CN108279181A - The method and apparatus of coke hydrogen-carbon ratio on a kind of measurement porous catalyst - Google Patents
The method and apparatus of coke hydrogen-carbon ratio on a kind of measurement porous catalyst Download PDFInfo
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- CN108279181A CN108279181A CN201710009177.1A CN201710009177A CN108279181A CN 108279181 A CN108279181 A CN 108279181A CN 201710009177 A CN201710009177 A CN 201710009177A CN 108279181 A CN108279181 A CN 108279181A
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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
- G01N31/12—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using combustion
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Abstract
The present invention provides a kind of methods and apparatus of coke hydrogen-carbon ratio on measurement porous catalyst.The equipment includes：Gas purge system, sample combustion system, smoke absorption system；Gas purge system includes inert gas gas cylinder, oxidizing gas gas cylinder, gas decompression mechanism, gas flowmeter measuring mechanism, triple valve, de- H2O drying towers, de- CO2Drying tower；Inert gas gas cylinder, oxidizing gas gas cylinder are connected with triple valve, and connecting pipe is equipped with gas decompression mechanism；Triple valve and de- H2O drying towers, de- CO2Drying tower is in series, and connecting pipe is equipped with gas flowmeter measuring mechanism；The first tubular heater and the second tubular heater that sample combustion system includes heating tube, is set in outside heating tube；Smoke absorption system includes concatenated H2O absorption tubes, NOx absorption tubes, CO2Absorption tube；Heating tube and de- CO2Drying tower, H2O absorption tubes connect.The present invention also provides the methods for measuring coke hydrogen-carbon ratio on porous catalyst using above equipment.
Description
Technical field
The present invention relates to a kind of method and apparatus of coke hydrogen-carbon ratio on measurement porous catalyst, belong to petrochemical technology
Field.
Background technology
Molecular sieve catalyst because its high activity, it is highly selective be widely used in petroleum chemical industry, but existing for its own
Duct can make some polymer substance dehydrogenative condensations in reaction process form coke species deposition wherein, block duct to shadow
Catalyst activity is rung, such coke species (hereinafter referred to as coke) its main component is C and H.
In the industrial production, pass through the measurement to hydrogen-carbon ratio of coke on catalyst, it can be determined that feedstock property in reactor,
The variation of the characteristics such as catalyst activity and process conditions.For example, in refinery catalytic cracking unit, hydrogen-carbon ratio is commonly used to judge
The height of the steam stripping efficiency of spent agent stripper, the height of hydrogen-carbon ratio have an effect on the carbon-burning load and reaction-regeneration system of regenerator
Thermal balance.Hydrogen-carbon ratio is mass ratio, and the place that specification does not explain is mass ratio.
The measurement of STRENGTH ON COKE hydrogen-carbon ratio, it is crucial that Accurate Determining H content, because catalyst has a large amount of micropores, tool
There is very high Kong Rong (0.3-0.6mL/g) and specific surface area (50-300m2/ g), therefore there is stronger water imbibition, and in zeolite
A certain proportion of OH groups and a certain amount of crystallization water may also be carried, the H in the water meeting STRENGTH ON COKE of the part in measurement process
The accurate measurement of content interferes, and keeps H content measured value higher, cannot finally obtain the exact value of coke hydrogen-carbon ratio.
Mainly there are flue gas analysis method, sour molten-element method, thermogravimetric-mass spectrum to the research of hydrogen-carbon ratio of coke on catalyst at present
Combination method.
Flue gas analysis method is that the flue gas composition after being burnt using STRENGTH ON COKE is analyzed, according to carbon dioxide in flue gas, one
The volume fraction of carbonoxide and oxygen calculates the hydrogen-carbon ratio in coke, but this method is completely dependent on oxycarbide and oxygen
The measurement of content, field experience show that its accuracy is relatively low, or even it sometimes appear that the case where exceeding theoretical limit.For example, having
When the hydrogen-carbon ratio that is calculated be even higher than the hydrogen-carbon ratio of cracked stock.
Sour molten-element method is that catalyst material is utilized to dissolve and the undissolved characteristic of coke in strong acid, after dissolving
Catalyst coke is stripped down from catalyst using centrifugal separation, be dried and dehydrated and fire coke, and profit again later
The product after burning is measured with elemental microanalysis method, finally calculates the content of C and H element in coke.But the method implements
It is very cumbersome, and the loss or segregation of sample are often resulted in the molten and centrifugal separation processes of acid, and finally influence measurement result
Accuracy.
TG-MS combination method is removed with inert gas high-temperature blowing in coked catalyst first in thermogravimetric analyzer
Adsorb water and combine water, after burn under oxygen, the gas after burning is passed through in mass spectrum, passes through mass spectrum quantitative analysis CO2Peak and
H2The peaks O finally obtain the hydrogen-carbon ratio of coke by accordingly converting.Sample size is measured by thermogravimetric analyzer to be limited, this method is only
The catalyst sample of Gamma Magnitude can be used, it is difficult to eliminate the uneven error brought of catalyst sampling.In addition, mass spectrograph is usually quantitative
Measurement effect is bad, be easy to cause larger experimental error.In addition, thermogravimetric analyzer and mass spectrograph are usually all costly
Precision instrument needs to be equipped with the senior technician by screwing up discipline, it is difficult in oil plant or chemical plant analysis room large area
Using.
Invention content
In order to solve the above technical problems, the purpose of the present invention is to provide a kind of surveys of carbon deposit porous catalyst coke hydrogen-carbon ratio
The equipment of amount, the device structure is simple, operating cost is cheaper, and can keep relatively high measurement accuracy, is suitble to general
It is used in logical oil plant or chemical plant analysis room.
In order to achieve the above objectives, the present invention provides a kind of equipment of coke hydrogen-carbon ratio on measurement porous catalyst, packets
It includes：Gas purge system, sample combustion system, smoke absorption system；Wherein：
Gas purge system includes inert gas gas cylinder, oxidizing gas gas cylinder, gas decompression mechanism, measurement of gas flow machine
Structure, triple valve, de- H2O drying towers, de- CO2Drying tower；Inert gas gas cylinder, oxidizing gas gas cylinder are connected with triple valve respectively, and three
Port valve is respectively equipped with gas decompression mechanism for switching inert gas and oxidizing gas in connecting pipe, be used for high pressure
Cyclinder gas be reduced to using pressure；Triple valve and de- H2O drying towers, de- CO2Drying tower is in series, also, in the company of three
Take over road is equipped with gas flowmeter measuring mechanism；De- H2O drying towers and de- CO2Drying tower is respectively used to eliminate in gas included
H2O and CO2Impurity；
Sample combustion system includes heating tube, the first tubular heater and the second tubular heater, wherein the first tubular type adds
Hot stove and the second tubular heater are set in the outside of heating tube；
Smoke absorption system includes concatenated H2O absorption tubes, NOx absorption tubes, CO2Absorption tube；
The entrance of heating tube and de- CO2The outlet of drying tower connects, the outlet of heating tube and H2The entrance of O absorption tubes connects.
In above equipment, it is preferable that the gas in inert gas gas cylinder is the gas that discord catalyst reacts, excellent
Select helium or argon gas；Gas in oxidizing gas gas cylinder is the gaseous mixture of compressed air, pure oxygen or pure oxygen and inert gas.
In above equipment, the heating pipeline section of first tube furnace package is for placing catalyst sample, in conjunction with passing through gas
The difference and the different tubular type furnace temperatures of control of body type can realize dehydration and the burning process of catalyst respectively, it is preferable that
It is equipped with porcelain boat in the part that heating tube is wrapped up by the first tubular heater, the placement and taking-up of sample, material are completed by porcelain boat
Material can be the heat-resisting materials such as quartz, ceramics.
In above equipment, it is preferable that heating tube is catalyzed oxygen by CO is placed in part that the second tubular heater wraps up
Change catalyst, effect is the CO in catalysis oxidation flue gas at high temperature, its total overall reaction is made to generate CO2, ensure the C in coke
Element generates CO2And finally fully absorbed in absorption system, which controls suitable temperature by burning process
The CO of middle generation is completely converted into CO2；Preferably, above-mentioned CO catalyst for catalytic oxidation is copper oxide.
In above equipment, it is preferable that sample combustion system further includes being set in the third tubular heater of heating tube；More
Preferably, the examination for absorbing sulfide, chloride or other impurity is placed in the part that heating tube is wrapped up by third tubular heater
Agent, for removing the sulphur/chlorine compound generated in coke combustion or other impurity, to reduce the shadow analyzed carbon
It rings, improves C in STRENGTH ON COKE, the accuracy that H element measures；It is highly preferred that the reagent for absorbing sulfide and chloride is plumbous chromate
And filamentary silver.
Temperature regulating device can be carried on all tubular heaters, operation temperature can be by autonomous control.For difference
Catalyst sample can suitably adjust catalyst sample amount, the diameter of heating tube and the heating tube in three heating furnaces
The quality of length, the quality of copper oxide, the quality of plumbous chromate and filamentary silver filled layer.
In above equipment, it is preferable that heating tube is quartz glass tube or stainless steel tube.
In above equipment, burns flue gas and pass through H successively2O absorption tubes, NOx absorption tubes and CO2Absorption tube, H therein2O、
Oxynitrides (NOx) and CO2It is absorbed successively.One CO2Absorption tube may not be able to fully absorb all CO2, therefore, can
Two CO are arranged2Absorption tube, i.e. smoke absorption system include concatenated H2O absorption tubes, NOx absorption tubes, two CO2Absorption tube.
In above equipment, it is preferable that H2Anhydrous calcium chloride or anhydrous magnesium chloride, above two object are filled in O absorption tubes
Matter has strong absorptive and will not absorb other gases, will not be impacted to the measurement of follow-up C element；In NOx absorption tubes
Filled with manganese dioxide, manganese dioxide can absorb the nitrogen oxides generated in gas after burning, reduce its shadow measured C element
It rings, therefore places it in CO2Before absorption tube；CO2Alkali asbestos are filled in absorption tube, alkali asbestos can fully absorb combustion gas
Carbon dioxide in body completes measurement to C element, since it can absorb water and nitrogen oxides, places it in H2O absorbs
After pipe and NOx absorption tubes.
In above equipment, it is preferable that CO2The outlet connection of absorption tube is free U-tube and bubble meter；Empty U-tube is placed
In CO2After absorption tube, buffering can be played the role of；It is highly preferred that being filled with the concentrated sulfuric acid in bubble meter.By the way that bubble is arranged
The concentrated sulfuric acid is counted and be packed into, the H in instrument extraneous air can be prevented2O and CO2Reflux anti-channeling enters absorption system, causes hydrocarbon member
The inaccuracy of plain measurement result, while whether can also visually observe the gas flow rate in test process uniform.
Specific embodiment according to the present invention, the equipment can be related to outfit certainly by adding computer control system
Control instrument and control mechanism realize the automation of instrumentation, to further accurately control each operating procedure stability and
Consistency reduces the error that manual operation is brought, it is ensured that the repeatability and accuracy of measurement result.Specific implementation method is as follows：
Being added in gas purge system can be by the gas flowmeter measuring mechanism of computer system real-time control and threeway
Valve, to realize the flow of computer system control inert gas and oxidizing gas, be passed through the time and switching between the two；
The temperature control mechanism of computer control, furnace temperature, heating rate and guarantor for controlling tubular heater are added in sample combustion system
Hold the time；Automatic on-line weighing system is added in smoke absorption system, for measuring the absorbent matter in each absorption tube in real time
The variation of amount can obtain and adsorb water on coked catalyst, the H that coke burning generates in real time2O and CO2Quality, save and surveying
The time for taking dress U-tube to weigh during examination, while reducing because of the human error brought in operating process, it is accurate to improve test
Degree.Computer control system is connect with gas flowmeter measuring mechanism, triple valve, temperature control mechanism, automatic on-line weighing system respectively.
By above-mentioned automatic instrument(s) and control mechanism and computer control system, the flow of inert gas and oxidizing gas can be controlled
Be passed through each absorption tube weightening in the switching of time, triple valve, control, the smoke absorption system respectively of three tube furnace furnace temperature
Real-time display and record, and finally the quality and hydrogen-carbon ratio of Hydrogen In The Coke carbon are obtained according to record data.
The present invention also provides it is a kind of measurement porous catalyst on coke hydrogen-carbon ratio method, be using above equipment into
Capable, this approach includes the following steps：
Appropriate porous catalyst sample is placed in the heating tube of the first tubular heater package, under appropriate drying temperature
It is passed through inert gas, remove the absorption water adsorbed in coked catalyst and combines water；
Inert gas is switched to oxidizing gas, at the same by the temperature of tubular heater rise to it is specified burn temperature, wait for
Time is enough after all burning down the coke in catalyst, measures H in this period2O absorption tubes, CO2The weightening of absorption tube,
Calculate the hydrogen-carbon ratio of coke.
Specific embodiment according to the present invention, it is preferable that the above method includes step in detail below：
Inert gas gas cylinder is opened, it is 50-150mL/min to adjust its flow, is accessed inert gas using triple valve, and
Verification system air-tightness, if air-tightness well carries out in next step；
The temperature of first tubular heater is adjusted to 100-380 DEG C, the temperature of the second tubular heater is adjusted to 600-850
DEG C, the temperature of third tubular heater is adjusted to 600-850 DEG C；
Wait for that the temperature of each tubular heater rises to assigned temperature, 0.1-20g samples, which are placed in the first tubular heater, to be wrapped
In the heating tube wrapped up in, be passed through inert gas and keep 5-40min, until in sample absorption water and eliminate completely in conjunction with water；
Remove H2O absorption tubes simultaneously close its cock, by NOx absorption tubes, CO2The cock of absorption tube is closed, and H is weighed2O inhales
The quality of closed tube, and compare to obtain absorption water with its original quality and combine the quality m of water1；
By H2The cock of O absorption tubes is opened and is connected, while by NOx absorption tubes, CO2The cock of absorption tube is opened；
It closes inert gas gas cylinder and opens oxidizing gas gas cylinder, it is 50-150mL/min to adjust its flow, utilizes threeway
Valve accesses oxidizing gas, and verifies system air-tightness, if air-tightness is good, the temperature of the first tubular heater is adjusted to 600-
850 DEG C, 10-60min is kept, to ensure the completely burned of coke；
It is to be combusted to close oxidizing gas gas cylinder after reaction, close H2O absorption tubes, NOx absorption tubes, CO2Absorption tube
Cock, and by H2O absorption tubes, CO2Absorption tube is removed and is weighed and the last time quality versus that weighs respectively obtains and burns combustion
Quality of heating up water m2And CO2Quality of adsorption m3；
Using following formula, the hydrogen-carbon ratio H/C of coke is calculated：
Inventor has carried out physics research using thermogravimetry to several carbon deposit porous catalysts, in different temperature
It is dehydrated and has been burnt under degree and time, determined corresponding thermogravimetric weightlessness figure, as a result show and inhaled on carbon deposit porous catalyst
The content of attached water and combination water is fixed, and its proportion is different in different catalysts, highest to account for total weight loss
40%, therefore, if not removing this part water in advance in carbon deposit porous catalyst hydrogen-carbon ratio test process, and this part water
When the water that mistake attribution is generated to H element burning, very big measurement error is will result in, so must be gone before coke burning
It removes this part water and does not influence coke chemical composition simultaneously.Inventor is by further research and test repeatedly, really
Determined using inert gas purge removal absorption water and combine water method, and determine suitable purge gas media type and
Tolerance, dehydration temperaturre and dewatering time.
The H that method and apparatus provided by the present invention is generated by measuring coke burning2O and CO2Content determines its hydrogen carbon
Than, increase inert gas purge process before burning process, to remove the absorption water adsorbed in coked catalyst and combine water,
The influence for avoiding it from measuring H content.In order to which the carbon ensured in all coke can be converted to CO2, burn stove (the first pipe
Formula heating furnace) it is provided with the Catalytic oxidation furnace (the second tubular heater) of CO later.In addition, being also provided in gas absorption system
Ensure H2O and CO2The measure (i.e. each absorption tube) being completely absorbed, to ensure final hydrogen-carbon ratio measurement accuracy.
Equipment provided by the invention is a kind of equipment suitable for commercial measurement carbon deposit porous catalyst coke hydrogen-carbon ratio, should
Measurement method used by equipment is compared with existing measurement method, and the sample size of bigger may be used, and ranges up to tens grams, can
The uneven measurement error brought is sampled to significantly reduce, is more suitable for the analysis of industrial process coked catalyst.The equipment system
Cause this lower, the requirement to operating personnel's technical ability is not also high, and can keep relatively high measurement accuracy, is suitble in common stone
It is used in change company or chemical plant analysis room, can be used for research institution and test indoor sample analysis.
Description of the drawings
Fig. 1 is the structural schematic diagram of the equipment for the measurement porous catalyst coke hydrogen-carbon ratio that embodiment 1 provides.
Main Reference label declaration：
1 inert gas gas cylinder, 2 oxidizing gas gas cylinders, 3 gas decompression mechanisms, 4 triple valves, 5 gas flowmeter measuring mechanisms, 6
Rubber plug, 7 copper wires, 8 porcelain boats, 9 heating tubes, 10 copper oxide particles, 11 plumbous chromates, 12 filamentary silvers, 13 water suction U-tubes, 14 nitrogen oxides U
Shape absorption tube, 15 carbon dioxide U-shaped absorption tubes, 16 blank U-tubes, 17 bubble meters, 18 third tube furnaces, 19 second tube furnaces,
20 first tube furnaces, 21 drying towers
Specific implementation mode
In order to which technical characteristic, purpose and the advantageous effect to the present invention are more clearly understood, now to the skill of the present invention
Art scheme carry out it is described further below, but should not be understood as to the present invention can practical range restriction.
Embodiment 1
A kind of equipment measuring coke hydrogen-carbon ratio on porous catalyst is present embodiments provided, structure is as shown in Figure 1.It should
Equipment includes gas purge system, sample combustion system and smoke absorption system three parts；Wherein：
Gas purge system includes 1, oxidizing gas gas cylinder 2 of an inert gas gas cylinder, gas decompression mechanism 3, three
5, two port valve 4, gas flowmeter measuring mechanism calcium chloride jars 21, inert gas gas cylinder 1, oxidizing gas gas cylinder 2 are respectively with three
Port valve 4 connects, and gas decompression mechanism 3 is respectively equipped in connecting pipe；Another outlet of triple valve 4 and a gas dry
The entrance of tower 21 connects, and two calcium chloride jars 21 are connected, and the capacity of calcium chloride jar 21 is 500mL, and inside contains absorption H2O
And CO2The adsorbent of impurity, to avoid H2O and CO2Into sample combustion system；
Sample combustion system includes mainly three different sizes and the tubular heater with temperature regulating device, gas lead to successively
It crosses the first tube furnace 20, the second tube furnace 19 and third tube furnace 18, three tube furnaces and is wrapped in the heating of an internal diameter 25mm
The outside of pipe 9 (quartz glass tube)；Porcelain boat 8 is equipped in 9 sections of the heating tube of first tube furnace 20, catalyst sample is placed on porcelain boat
On 8, this part is used to complete the dehydration and drying of catalyst sample and burns, and is filled in 9 sections of the heating tube of the second tube furnace 19
There is copper oxide particle 10, plumbous chromate 11 and filamentary silver 12 are filled in 9 sections of the heating tube of third tube furnace 18；
The entrance of heating tube 9 is connect with the outlet of drying tube 21, also, the inlet of heating tube 9 is equipped with rubber plug 6, and
Copper wire 7, and copper wire 7 is designed between each filler in heating tube, the effect of copper wire 7 is the fixed each filler of isolation,
CO catalysis oxidations can also be played the role of by reacting the copper oxide generated with oxygen at high temperature simultaneously；
Absorption system includes mainly five U-shaped absorption tubes, that is, absorb water U-tube 13, nitrogen oxides U-shaped absorption tube 14, two
Carbon dioxide U-shaped absorption tube 15, blank U-tube 16 and a bubble meter 17, the volume of five U-shaped absorption tubes is respectively 250mL,
For H2O and CO2Absorption and mass measurement.Wherein, filling anhydrous calcium chloride or anhydrous magnesium chloride, nitrogen oxygen in water suction U-tube 13
Manganese dioxide is filled in compound U-shaped absorption tube 14, and alkali asbestos, blank U-shaped absorption tube 16 are filled in carbon dioxide U-shaped absorption tube 15
It is placed on behind carbon dioxide U-shaped absorption tube, the concentrated sulfuric acid is housed in bubble meter 17.
It is about that the step of porous coked catalysts of 4-8% are detected is as follows to a certain type coke quality content：
1) equipment each section is connected by Fig. 1 modes, and opens the cock of each U-tube；
2) inert gas gas cylinder is opened, it is 120mL/min to adjust its flow, is accessed inert gas using triple valve, and
Verification system air-tightness, if air-tightness well carries out in next step；
3) temperature of the first tube furnace 20 is adjusted to 350 DEG C, the temperature of the second tube furnace 19 is adjusted to 800 DEG C, third tubular type
The temperature of stove 18 is adjusted to 600 DEG C；
4) inert gas gas cylinder 1 is opened, it is 120mL/min to adjust its flow, 16 cock of blank U-tube is closed, if gas
The registration of flowmeter body measuring mechanism 5 is down to 20mL/min hereinafter, then proving that the system air-tightness is good, otherwise checks each connection
Place until air-tightness is good, and opens 16 cock of blank U-tube；
5) wait for that each furnace temperature rises to assigned temperature, weighing 2.5002g samples using precision balance is placed in porcelain boat 8, utilizes
Push-rods push it into the first tube furnace 20, be passed through inert gas keep 30min, until in sample absorption water and combine water
It eliminates completely；
6) it removes water suction U-tube 13 and closes its cock, the cock of remaining U-tube is closed, is claimed using precision balance
The quality of water suction U-tube 13 is taken, and compares to obtain absorption water with its original quality and combines the quality m of water1For 0.0584g；
7) cock for the U-tube 13 that absorbs water is opened and is attached by Fig. 1, while the cock of remaining U-tube being opened；
8) it closes inert gas gas cylinder 1 and opens oxidizing gas gas cylinder 2, it is 120mL/min to adjust its flow, utilizes threeway
Valve 4 verifies system air-tightness by oxidizing gas access system, and according to step 3), if air-tightness is good, by the first tube furnace
20 temperature is adjusted to 850 DEG C, 30min is kept, to ensure the completely burned of coke；
9) it is to be combusted after reaction, close oxidizing gas gas cylinder 2, close the cock of each U-tube, and the U-tube that will absorb water
13, carbon dioxide U-shaped absorption tube 15, which is removed, weighs it with precision balance and the last time quality versus that weighs respectively obtains
Burn burning water quality m2For 0.0807g and CO2Quality of adsorption m3For 0.4625g；
10) following formula is utilized, the hydrogen-carbon ratio that can obtain coke is 7.1087%；
Before being tested, need to carrying out blank assay (do not place sample in porcelain boat and repeat the above experiment step), with
Remove the influence of other substances such as the water in porcelain boat and air.
Laboratory detection result shows after analyzing personnel's skilled operation, measuring result error can control value within 3%.
Embodiment 2
The present embodiment use known hydrogen carbon molecules than standard substance (hydrogen carbon molecules ratio for 2) examine and measure porous catalyst
The accuracy of the equipment of upper coke hydrogen-carbon ratio, specific implementation step are as follows：
1) equipment each section is connected by Fig. 1 modes, and opens the cock of each U-tube；
2) temperature of the first tube furnace 20 is adjusted to 800 DEG C, the temperature of the second tube furnace 19 is adjusted to 800 DEG C, third tubular type
The temperature of stove 18 is adjusted to 600 DEG C；
3) oxidizing gas gas cylinder 2 is opened, it is 120mL/min to adjust its flow, 16 cock of blank U-tube is closed, if gas
The registration of flowmeter body measuring mechanism 5 is down to 20mL/min hereinafter, then proving that the system air-tightness is good, otherwise checks each connection
Place until air-tightness is good, and opens 16 cock of blank U-tube；
4) wait for that each furnace temperature rises to assigned temperature, weighing 0.2124g samples using precision balance is placed in porcelain boat 8, utilizes
Push-rods push it into the first tube furnace 20, are passed through oxidizing gas and keep 30min, until sample completely burned；
5) it is to be combusted after reaction, close oxidizing gas gas cylinder 2, close the cock of each U-tube, and the U-tube that will absorb water
13, carbon dioxide U-shaped absorption tube 15, which is removed, weighs it with precision balance and the last time quality versus that weighs respectively obtains
Burn burning water quality m2For 0.2595g and CO2Quality of adsorption m3For 0.6314g；
6) following formula is utilized, the hydrogen carbon molecules ratio that can obtain standard substance is 2.0093, and relative error is
0.4645%；
Claims (10)
1. a kind of equipment measuring coke hydrogen-carbon ratio on porous catalyst comprising：Gas purge system, sample combustion system,
Smoke absorption system；Wherein：
The gas purge system includes inert gas gas cylinder, oxidizing gas gas cylinder, gas decompression mechanism, measurement of gas flow machine
Structure, triple valve, de- H2O drying towers, de- CO2Drying tower；The inert gas gas cylinder, the oxidizing gas gas cylinder respectively with it is described
Triple valve is connected, and gas decompression mechanism is respectively equipped in connecting pipe；The triple valve and the de- H2O drying towers take off
CO2Drying tower is in series, also, gas flowmeter measuring mechanism is equipped in the connecting pipe of three；
The sample combustion system includes heating tube, the first tubular heater and the second tubular heater, and first tubular type adds
Hot stove and the second tubular heater are set in the outside of the heating tube；
The smoke absorption system includes concatenated H2O absorption tubes, NOx absorption tubes, CO2Absorption tube；
The entrance of the heating tube and the de- CO2The outlet of drying tower connects, the outlet of the heating tube and the H2O absorbs
The entrance of pipe connects.
2. equipment according to claim 1, wherein the gas in the inert gas gas cylinder is that discord catalyst occurs instead
The gas answered, preferably helium or argon gas, the gas in the oxidizing gas gas cylinder are compressed air, pure oxygen or pure oxygen and inertia
The gaseous mixture of gas.
3. equipment according to claim 1, wherein in the part that the heating tube is wrapped up by first tubular heater
Equipped with porcelain boat, it is preferable that the material of the porcelain boat is quartz or ceramics.
4. equipment according to claim 1 or 3, wherein the portion that the heating tube is wrapped up by second tubular heater
It is placed with CO catalyst for catalytic oxidation in point；Preferably, the CO catalyst for catalytic oxidation is copper oxide.
5. equipment according to claim 1, wherein the sample combustion system further includes being set in outside the heating tube
Third tubular heater；Preferably, it is placed in the part that the heating tube is wrapped up by the third tubular heater and absorbs sulphur
The reagent of compound, chloride or other impurities；It is highly preferred that the reagent is plumbous chromate and filamentary silver.
6. equipment according to claim 1, wherein the heating tube is quartz glass tube or stainless steel tube.
7. equipment according to claim 1, wherein the H2Anhydrous calcium chloride and/or anhydrous chlorine are filled in O absorption tubes
Change magnesium, manganese dioxide, the CO are filled in the NOx absorption tubes2Alkali asbestos are filled in absorption tube；
Preferably, the smoke absorption system includes concatenated H2O absorption tubes, NOx absorption tubes, two CO2Absorption tube.
8. equipment according to claim 1 or claim 7, wherein the CO2The outlet connection of absorption tube is free U-tube and bubble
Meter；Preferably, the concentrated sulfuric acid is filled in the bubble meter.
9. according to claim 1-8 any one of them equipment, wherein the equipment further includes computer control system, temperature controlling machine
Structure, automatic on-line weighing system；
The computer control system respectively with the gas flowmeter measuring mechanism, triple valve, the temperature control mechanism, described
Automatic on-line weighing system connects；
The temperature control mechanism is used to control the temperature of tubular heater；
The automatic on-line weighing system is used to measure the variation of the absorbent quality in each absorption tube in real time.
10. a kind of method measuring coke hydrogen-carbon ratio on porous catalyst, is set using claim 1-9 any one of them
Standby progress, this approach includes the following steps：
Appropriate porous catalyst sample is placed in the heating tube of the first tubular heater package, is passed through under appropriate drying temperature
Inert gas removes the absorption water adsorbed in coked catalyst and combines water；
Inert gas is switched to oxidizing gas, at the same by the temperature of tubular heater rise to it is specified burn temperature, wait for the time
It is enough after all burning down the coke in catalyst, measures H in this period2O absorption tubes, CO2The weightening of absorption tube calculates
Go out the hydrogen-carbon ratio of coke；
Preferably, this method includes step in detail below：
Inert gas gas cylinder is opened, and it is 50-150mL/min to adjust its flow, inert gas is accessed using triple valve, and verify
System air-tightness, if air-tightness well carries out in next step；
The temperature of first tubular heater is adjusted to 100-380 DEG C, the temperature of the second tubular heater is adjusted to 600-850 DEG C, and
The temperature of three-tube type heating furnace is adjusted to 600-850 DEG C；
It waits for that the temperature of each tubular heater rises to assigned temperature, 0.1-20g samples is placed in what the first tubular heater was wrapped up
In heating tube, be passed through inert gas and keep 5-40min, until in sample absorption water and eliminate completely in conjunction with water；
Remove H2O absorption tubes simultaneously close its cock, by NOx absorption tubes, CO2The cock of absorption tube is closed, and H is weighed2O absorption tubes
Quality, and compare to obtain absorption water with its original quality and combine the quality m of water1；
By H2The cock of O absorption tubes is opened and is connected, while by NOx absorption tubes, CO2The cock of absorption tube is opened；
It closes inert gas gas cylinder and opens oxidizing gas gas cylinder, it is 50-150mL/min to adjust its flow, will using triple valve
Oxidizing gas accesses, and verifies system air-tightness, if air-tightness is good, the temperature of the first tubular heater is adjusted to 600-850
DEG C, 10-60min is kept, to ensure the completely burned of coke；
It is to be combusted to close oxidizing gas gas cylinder after reaction, close H2O absorption tubes, NOx absorption tubes, CO2The cock of absorption tube,
And by H2O absorption tubes, CO2Absorption tube is removed and is weighed and the last time quality versus that weighs respectively obtains and burns burning water quality
Measure m2And CO2Quality of adsorption m3；
Using following formula, the hydrogen-carbon ratio H/C of coke is calculated：
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111272946A (en) * | 2020-03-30 | 2020-06-12 | 合肥工业大学 | Device and method for measuring content of organic carbon in industrial waste salt |
| CN111366678A (en) * | 2020-04-03 | 2020-07-03 | 河南华豫达消防安全检测有限公司 | Drying device for air pipeline of paving material combustion test device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103604910A (en) * | 2013-12-02 | 2014-02-26 | 中国天辰工程有限公司 | Method for detection of hydrogen-carbon ratio of coke on catalyst |
| CN104914130A (en) * | 2014-03-10 | 2015-09-16 | 河北联合大学 | Small particle coke gasification reactivity determination method and small particle coke gasification reactivity determination apparatus |
| CN206348249U (en) * | 2017-01-06 | 2017-07-21 | 中国石油大学(北京) | The equipment of coke hydrogen-carbon ratio on a kind of measurement porous catalyst |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103604910A (en) * | 2013-12-02 | 2014-02-26 | 中国天辰工程有限公司 | Method for detection of hydrogen-carbon ratio of coke on catalyst |
| CN104914130A (en) * | 2014-03-10 | 2015-09-16 | 河北联合大学 | Small particle coke gasification reactivity determination method and small particle coke gasification reactivity determination apparatus |
| CN206348249U (en) * | 2017-01-06 | 2017-07-21 | 中国石油大学(北京) | The equipment of coke hydrogen-carbon ratio on a kind of measurement porous catalyst |
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| J. BARBIER等: "《CHARACTERIZATION OF COKE BY HYDROGEN AND CARBON ANALYSIS》", 《REACT. KINET. CATAL. LETT.》, vol. 29, no. 2, pages 323 - 330 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111272946A (en) * | 2020-03-30 | 2020-06-12 | 合肥工业大学 | Device and method for measuring content of organic carbon in industrial waste salt |
| CN111366678A (en) * | 2020-04-03 | 2020-07-03 | 河南华豫达消防安全检测有限公司 | Drying device for air pipeline of paving material combustion test device |
| CN111366678B (en) * | 2020-04-03 | 2022-06-10 | 河南华豫达工程技术有限公司 | Drying device for air pipeline of paving material combustion test device |
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