CN106226190A - A kind of system of laboratory evaluation Raney nickel inactivation performance - Google Patents
A kind of system of laboratory evaluation Raney nickel inactivation performance Download PDFInfo
- Publication number
- CN106226190A CN106226190A CN201610673541.XA CN201610673541A CN106226190A CN 106226190 A CN106226190 A CN 106226190A CN 201610673541 A CN201610673541 A CN 201610673541A CN 106226190 A CN106226190 A CN 106226190A
- Authority
- CN
- China
- Prior art keywords
- nickel
- raney nickel
- sample
- inactivation
- performance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Abstract
The system of a kind of laboratory evaluation Raney nickel inactivation performance that the present invention provides, can test Raney nickel containing the weightless data caused because forming Nickel tetracarbonyl. in CO atmosphere, and thus judge its inactivation trend during actual response.This system embedded in Nickel tetracarbonyl. and absorb decomposer so that system more safety and environmental protection.
Description
Technical field
The present invention relates to the system of a kind of laboratory evaluation Raney nickel inactivation performance, be specifically related to a kind of nickel of evaluating and be catalyzed
The system of performance is inactivated when agent uses in containing CO environment.
Background technology
Raney nickel is a kind of use catalyst prod the most widely in chemical industry, is especially being hydrogenated with
Cheng Zhong, 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 very
It is the most all to use Raney nickel in multi-field.Such as, during cracking separates preparing ethylene, propylene, suitable with by-product
The hydrogen-rich fraction of quantity, 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 inactivate, and the most this hydrogen-rich can not directly be made to be hydrogenated with hydrogen source, and must first be taken off by wherein CO
Remove.Industrial method the removing CO, i.e. CO+3H just utilizing methanation2↔CH4+H2O.At synthesis ammonia plant and some device for producing hydrogen
In, methanation is also H2The final step purified.Ethylene unit and the optimal behaviour of methanation catalyst in synthetic ammonia installation at present
Make temperature range substantially at about 300 DEG C, if the use temperature of catalyst can be dropped to less than 200 DEG C, and can reach same
Decontamination index, then low temperature methanation process energy-saving and cost-reducing and urge into the advantage in terms of safety in production will be clearly
's.
Low temperature methanation process no doubt has a lot of advantage, but there is also serious hidden danger, because nickel metal is at low temperatures
It is easy to and the Ni (CO) having hypertoxicity of the CO formation gaseous state in gas phase4, and it is carried over reaction system, cause active component stream
Lose, final catalysqt deactivation.The catalyst that thus be accordingly used in low temperature methanation process have to be to formation Nickel tetracarbonyl. under its low temperature
The performance of inactivation is evaluated, and forms, according to it, the complexity application as one sees fit that Nickel tetracarbonyl. causes nickel to run off.
Summary of the invention
It is an object of the invention to provide one can conveniently and effectively evaluate Raney nickel because formed Nickel tetracarbonyl. and cause lose
The laboratory evaluation system of the performance lived.This system is built upon on thermogravimetric analysis platform, by under detection uniform temperature
When the gas containing CO flows through the nickel catalyst surface of reduction-state, the situation of change of catalyst sample weight judges in catalyst
Active component nickel forms the wastage of Nickel tetracarbonyl., and absorbs decomposer by being connected to the Nickel tetracarbonyl. of System Back-end, will be from
In the tail gas flowed out in 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 and can form Nickel tetracarbonyl., and carbonyl
Nickel can decompose again more than 180 DEG C, and Nickel tetracarbonyl. can generate the nitrate of nickel with nitric acid reaction and be decomposed.According to above-mentioned spy
Point, the steady temperature in the system of this evaluation Raney nickel inactivation performance uses the temperature range of less than 180 DEG C in the present invention
And the mode extending heat time heating time monitor catalyst experience at different temperatures different time containing sample weight after CO gas treatment
Amount situation of change, according to the data of monitoring, calculates the average weight loss rate of unit interval inner catalyst, judges that nickel is catalyzed with this
Agent causes the trend size of inactivation because forming Nickel tetracarbonyl., and generates nickel nitrate by the nitric acid in Drexel bottle and Nickel tetracarbonyl. reaction
And CO, 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, and carbon distribution is one
The process of sample system weightening finish, and form the process that gaseous state Nickel tetracarbonyl. is a sample system weightlessness, the process relatively carried out is such as
Fruit generation simultaneously can make that the result of thermogravimetric analysis is intricate even cannot be resolved, just because of the system apply present invention
Saying, the temperature that Nickel tetracarbonyl. is formed is well below the lower limit temperature of formation carbon distribution, and this just completely avoid the interference of carbon distribution process, makes
The trend that thermogravimetric analysis platform convenient acquisition Raney nickel must be utilized to inactivate because forming Nickel tetracarbonyl. is possibly realized.
The flow process of this system is as it is shown in figure 1, the gas controlled by mass flowmenter (MFC) enters thermogravimetric by gas line
Analyser (TGA), flows through sample cell therein (SAM), and the tail gas of generation enters Nickel tetracarbonyl. and absorbs decomposer (ADP) through decomposing
Rear emptying.Nickel tetracarbonyl. absorb decomposer be one be arranged in gas emptying before, equipped with the Drexel bottle of salpeter solution.
Concrete test process is, nickel catalyst sample to be measured is put in the sample cell of thermogravimetric analysis equipment, is passed through
H2Reduce, reduce after terminating at H2In be down to room temperature；Then, the gas containing CO is passed through sample cell, uses steady temperature
The mode extending heat time heating time carries out heat treatment to sample, and the delta data of example weight recorded by the thermobalance in TGA, from sample
In product pond flow out tail gas be passed through Nickel tetracarbonyl. absorb decomposer so that it is in Nickel tetracarbonyl. decompose, then empty.
Parameter during concrete test, controls H during reduction2Flow is at 2mL min-1•g-1Catalyst is to 20mL min-1•g-1Catalysis
In the range of agent, reduction temperature controls in the range of 200 DEG C to 400 DEG C, 1 hour to 4 hours recovery time；Gas stream containing CO
Amount 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 system of a kind of laboratory evaluation Raney nickel inactivation performance that the present invention provides, can test Raney nickel and contain
The weightless data caused because forming Nickel tetracarbonyl. in CO atmosphere, and thus judge that its inactivation during actual response becomes
Gesture, this test system stability is effective, and test result is the most credible, and absorbs decomposer owing to being connected to Nickel tetracarbonyl. so that
System more safety and environmental protection.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of a kind of laboratory evaluation Raney nickel inactivation performance system of the present invention.
Detailed description of the invention
With embodiment, the present invention is further detailed below in conjunction with the accompanying drawings:
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
A kind of system of laboratory evaluation Raney nickel inactivation performance, including a set of thermogravimetric analyzer (TA Q50), and a carbonyl
Base nickel absorbs decomposer.It is 0.5mol/L that Nickel tetracarbonyl. absorbs the concentration of nitric acid in the Drexel bottle in decomposer.
With catalyst company limited of Xinhua of this system evaluation Raney's nickel catalyst RTH-311(Suzhou City) 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, 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 H2Sample is made to close H after being cooled to room temperature2, by the gaseous mixture of CO and N2, (CO accounts for always simultaneously
The 20% of molal quantity) it is passed through sample cell, make sample rise to 160 DEG C from room temperature with the speed of 20 DEG C/min, then keep temperature, 3 is little
Shi Hou, stops test, and now example weight is 1.0313g, therefore at 160 DEG C, and the average mistake of sample RTH-311 in 3 hours
Weight speed v=(1.2047-1.0313)/1.2047/3=0.048 hr-1, the most under test conditions, sample has 4.8% per hour
Weight run off.
Embodiment 2
A kind of system of laboratory evaluation Raney nickel inactivation performance, including a set of thermogravimetric analyzer (TA Q50), and a carbonyl
Base nickel absorbs decomposer.In Drexel bottle in Nickel tetracarbonyl. absorption decomposer, the concentration of nitric acid is at 5mol/L.
With catalyst company limited of Xinhua of this system evaluation Raney's nickel catalyst RTH-211(Suzhou City) 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, 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 H2Sample is made to close H after being cooled to room temperature2, by the gaseous mixture of CO and N2, (CO accounts for always simultaneously
The 50% of molal quantity) it is passed through sample cell, make sample rise to 120 DEG C from room temperature with the speed of 10 DEG C/min, then keep temperature, 4 is little
Shi Hou, stops test, and now example weight is 0.9174g, therefore at 120 DEG C, and the average mistake of sample RTH-211 in 4 hours
Weight speed v=(1.2196-0.9174)/1.2196/4=0.062 hr-1, the most under test conditions, sample has 6.2% per hour
Weight run off.
Claims (5)
1. the system of a laboratory evaluation Raney nickel inactivation performance, it is characterised in that this system is can pass through heat
Weight analysis is evaluated Raney nickel and is caused the performance of inactivation because forming Nickel tetracarbonyl. loss, and connection has Nickel tetracarbonyl. absorption to decompose dress
Put the laboratory test platform of (ADP).
The system of a kind of laboratory evaluation Raney nickel the most according to claim 1 inactivation performance, it is characterised in that carbonyl
Nickel absorbs decomposer (ADP), before one is arranged in gas emptying, equipped with the Drexel bottle of salpeter solution.
The system of a kind of laboratory evaluation Raney nickel the most according to claim 2 inactivation performance, it is characterised in that gas washing
In Ping, the concentration of nitric acid is in the range of 0.5mol/L to 5mol/L.
The system of a kind of laboratory evaluation Raney nickel the most according to claim 1 inactivation performance, it is characterised in that this is real
The flow process testing room evaluation system is that the gas controlled by mass flowmenter (MFC) enters thermogravimetric analyzer by gas line
(TGA), flowing through sample cell therein (SAM), the tail gas of generation enters Nickel tetracarbonyl. absorption decomposer (ADP) and is vented afterwards；Operation
Step is, catalyst to be measured is put in sample cell, is passed through H2Reduce, reduce after terminating at H2In be down to room temperature；Then, will
Gas containing CO is passed through sample cell, and the mode using steady temperature to extend heat time heating time carries out heat treatment to sample, from sample
The tail gas flowed out in pond is passed through Nickel tetracarbonyl. and absorbs decomposer emptying after decomposing.
The system of a kind of laboratory evaluation Raney nickel the most according to claim 4 inactivation performance, it is characterised in that this is real
Test in the operating procedure that system is evaluated in room, when the mode using steady temperature to extend heat time heating time carries out heat treatment to sample, institute
The steady temperature scope stated is 80 DEG C to 180 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610673541.XA CN106226190A (en) | 2016-08-16 | 2016-08-16 | A kind of system of laboratory evaluation Raney nickel inactivation performance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610673541.XA CN106226190A (en) | 2016-08-16 | 2016-08-16 | A kind of system of laboratory evaluation Raney nickel inactivation performance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106226190A true CN106226190A (en) | 2016-12-14 |
Family
ID=57552424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610673541.XA Pending CN106226190A (en) | 2016-08-16 | 2016-08-16 | A kind of system of laboratory evaluation Raney nickel inactivation performance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106226190A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106841293A (en) * | 2017-01-26 | 2017-06-13 | 芜湖市纽泰知识产权信息咨询有限公司 | A kind of method that utilization difference quotient thermogravimetric evaluates catalyst |
| CN109894157A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of method for inhibiting Raney nickel nickel to be lost and its application in methanation reaction |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210867A (en) * | 2006-12-27 | 2008-07-02 | 中国石油化工股份有限公司 | Hydrodesulphurization catalyst activity measuring method and device for implementing the method |
| CN101907591A (en) * | 2010-07-20 | 2010-12-08 | 北京化工大学 | Multi-atmosphere dynamic thermogravimetric-differential thermal analyzer and application thereof in sulfur transfer performance simulation and evaluation of flue gas |
-
2016
- 2016-08-16 CN CN201610673541.XA patent/CN106226190A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210867A (en) * | 2006-12-27 | 2008-07-02 | 中国石油化工股份有限公司 | Hydrodesulphurization catalyst activity measuring method and device for implementing the method |
| CN101907591A (en) * | 2010-07-20 | 2010-12-08 | 北京化工大学 | Multi-atmosphere dynamic thermogravimetric-differential thermal analyzer and application thereof in sulfur transfer performance simulation and evaluation of flue gas |
Non-Patent Citations (4)
| Title |
|---|
| 孙晓明 等: "羰基镍的形成原因分析及预防措施", 《齐鲁石油化工》 * |
| 孙经东: "传统合成氨工艺中甲烷化催化剂的失活和预防", 《炼油与化工》 * |
| 胡大成 等: "甲烷化催化剂及反应机理的研究进展", 《过程工程学报》 * |
| 赵安民: "合成气甲烷化镍基催化剂的研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106841293A (en) * | 2017-01-26 | 2017-06-13 | 芜湖市纽泰知识产权信息咨询有限公司 | A kind of method that utilization difference quotient thermogravimetric evaluates catalyst |
| CN106841293B (en) * | 2017-01-26 | 2019-05-28 | 王宏铭 | A method of catalyst is evaluated using difference quotient thermogravimetric |
| CN109894157A (en) * | 2017-12-07 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of method for inhibiting Raney nickel nickel to be lost and its application in methanation reaction |
| CN109894157B (en) * | 2017-12-07 | 2021-09-07 | 中国科学院大连化学物理研究所 | Method for inhibiting nickel loss of nickel catalyst and application of method in methanation reaction |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ming et al. | Characterization of cobalt Fischer-Tropsch catalysts I. Unpromoted cobalt-silica gel catalysts | |
| Antonetti et al. | Novel microwave synthesis of ruthenium nanoparticles supported on carbon nanotubes active in the selective hydrogenation of p-chloronitrobenzene to p-chloroaniline | |
| Pitkäaho et al. | Oxidation of dichloromethane over Pt, Pd, Rh, and V2O5 catalysts supported on Al2O3, Al2O3–TiO2 and Al2O3–CeO2 | |
| CA2718506C (en) | Production method of liquid hydrocarbons from natural gas | |
| CA2718960C (en) | Production method of liquid hydrocarbons from natural gas | |
| Kabe et al. | Hydrodesulfurization and hydrogenation reactions on noble metal catalysts: I. Elucidation of the behavior of sulfur on alumina-supported platinum and palladium using the 35S radioisotope tracer method | |
| Strucks et al. | A short review on Ni‐catalyzed methanation of CO2: reaction mechanism, catalyst deactivation, dynamic operation | |
| Dandl et al. | Mechanistic approach for the kinetics of the decomposition of nitrous oxide over calcined hydrotalcites | |
| CN106226190A (en) | A kind of system of laboratory evaluation Raney nickel inactivation performance | |
| CN104888783A (en) | Methanation catalyst, preparation method and application thereof | |
| CN106018664B (en) | A kind of method of laboratory evaluation Raney nickel inactivation performance | |
| EP2318482B1 (en) | Process to purify ethylene-containing off-gas feed streams | |
| CN102249835B (en) | Selective hydrogenation method of alkyne and alkadiene in C4 hydrocarbon material flow | |
| CN105457637B (en) | A kind of carbon dioxide methanation catalyst and the preparation method and application thereof | |
| Wang | Degradation of aqueous 2-Amino-2-methyl-1-propanol for carbon dioxide capture | |
| CN102249834B (en) | Selective hydrogenation method of alkyne and dialkene in alkene stream | |
| Inayat et al. | Decomposition of N2O at low temperature over Co3O4 prepared by different methods | |
| Jing et al. | Promotional Effect of Ag on the Catalytic Decomposition of N2O in the Presence of O2 over the Al2O3-Supported Rh Catalyst | |
| CN106018155A (en) | System for evaluating nickel catalyst inactivation performance | |
| CN203405453U (en) | Detection device for catalyst activity of SCR denitration system | |
| CN112452340A (en) | Catalyst for preparing propylene by selective hydrogenation of propyne, and preparation method and application thereof | |
| CN1327955C (en) | Method for preparing platinum sulfide dehydrogenation catalyst | |
| CN105601592A (en) | Method for preparation of 2-methyltetrahydrofuran through one-step hydrogenation | |
| US20230219834A1 (en) | Treatment of nitrogen compounds in spent caustic | |
| CN102250638B (en) | Hydrogenation method for unsaturated hydrocarbon in hydrocarbon stream |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161214 |
|
| RJ01 | Rejection of invention patent application after publication |