CN106018664A - Method for evaluating inactivation performance of nickel catalyst in laboratory - Google Patents
Method for evaluating inactivation performance of nickel catalyst in laboratory Download PDFInfo
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- CN106018664A CN106018664A CN201610673693.XA CN201610673693A CN106018664A CN 106018664 A CN106018664 A CN 106018664A CN 201610673693 A CN201610673693 A CN 201610673693A CN 106018664 A CN106018664 A CN 106018664A
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- nickel
- catalyst
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- raney nickel
- inactivation performance
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/10—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using catalysis
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N5/00—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid
- G01N5/04—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by removing a component, e.g. by evaporation, and weighing the remainder
Abstract
The invention relates to a laboratory evaluating system capable of conveniently and effectively evaluating inactivation, caused by nickel carbonyl formation, of a nickel catalyst. The system is based on a thermogravimetric analysis platform, the change condition of the weight of a catalyst sample is detected when gas containing CO flows through the nickel catalyst in a reduced state at certain temperature, so that the loss condition that active component nickel in the catalyst forms nickel carbonyl is judged, and nickel carbonyl possibly existing in tail gas flowing out of a sample cell is decomposed through a nickel carbonyl absorbing and decomposing device connected to the rear end of the system.
Description
Technical field
The method that the present invention relates to a kind of laboratory evaluation Raney nickel inactivation performance, is specifically related to a kind of method evaluated and inactivate performance when Raney nickel uses in containing CO environment.
Background technology
Raney nickel is a kind of use catalyst prod the most widely in chemical industry, and especially in hydrogenation process, Raney nickel hydrogenation activity is high, and the comparatively expensive metallic catalyst of price also has great advantage, so Raney nickel has high cost performance.In many hydrogenation process, the hydrogenation process (CO+3H of CO2↔CH4+H2O), namely methanation is the most all to use Raney nickel in a lot of fields.Such as, during cracking separates preparing ethylene, propylene, with by-product a considerable amount of hydrogen-rich fraction, about hydrogen 90～96%, there is also the carbon monoxide of 0.1～1.0% simultaneously.Owing to CO can cause carbon two, C_3 hydrogenation catalyst poisoning to inactivate, the most this hydrogen-rich can not directly make to be hydrogenated with hydrogen source, and must first be removed by wherein CO.Industrial method the removing CO, i.e. CO+3H just utilizing methanation2↔CH4+H2O.In synthesis ammonia plant and some device for producing hydrogen, methanation is also H2The final step purified.Ethylene unit and the optimum operating temperature scope of methanation catalyst in synthetic ammonia installation are substantially at about 300 DEG C at present, if the use temperature of catalyst can be dropped to less than 200 DEG C, and same decontamination index can be reached, then low temperature methanation process energy-saving and cost-reducing and urge into the advantage in terms of safety in production will be obviously.
Low temperature methanation process no doubt has a lot of advantage, but there is also serious hidden danger, because nickel metal is easy to and the Ni (CO) having hypertoxicity of the CO formation gaseous state in gas phase at low temperatures4, and it is carried over reaction system, cause loss of active component, final catalysqt deactivation.The catalyst that thus be accordingly used in low temperature methanation process have to be formed, according to it, the complexity that Nickel tetracarbonyl. causes nickel to run off take the circumstances into consideration to apply to forming Nickel tetracarbonyl. under its low temperature and the performance that inactivate is evaluated.
Summary of the invention
It is an object of the invention to provide a kind of Raney nickel of can conveniently and effectively evaluating and cause the laboratory evaluation method of the performance inactivated because forming Nickel tetracarbonyl..The method is built upon on thermogravimetric analysis platform, by detection uniform temperature under when the gas containing CO flows through the nickel catalyst surface of reduction-state, the situation of change of catalyst sample weight judges that in catalyst, active component nickel forms the wastage of Nickel tetracarbonyl., and absorbing decomposer by the Nickel tetracarbonyl. before being connected to gas emptying, in the tail gas that will flow out from sample cell, the Nickel tetracarbonyl. of hypertoxicity that may be present decomposes.
Metallic nickel and CO form Nickel tetracarbonyl. and could occur the most at a lower temperature, as document (PM technique, 2011, volume 29 the 4th phase, 290-295 page) point out, at 38 DEG C-93 DEG C, CO contacts with active nickel can form Nickel tetracarbonyl., and Nickel tetracarbonyl. can decompose more than 180 DEG C, and Nickel tetracarbonyl. can generate the nitrate of nickel with nitric acid reaction and be decomposed.According to These characteristics, steady temperature in the method for this evaluation Raney nickel inactivation performance uses the temperature range of less than 180 DEG C in the present invention and the mode that extends heat time heating time monitor catalyst experience at different temperatures different time containing example weight situation of change after CO gas treatment, data according to monitoring, calculate the average weight loss rate of unit interval inner catalyst, judge that Raney nickel causes the trend size of inactivation because forming Nickel tetracarbonyl. with this, and generate nickel nitrate and CO by the nitric acid in Drexel bottle and Nickel tetracarbonyl. reaction, thus eliminate the Nickel tetracarbonyl. of severe toxicity.
On the other hand, metallic catalyst has the generation of carbon distribution reaction in the reaction atmosphere exist CO, carbon distribution is the process of a sample system weightening finish, and form the process that gaseous state Nickel tetracarbonyl. is a sample system weightlessness, if the process relatively carried out generation simultaneously can make, the result of thermogravimetric analysis is intricate even cannot be resolved, just because of for the system that the present invention applies, the temperature that Nickel tetracarbonyl. is formed is well below the lower limit temperature forming carbon distribution, this just completely avoid the interference of carbon distribution process, the trend utilizing thermogravimetric analysis platform convenient acquisition Raney nickel to inactivate because forming Nickel tetracarbonyl. is possibly realized.
The method of testing that the present invention provides, concrete test process is, nickel catalyst sample to be measured is put in the sample cell of thermogravimetric analysis equipment, is passed through H2Reduce, after reduction terminates, at H2In be down to containing the temperature required for CO gas treatment sample；Close H2The most again the gas containing CO is passed through sample cell, the mode using steady temperature to extend heat time heating time carries out heat treatment to sample, the delta data of example weight recorded by thermobalance, the tail gas flowed out from sample cell is passed through Nickel tetracarbonyl. and absorbs decomposer, the absorbing liquid wherein held be concentration be the high concentration salpeter solution of 6-8mol/L, make the Nickel tetracarbonyl. in tail gas decompose by chemical reaction, then empty.
Parameter during concrete test, controls H during reduction2Flow is at 2mL min-1•g-1Catalyst is to 20mL min-1•g-1In range of catalysts, reduction temperature controls in the range of 200 DEG C to 400 DEG C, 1 hour to 4 hours recovery time；Gas flow containing CO controls at 2mL min-1•g-1Catalyst is to 20mL min-1•g-1In range of catalysts, wherein the molar content of CO is 10% to 100%, with containing CO gas treatment reduce after nickel catalyst sample time temperature control between 80 DEG C to 180 DEG C.
The method of a kind of laboratory evaluation Raney nickel inactivation performance that the present invention provides, Raney nickel can be tested containing the weightless data caused because forming Nickel tetracarbonyl. in CO atmosphere, and thus judge its inactivation trend during actual response, this method of testing is stablized effective, test result is the most credible, and absorb decomposer owing to being connected to Nickel tetracarbonyl. so that the method more safety and environmental protection.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further detailed:
The following examples are only used for explaining in detail the explanation present invention, and limit the scope of the present invention never in any form.
Embodiment 1
The method of a kind of laboratory evaluation Raney nickel inactivation performance, the instrument and equipment used includes a set of thermogravimetric analyzer (TA Q50), and a Nickel tetracarbonyl. absorbs decomposer.It is 6mol/L that Nickel tetracarbonyl. absorbs the concentration of nitric acid in the Drexel bottle in decomposer.
Evaluate Raney's nickel catalyst RTH-311(Suzhou City catalyst company limited of Xinhua by the method) inactivation performance, 1.6732g sample RTH-311 is put in the sample cell of thermogravimetric analyzer, H2With 10mL min-1•g-1The speed of catalyst flows through sample cell, and heating sample is to 350 DEG C, and after 130min, example weight is constant, illustrates that reduction process terminates, and now example weight is 1.2047g, stops heating and continues logical H2H is closed after making sample be cooled to 160 DEG C2The gaseous mixture (CO accounts for the 20% of total mole number) of CO and N2 is passed through sample cell simultaneously, keep temperature 160 DEG C, after 3 hours, stop test, now example weight is 1.0313g, therefore at 160 DEG C, and average weight loss rate v=(the 1.2047-1.0313)/1.2047/3=0.048 of sample RTH-311 in 3 hours
hr-1, the most under test conditions, sample has the weight of 4.8% per hour and runs off.
Embodiment 2
The method of a kind of laboratory evaluation Raney nickel inactivation performance, the instrument and equipment used includes a set of thermogravimetric analyzer (TA Q50), and a Nickel tetracarbonyl. absorbs decomposer.In Drexel bottle in Nickel tetracarbonyl. absorption decomposer, the concentration of nitric acid is at 8mol/L.
Evaluate Raney's nickel catalyst RTH-211(Suzhou City catalyst company limited of Xinhua by the method) inactivation performance, 1.6911g sample RTH-211 is put in the sample cell of thermogravimetric analyzer, H2With 15mL min-1•g-1The speed of catalyst flows through sample cell, and heating sample is to 400 DEG C, and after 110min, example weight is constant, illustrates that reduction process terminates, and now example weight is 1.2196g, stops heating and continues logical H2H is closed after making sample be cooled to 120 DEG C2, the gaseous mixture (CO accounts for the 50% of total mole number) of CO and N2 is passed through sample cell simultaneously, keeps temperature 120 DEG C, after 4 hours, stopping test, now example weight is 0.9174g, therefore at 120 DEG C, the average weight loss rate v=(1.2196-0.9174) of sample RTH-211 in 4 hours/
1.2196/4=0.062 hr-1, the most under test conditions, sample has the weight of 6.2% per hour and runs off.
Claims (4)
1. the method for a laboratory evaluation Raney nickel inactivation performance, it is characterised in that the inactivation performance caused because forming Nickel tetracarbonyl. loss by thermogravimetric analysis Raney nickel, operating procedure order is to put in sample cell by catalyst to be measured, is passed through H2Reduce, after reduction terminates, at H2In be cooled to next step with containing temperature required during CO gas treatment sample, at this moment close H2, then the gas containing CO is passed through sample cell, the mode using steady temperature to extend heat time heating time carries out heat treatment, the data of thermobalance record catalyst weight change to sample, calculates the average weight loss rate of unit interval inner catalyst.
The method of a kind of laboratory evaluation Raney nickel the most according to claim 1 inactivation performance, it is characterised in that the hardware platform realizing the method is, one is enclosed within the thermogravimetric analyzer being connected to Drexel bottle before gas is vented.
The method of a kind of laboratory evaluation Raney nickel the most according to claim 2 inactivation performance, it is characterised in that in Drexel bottle, the concentration of nitric acid is in the range of 6mol/L to 8mol/L.
The method of a kind of laboratory evaluation Raney nickel the most according to claim 1 inactivation performance, it is characterised in that when the mode using steady temperature to extend heat time heating time carries out heat treatment to sample, in the range of described steady temperature is 80 DEG C to 180 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106770452A (en) * | 2017-01-26 | 2017-05-31 | 芜湖市纽泰知识产权信息咨询有限公司 | A kind of method that utilization thermal analysis system evaluates catalyst |
| CN113494715A (en) * | 2021-05-26 | 2021-10-12 | 南大恩洁优环境技术(江苏)股份公司 | VOCs circulating catalytic combustion purification device |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105277534A (en) * | 2014-06-18 | 2016-01-27 | 内蒙古大唐国际克什克腾煤制天然气有限责任公司 | Method for analyzing trace amounts of carbonyl iron and nickel carbonyl in methanation raw gas and system thereof |
-
2016
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105277534A (en) * | 2014-06-18 | 2016-01-27 | 内蒙古大唐国际克什克腾煤制天然气有限责任公司 | Method for analyzing trace amounts of carbonyl iron and nickel carbonyl in methanation raw gas and system thereof |
Non-Patent Citations (7)
| Title |
|---|
| CALVIN H. BARTHOLOMEW: "Chemistry of Nickel-Alumina Catalysts", 《JOURNAL OF CATALYSLS》 * |
| CALVIN H. BARTHOLOMEW: "Mechanisms of catalyst deactivation", 《APPLIED CATALYSIS A: GENERAL 》 * |
| 中国科学技术情报研究所: "《国外专利资料专辑 流态化气体炼铁》", 31 December 1977 * |
| 刁望升: "加氢装置中羰基镍的生成及预防", 《危险化学品管理》 * |
| 孙晓明 等: "羰基镍的形成原因分析及预防措施", 《工业技术》 * |
| 林西平: "《石油化工催化概论》", 31 December 2008 * |
| 田大勇: "宽温型镍基甲烷化催化剂制备及催化性能", 《工业催化》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106770452A (en) * | 2017-01-26 | 2017-05-31 | 芜湖市纽泰知识产权信息咨询有限公司 | A kind of method that utilization thermal analysis system evaluates catalyst |
| CN106770452B (en) * | 2017-01-26 | 2019-05-28 | 王宏铭 | A method of catalyst is evaluated using thermal analysis system |
| CN113494715A (en) * | 2021-05-26 | 2021-10-12 | 南大恩洁优环境技术(江苏)股份公司 | VOCs circulating catalytic combustion purification device |
| CN113494715B (en) * | 2021-05-26 | 2023-02-14 | 南大恩洁优环境技术(江苏)股份公司 | VOCs circulating catalytic combustion purification device |
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Effective date of registration: 20230421 Address after: 163000 Hongwei Park, Daqing High tech Zone, Daqing City, Heilongjiang Province (No. A-01-2, South Third Road West) Patentee after: Daqing svanda New Material Co.,Ltd. Address before: 241000-302 anding garden, Fanchang District, Wuhu City, Anhui Province Patentee before: Wang Hongming |