CN106018664B - A kind of method of laboratory evaluation Raney nickel inactivation performance - Google Patents
A kind of method of laboratory evaluation Raney nickel inactivation performance Download PDFInfo
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- CN106018664B CN106018664B CN201610673693.XA CN201610673693A CN106018664B CN 106018664 B CN106018664 B CN 106018664B CN 201610673693 A CN201610673693 A CN 201610673693A CN 106018664 B CN106018664 B CN 106018664B
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- G—PHYSICS
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- 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
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Abstract
A kind of laboratory evaluation system that can conveniently and effectively evaluate Raney nickel and lead to the performance of inactivation because forming carbonyl nickel.The system is built upon on thermogravimetric analysis platform, by detecting under certain temperature when the gas containing CO flows through the nickel catalyst surface of reduction-state, the situation of change of catalyst sample weight judges the wastage of active component nickel formation carbonyl nickel in catalyst, and the carbonyl nickel by being connected to System Back-end absorbs decomposer, and the carbonyl nickel of the hypertoxicity that may be present from the tail gas flowed out in sample cell is decomposed.
Description
Technical field
The present invention relates to a kind of methods that laboratory evaluation Raney nickel inactivates performance, and in particular to a kind of evaluation nickel catalysis
The method that performance is inactivated when agent uses in environment containing CO.
Background technology
Raney nickel is a kind of extremely extensive catalyst prod of use in chemical industry, is especially adding hydrogen mistake
Cheng Zhong, Raney nickel hydrogenation activity is high, and price also has great advantage with respect to noble metal catalyst, so Raney nickel is with high
Cost performance.In many hydrogenation process, the hydrogenation process of CO（CO+3H2↔CH4+H2O）, that is, methanation is very
Also all it is to use Raney nickel in multi-field.For example, during cracking separation preparing ethylene, propylene, it is suitable with by-product
The hydrogen-rich fraction of quantity, about hydrogen 90~96%, while there is also 0.1~1.0% carbon monoxide.Since CO can be caused
Carbon two, C_3 hydrogenation catalyst poisoning inactivation, therefore this hydrogen-rich cannot directly make plus hydrogen hydrogen source, and must first take off wherein CO
It removes.It is industrial just to remove CO, i.e. CO+3H using the method for methanation2↔CH4+H2O.In synthesis ammonia plant and some device for producing hydrogen
In, methanation is also H2The final step of purification.The best behaviour of ethylene unit and methanation catalyst in synthetic ammonia installation at present
Make temperature range substantially at 300 DEG C or so, if the temperature in use of catalyst can be dropped to 200 DEG C hereinafter, and can reach same
Decontamination index, then low temperature methanation process will be energy-saving and to urge into the advantage in terms of safety in production will be clearly
's.
Low temperature methanation process no doubt has many advantages, but there is also serious hidden danger, because nickel metal is at low temperature
It is easy to form the gaseous Ni (CO) for having hypertoxicity with the CO in gas phase4, and it is carried over reaction system, cause activearm to shunt
It loses, final catalyst inactivation.Be accordingly used in low temperature methanation process catalyst have to under its low temperature formed carbonyl nickel and
The performance of inactivation is evaluated, and forming the complexity that carbonyl nickel causes nickel to be lost according to it takes the circumstances into consideration to apply.
Invention content
Can conveniently and effectively evaluate Raney nickel the object of the present invention is to provide one kind causes to lose because forming carbonyl nickel
The laboratory evaluation method of performance living.This method is built upon on thermogravimetric analysis platform, by detecting under certain 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 formed carbonyl nickel wastage, and by be connected to gas emptying before carbonyl nickel absorb decomposer, will
The carbonyl nickel of hypertoxicity that may be present decomposes from the tail gas flowed out in sample cell.
Metallic nickel forms carbonyl nickel with CO and could only occur at a lower temperature, as document（PM technique,
2011, the phase of volume 29 the 4th, 290-295 pages）It points out, at 38 DEG C -93 DEG C, CO is contacted with active nickel can form carbonyl nickel, and carbonyl
Nickel can decompose again at 180 DEG C or more, and carbonyl nickel can generate the nitrate of nickel with nitric acid reaction and be decomposed.According to above-mentioned spy
Point, the method for this evaluation Raney nickel inactivation performance is using the steady temperature in 180 DEG C of temperature ranges below in of the invention
And the mode for extending heating time monitors catalyst and undergoes sample weight after the gas treatment containing CO of different time at different temperatures
Amount situation of change calculates the average weight loss rate of catalyst in the unit interval according to the data of monitoring, judges that nickel is catalyzed with this
Agent causes the trend size of inactivation because forming carbonyl nickel, and passes through the nitric acid and carbonyl nickel reactant generation nickel nitrate in drexel bottle
And CO, to eliminate the carbonyl nickel of severe toxicity.
On the other hand, metallic catalyst has the generation of carbon distribution reaction in the reaction atmosphere there are CO, and carbon distribution is one
The process of sample system weightening, and the process that gaseous state carbonyl nickel is a sample system weightlessness is formed, the opposite process carried out is such as
Fruit simultaneously occurs that the result of thermogravimetric analysis can be made intricate or even can not parse, and comes just because of the system applied to the present invention
It says, well below the lower limit temperature for forming carbon distribution, this just completely avoids the interference of carbon distribution process, makes the temperature that carbonyl nickel is formed
The trend inactivated because forming carbonyl nickel using the convenient acquisition Raney nickel of thermogravimetric analysis platform is obtained to be possibly realized.
Test method provided by the invention, specific test process are that nickel catalyst sample to be measured is put into thermogravimetric point
In the sample cell of desorption device, it is passed through H2It is restored, after reduction, in H2In to be down to the sample of gas treatment containing CO required
Temperature；Close H2, the gas containing CO is then passed through sample cell again, to sample in such a way that steady temperature extends heating time
Product are heat-treated, and thermobalance records the delta data of example weight, and the tail gas flowed out from sample cell is passed through carbonyl nickel suction
Decomposer is received, wherein the absorbing liquid held is the high concentration salpeter solution of a concentration of 6-8mol/L, tail is made by chemical reaction
Carbonyl nickel in gas decomposes, and then empties.
Parameter when specific test, when reduction, control H2Flow is in 2mL min-1•g-1Catalyst is to 20mL min-1•g-1Catalysis
Within the scope of agent, reduction temperature controls within the scope of 200 DEG C to 400 DEG C, 1 hour to 4 hours recovery time；Gas stream containing CO
Amount control is in 2mL min-1•g-1Catalyst is to 20mL min-1•g-1In range of catalysts, the wherein molar content of CO is
10% to 100%, with containing CO gas treatment reduction after nickel catalyst sample when temperature control between 80 DEG C to 180 DEG C.
A kind of method of laboratory evaluation Raney nickel inactivation performance provided by the invention, can test Raney nickel containing
Data weightless caused by due to forming carbonyl nickel in CO atmosphere, and thus judge that its inactivation during actual response becomes
Gesture, the test method are stablized effectively, and test result is directly credible, and absorb decomposer due to being connected to carbonyl nickel so that
This method more safety and environmental protection.
Specific implementation mode
The present invention is further detailed with reference to embodiment：
The following examples, which are only used for explaining in detail, illustrates the present invention, does not limit the scope of the invention in any way.
Embodiment 1
A kind of method of laboratory evaluation Raney nickel inactivation performance, the instrument and equipment used includes a set of thermogravimetric analysis
Instrument（TA Q50）And a carbonyl nickel absorbs decomposer.Carbonyl nickel absorbs the concentration of nitric acid in the drexel bottle in decomposer
For 6mol/L.
With this method evaluation Raney's nickel catalyst RTH-311（Catalyst Co., Ltd of Xinhua of Suzhou City）Inactivation performance,
1.6732g samples RTH-311 is put into the sample cell of thermogravimetric analyzer, H2With 10mL min-1•g-1The speed of catalyst flows through
Sample cell, for heating sample to 350 DEG C, example weight is constant after 130min, illustrates that reduction process terminates, example weight is at this time
1.2047g stops heating and continuing logical H2H is closed after so that sample is cooled to 160 DEG C2, while by the gaseous mixture of CO and N2（CO is accounted for
The 20% of total mole number）It is passed through sample cell, after keeping 160 DEG C, 3 hours of temperature, stops test, example weight is at this time
1.0313g, therefore at 160 DEG C, average weight loss rate v=(1.2047-1.0313) of sample RTH-311 in 3 hours/
1.2047/3=0.048 hr-1, i.e., under test conditions, the weight that sample has 4.8% per hour is lost in.
Embodiment 2
A kind of method of laboratory evaluation Raney nickel inactivation performance, the instrument and equipment used includes a set of thermogravimetric analysis
Instrument（TA Q50）And a carbonyl nickel absorbs decomposer.Carbonyl nickel absorbs the concentration of nitric acid in the drexel bottle in decomposer
In 8mol/L.
With this method evaluation Raney's nickel catalyst RTH-211（Catalyst Co., Ltd of Xinhua of Suzhou City）Inactivation performance,
1.6911g samples RTH-211 is put into the sample cell of thermogravimetric analyzer, H2With 15mL min-1•g-1The speed of catalyst flows through
Sample cell, for heating sample to 400 DEG C, example weight is constant after 110min, illustrates that reduction process terminates, example weight is at this time
1.2196g stops heating and continuing logical H2H is closed after so that sample is cooled to 120 DEG C2, while by the gaseous mixture of CO and N2（CO is accounted for
The 50% of total mole number）It is passed through sample cell, after keeping 120 DEG C, 4 hours of temperature, stops test, example weight is at this time
0.9174g, therefore at 120 DEG C, average weight loss rate v=(1.2196-0.9174) of sample RTH-211 in 4 hours/
1.2196/4=0.062 hr-1, i.e., under test conditions, the weight that sample has 6.2% per hour is lost in.
Claims (4)
1. a kind of method of laboratory evaluation Raney nickel inactivation performance, which is characterized in that by thermogravimetric analysis Raney nickel because
It is formed and inactivates performance caused by carbonyl nickel loss, operating procedures order is that catalyst to be measured is put into sample cell, is passed through H2
It is restored, when reduction controls H2Flow is in 2mL min-1∙g-1Catalyst is to 20 mL min-1∙g-1Catalyst, reduction temperature control
System is at 200 DEG C to 400 DEG C, 1 hour to 4 hours recovery time；After reduction, in H2In be cooled in next step with contain CO gas
Body handles temperature required when sample, at this moment closes H2, then the gas containing CO is passed through sample cell, the wherein Mole percent of CO
Content is 10% to 100%, range of flow 2mL min-1∙g-1Catalyst is to 20 mL min-1∙g-1Catalyst；Gas containing CO
After being passed through, using steady temperature extend heating time by the way of sample is heat-treated, hot day equal a record catalyst weight change
The data of change calculate the average weight loss rate of catalyst in the unit interval.
2. a kind of method of laboratory evaluation Raney nickel inactivation performance according to claim 1, it is characterised in that realize
The hardware platform of this method is that one is sleeved on the thermogravimetric analyzer that drexel bottle is connected to before gas is vented.
3. a kind of method of laboratory evaluation Raney nickel inactivation performance according to claim 2, it is characterised in that gas washing
The concentration of nitric acid is within the scope of 6mol/L to 8mol/L in bottle.
4. a kind of method of laboratory evaluation Raney nickel inactivation performance according to claim 1, it is characterised in that use
When the mode that steady temperature extends heating time is heat-treated sample, the steady temperature is 80 DEG C to 180 DEG C ranges
It is interior.
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