CN100438975C - Catalyst for ethylene reaction produced by acetylene selective hydrogenation and its preparing method - Google Patents
Catalyst for ethylene reaction produced by acetylene selective hydrogenation and its preparing method Download PDFInfo
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- CN100438975C CN100438975C CNB021281289A CN02128128A CN100438975C CN 100438975 C CN100438975 C CN 100438975C CN B021281289 A CNB021281289 A CN B021281289A CN 02128128 A CN02128128 A CN 02128128A CN 100438975 C CN100438975 C CN 100438975C
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- catalyst
- selective hydrogenation
- palladium
- based catalyst
- acetylene selective
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a low-temperature, high-activity and high-selectivity catalyst for an ethyne selective hydrogenation reaction and a preparation method thereof, which is characterized in that the discharge processing for the prosoma of a platinum catalyst modified by an auxiliary agent loaded by alpha-Al2O3 modified by MgO is carried out, namely that the prosoma of the platinum catalyst reacts with high-energy active species in radio frequency plasma bodies and is rapidly activated under the mild condition; the processing time is short, the process is easy to control, and the process is clean and has no pollution. The catalyst has the advantages of low temperature, high activity (the conversion rate can reach 100% at 50 DEG C), high ethene selectivity (71.3%), low green oil (by-product) content and good stability, and furthermore, the catalyst has good application prospects.
Description
The present invention is a kind of ethylene reaction produced by acetylene selective hydrogenation low temperature high activity, high-selectivity catalyst, belong to the new catalytic material technical field, be particularly related to and utilize the radio frequency plasma body technique that catalyst precarsor is activated rapidly, react the catalyst that superior combination property is arranged thereby make for acetylene selective hydrogenation.
Background of the present invention:
Carbon two (C
2) the cut fraction hydrogenation key problem in technology that removes acetylene technology is to select hydrogenation catalyst.Finding that acetylene and ethene exist competitive Adsorption to make palladium-based catalyst have high activity in the research and inquirement on palladium for a long time, but the weak point that this kind catalyst exists is:
1. conventional preparation method length not only consuming time, the temperature conditions height makes that energy consumption height, production cost height and process are wayward when calcining or reduction, seldom arrives the catalyst of good combination property.
2. the acetylene deep hydrogenation is that the generation of ethane and oligomer is seriously restricting conventional palladium-based catalyst and optionally further improves.
3. palladium-based catalyst is easily poisoned, and activity easily descends in time.
4. the local poisoned technique that usually adopts improves catalyst selectivity and need consume other raw material, increase preparation process, and subsequent treatment is not enough as still existing as described in 1, is difficult to prepare the catalyst of good combination property.
The objective of the invention is to avoid above-mentioned the deficiencies in the prior art and the high activity of a kind of acetylene selective hydrogenation reaction, the novel palladium-based catalyst of high selectivity be provided, the palladium-based catalyst precursor of the conventional dipping of employing radio frequency glow plasma technical finesse reacts the catalyst that superior combination property is arranged thereby its rapid at low temperatures activation is made for acetylene selective hydrogenation.
The present invention can reach by following measure: take equi-volume impregnating to prepare to baking step in carrier and active component (auxiliary agent) solution, adopt the radio frequency glow discharge Low Temperature Plasma Treating.Place discharge tube to feed N the catalyst that supports active component
2Decompose, the back feeds hydrogen and reduces, in discharge process, slowly rotate discharge tube, handle 85min, thus make its at low temperatures rapidly activation make reaction and have low temperature high activity, high selectivity, low green oil (accessory substance) output, stable new catalyst for acetylene selective hydrogenation.
Compared with the prior art the present invention has following advantage:
1. adopt the radio frequency plasma body technique that conventional impregnated catalyst precursor is carried out discharge process, because the effect of high energy particle in the plasma, therefore approach under the condition of room temperature, effective activating catalyst at short notice, the catalyst that makes has excellent comprehensive performances.
2. reaction has advantages such as low temperature high activity (50 ℃ of conversion ratios can reach 100%), high ethylene selectivity (71.3%), low green oil output (trace), good stability to this catalyst for acetylene selective hydrogenation, and the processing time is short, process is easy to control and cleanliness without any pollution.
The present invention is further illustrated below in conjunction with embodiment:
Reference example:
Take by weighing an amount of carrier: 20～40 order Alpha-aluminas (MgO modification), the certain density acid chlorization palladium solution of metering added in the carrier and add an amount of distilled water take equi-volume impregnating, 110 ℃ of dryings of baking oven are put in 80 ℃ of left and right sides water bath methods (constantly stirring simultaneously) in the back.Adopt conventional roasting (450 ℃ of following 3h) and hydrogenating reduction (450 ℃ of following 0.5h) activating catalyst precursor.Preparation palladium content is respectively 0.3%, 0.15%, 0.1%, 0.05% 4 loaded catalyst, is labeled as reference sample A-1 respectively, A-2, A-3, A-4.
Embodiment one:
Take by weighing an amount of carrier: 20～40 order Alpha-aluminas (MgO modification), the certain density acid chlorization palladium solution of metering added in the carrier and add an amount of distilled water take equi-volume impregnating, 110 ℃ of dryings of baking oven are put in 80 ℃ of left and right sides water bath methods (constantly stirring simultaneously) in the back.Place discharge tube to feed N the catalyst precarsor that supports active component
2In RF plasma generator, decompose, feed hydrogen then and reduce, in discharge process, slowly rotate discharge tube, make carrier surface by uniform treatment.Radio frequency 13.56MHz; Discharge parameter is voltage 100V, sun stream 100 ± 10mA, grid current 50 ± 10mA; Processing time amounts to 85min.It is 0.3% new catalyst that the present invention prepares palladium content, is labeled as A-1+P, and its reference A-1 sees reference example.
Activity rating: acetylene hydrogenation is reflected in the fixed bed reactors that flow and carries out.Reaction tube is the glass tube of an internal diameter 4mm, long 33cm, and reaction temperature is recorded by the thermocouple that places the reaction tube centre, and service routine intensification controller control reaction temperature.Unstripped gas is analytically pure acetylene, high-purity hydrogen and nitrogen, the control of throughput mass flowmenter, catalyst amount 200mg.Reaction condition is as follows: H
2/ C
2H
2=2/1, total gas flow rate 110ml/min.The reaction gas-phase product detects with hydrogen flames F exiting ID, and detector, temperature of vaporization chamber are 90 ℃, and data are by chromatographic work station N2000 record.
Reaction result shows that the content that is used for ethylene reaction produced by acetylene selective hydrogenation that the present invention uses plasma technique development is Pd/ α-Al of 0.3%
2O
3(MgO modification) catalyst at low temperatures (70 ℃) conversion ratio can reach 100%, and conventional reference sample A-1 need be greater than 100 ℃ reaction temperature; From the ethylene selectivity aspect, the both presents peak shape with the rising of reaction temperature and optimum value appears at 90 ℃, the prepared sample of the present invention is significantly increased than reference sample, and selectivity of the present invention is 49.75% and the ethylene selectivity of reference sample A-1 is 30.71%.
Embodiment two:
Be similar to the method for preparing catalyst of embodiment one, support the catalyst precarsor of active component with the radio frequency Low Temperature Plasma Treating, preparation palladium content is respectively 0.1%, 0.05% new catalyst, is labeled as A-3+P, A-4+P.With the acetylene catalytic hydrogenation it is carried out activity rating.
The result draws: the reaction temperature that the prepared new catalyst of the present invention reaches high conversion (100%) has reduced by 20 ℃ than the support type sample of conventional method; It is that 0.1% new catalyst improves and stablizes ethylene selectivity in about 20.5% that the present invention uses content that plasma technique makes, and content is that 0.05% catalyst can keep exceeding nearly one times ethylene selectivity with reference to sample A-4.Concrete outcome can be joined and is shown in Table 1.
Reactivity contrast (90 ℃) on the sample of table 1 conventional method and plasma treatment
| Sample number | A-1 | A-1+P | A-3 | A-3+P | A-4 | A-4+P |
| Palladium content % | 0.3 | 0.3 | 0.1 | 0.1 | 0.05 | 0.05 |
| Conversion ratio % | 99.36 | 100.0 | 12.43 | 99.52 | 11.44 | 99.40 |
| Ethylene selectivity % | 30.71 | 49.75 | 9.67 | 20.53 | 8.87 | 15.36 |
(H
2/ C
2H
2=2: 1, air-flow total amount 110ml/min ,+P are plasma-treated samples)
Embodiment three:
Use the catalyst precarsor (step, discharge parameter as embodiment one as described in) of radio frequency plasma technical finesse wet dip method preparation, make palladium content and be 0.15% new catalyst A-2+P and be improved than reference sample A-2.
(50 ℃) the present invention conversion ratio and selectivity of preparing sample is respectively 100%, 71.27% at low temperatures, corresponding reference sample data are 0.96%, 4.22%: the present invention prepared sample when reaction temperature rose to 70 ℃ conversion ratio and selectivity are respectively 100%, 52.63%, the data of corresponding reference sample A-2 are 4.74%, 6.50%, react (20h) investigation down for a long time by 70 ℃ simultaneously and find that it is activity stabilized after the induction period of short-term in the investigation time that the present invention uses the prepared new catalyst of plasma technique.The conversion ratio that reaches 110 ℃ of two kinds of catalyst when reaction temperature remains basically stable, but the selectivity of the new catalyst A-2+P of plasma treatment is still up to 45.84%, and reference sample A-2 is 10.96% (also being its best point).
Embodiment four:
Add the ammonium ceric nitrate dipping of metering simultaneously at the preparation palladium-based catalyst, after water bath method, drying, the conventional roasting (450 ℃ of following 3h) of catalyst precarsor and the hydrogenating reduction (450 ℃ of following 0.5h) that will support active component again activate.It is 0.3% that the present invention prepares palladium content, and cerium content is 1.0% new catalyst, is labeled as A-1+Ce.
The result shows that conversion ratio and ethylene selectivity to palladium-based catalyst behind the adding auxiliary agent cerium oxide all have greatly improved.The reaction temperature that the prepared new catalyst of the present invention reaches high conversion (100%) has reduced by 20 ℃ than with reference to sample; To prepare the selectivity of sample be 14.37% in the present invention in the time of 50 ℃, and reference sample A-1 is 7.71%; After reaction temperature rose to 70 ℃, the ethylene selectivity of A-1+Ce reached 42.77%, and the reference sample selective data is 6.66%; Even (130 ℃) the present invention at high temperature prepares the selectivity still higher (32.54%) of sample, reference sample then is 17.98%.
Claims (4)
1. an acetylene selective hydrogenation reacts and uses palladium-based catalyst, it is characterized in that this catalyst precarsor is the palladium-based catalyst that the alpha-alumina supports of modifying through MgO that adopts infusion process to make supports, its precursor is promptly used high energy active specy and its effect in the radio frequency plasma via discharge process, makes its rapid activation at low temperatures.
2. palladium-based catalyst is used in a kind of acetylene selective hydrogenation reaction as claimed in claim 1, and the carrier that it is characterized in that catalyst is α-Al that MgO modifies
2O
3Active component is a metal Pd, and auxiliary agent is CeO
2
3. palladium-based catalyst is used in a kind of acetylene selective hydrogenation reaction as claimed in claim 1, it is characterized in that its precursor adopts the low-pressure low-temperature RF plasma processing, and discharge parameter is voltage 100V, sun stream 100 ± 10mA, grid current 50 ± 10mA; Processing time amounts to 85min.
4. palladium-based catalyst is used in a kind of acetylene selective hydrogenation reaction as claimed in claim 1, and the precursor that it is characterized in that this catalyst is by equi-volume impregnating or the preparation of wet dip method.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021281289A CN100438975C (en) | 2002-12-30 | 2002-12-30 | Catalyst for ethylene reaction produced by acetylene selective hydrogenation and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021281289A CN100438975C (en) | 2002-12-30 | 2002-12-30 | Catalyst for ethylene reaction produced by acetylene selective hydrogenation and its preparing method |
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| CN1511634A CN1511634A (en) | 2004-07-14 |
| CN100438975C true CN100438975C (en) | 2008-12-03 |
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| CNB021281289A Expired - Fee Related CN100438975C (en) | 2002-12-30 | 2002-12-30 | Catalyst for ethylene reaction produced by acetylene selective hydrogenation and its preparing method |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110288353A1 (en) | 2008-11-26 | 2011-11-24 | Wei Dai | Metal loaded catalyst and preparation method thereof |
| CN104549560A (en) * | 2013-10-10 | 2015-04-29 | 中国石油化工股份有限公司 | Method for activating hydrogenation catalyst |
| CN111185222A (en) * | 2020-01-13 | 2020-05-22 | 石河子大学 | Zinc-based catalyst for catalyzing acetylene hydration reaction and preparation method thereof |
| CN111185163A (en) * | 2020-02-20 | 2020-05-22 | 厦门大学 | Preparation method and application of catalyst for preparing β -phenethyl alcohol by hydrogenation of styrene oxide |
| CN114733569B (en) * | 2022-03-31 | 2024-03-29 | 浙江工业大学 | Preparation method and application of covalent organic framework supported palladium catalyst for preparing ethylene by acetylene hydrogenation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347394A (en) * | 1999-01-21 | 2002-05-01 | Abb拉默斯环球有限公司 | Selective hydrogenation process and catalyst therefor |
| CN1362476A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Selectively hydrogenating catalyst |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347394A (en) * | 1999-01-21 | 2002-05-01 | Abb拉默斯环球有限公司 | Selective hydrogenation process and catalyst therefor |
| US6388150B1 (en) * | 1999-01-21 | 2002-05-14 | Abb Lummus Global Inc. | Selective hydrogenation process and catalyst therefor |
| CN1362476A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Selectively hydrogenating catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 等离子体技术制备Ni/a-AL2O3催化剂. 张勇，储伟等.天然气化工，第25卷. 2000 |
| 等离子体技术制备Ni/a-AL2O3催化剂. 张勇，储伟等.天然气化工，第25卷. 2000 * |
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Granted publication date: 20081203 Termination date: 20100201 |