows the increase along with palladium content, catalyst activity increases successively, light-off temperature decreases, and to rise to amplitude big when palladium content activity of sample less than 0.15% time, conversion of alkyne rises to 86.2% from 0.07%, but since the catalyst activity position can be along with the continuation increase of palladium amount the activity of marked change palladium content from 0.15%～3.00% to promote amplitude little, the weight percentage of palladium surpasses low temperature (40 ℃) activity of 1% rear catalyst sample all near 100%.For selectivity, the selectivity of each sample almost maintained an equal level when the sample of less palladium content reached optimal conversion, and all about 95%, and the green oil generating amount difference that works the rear catalyst of living is not very big; But selectivity can descend along with the raising of activity when palladium content increased gradually.Along with the rising target product yield of palladium content presents peak shape, its maximum appears at that to contain the palladium amount in the catalyst overall weight be 1% sample spot.
Embodiment four:
Be similar to embodiment two, according to the wet dip method, in dipping active component palladium salt, add the appropriate amount of addition agent salting liquid, then drying, roasting, also original preparation contains the titania supported palladium series catalyst of auxiliary agent, remains on 0.15% in the active component palladium content of catalyst overall weight.The activity rating device is the same.Reaction result sees Table 3.
Promoter effect on the palladium series catalyst of table 3 titania supported
Table 3 Role of different promoter on the performance
| Catalyst (Pd0.15％) | Conv.(％) | Sele.(％) | Yield(％) | Ratio of C 2H 4/C 2H 6 |
| Pd Pd-Fe Pd-Na Pd-Mg | 47.63 76.89 82.78 82.42 | 96.34 94.43 95.65 97.37 | 45.89 72.61 79.17 80.25 | 26.32 16.95 21.97 37.02 |
T＝60℃，t＝30min，Support＝TiO
2，Pd/promoter＝1∶1
Add as can be seen from the results transition metal, alkali and alkaline-earth metal titania supported bimetallic catalyst under the lower reaction temperature compared to not having the adding assistant sample keeping under 95% the high selectivity its activity being improved significantly, thereby improved the yield of target product greatly.
Claims (5)
1. a selective acetylene hydrocarbon hydrogenation is the carried palladium catalyst of carrier in order to titanium dioxide, it is characterized in that this catalyst contains the auxiliary agent of at least a element in 0.01% to 5wt% main active component palladium and I main group, II main group and the group VIII, wherein said auxiliary agent is one or more among element Na, K, Mg, Ca, Sr, Ba, Fe, Co, the Ni, and the mol ratio of auxiliary element and palladium is an auxiliary agent: palladium=1: 1.
2. selection hydrogenation catalyst as claimed in claim 1 is characterized in that the carrier of loaded catalyst adopts the titanium dioxide in various sources, comprises the titanium dioxide of anatase, rutile and the brookite type of coprecipitation, Prepared by Sol Gel Method.
3. selection hydrogenation catalyst as claimed in claim 1 is characterized in that active component palladium content is 0.03 to 1.0wt.%.
4. selection hydrogenation catalyst as claimed in claim 1 is characterized in that preparation process is a palladium salt solution impregnation finished product titanium dioxide, or adds the salting liquid of active component and auxiliary element, drying, roasting, reduction then in the titania support forming process.
5. selection hydrogenation catalyst as claimed in claim 1 is characterized in that being applicable to the acetylene catalysis selective hydrogenation reaction in the mixed atmosphere, and reaction temperature is from room temperature～200 ℃.
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100417712C (en) * | 2005-09-29 | 2008-09-10 | 中国石油化工股份有限公司 | Selective acetylene hydrocarbon hydrogenation catalyst, its production and use |
| KR101644665B1 (en) | 2008-12-18 | 2016-08-01 | 사우디 베이식 인더스트리즈 코포레이션 | Selective catalytic hydrogenation of alkynes to corresponding alkenes |
| CN103418378B (en) * | 2013-08-01 | 2016-04-27 | 济南开发区星火科学技术研究院 | A kind of cracking c_4 fraction selective hydrogenation palladium-based catalyst |
| CN106928014B (en) * | 2015-12-31 | 2019-12-10 | 中国石油天然气股份有限公司 | Alkyne removing method for preparing low-carbon olefin from methanol |
| CN106928002B (en) * | 2015-12-31 | 2019-12-06 | 中国石油天然气股份有限公司 | Method for removing alkyne by hydrogenation after carbon dioxide |
| CN106928006B (en) * | 2015-12-31 | 2020-04-10 | 中国石油天然气股份有限公司 | Method for preparing polymer-grade ethylene by hydrogenation |
| CN107362798B (en) * | 2017-07-21 | 2020-06-16 | 北京华福工程有限公司 | Preparation method of Pd-M-based metal catalyst for preparing ethylene by hydrogenation of high-purity acetylene and method for preparing ethylene |
| CN111054328B (en) * | 2018-10-16 | 2023-04-11 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for alkylation raw material and preparation method thereof |
| CN114181031A (en) * | 2020-09-14 | 2022-03-15 | 中国石油化工股份有限公司 | Method for recovering methane from ethylene waste gas produced by oxidative coupling of methane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5889187A (en) * | 1994-06-09 | 1999-03-30 | Institut Francais Du Petrole | Catalytic hydrogenation process and a catalyst for use in the process |
| CN1409655A (en) * | 1999-12-08 | 2003-04-09 | 巴斯福股份公司 | Carrier catalyst for selective hydrogenation of alkines and dienes |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5889187A (en) * | 1994-06-09 | 1999-03-30 | Institut Francais Du Petrole | Catalytic hydrogenation process and a catalyst for use in the process |
| CN1409655A (en) * | 1999-12-08 | 2003-04-09 | 巴斯福股份公司 | Carrier catalyst for selective hydrogenation of alkines and dienes |
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