CN110346473B - Device and method for measuring carbon deposition rate of catalytic reforming catalyst - Google Patents
Device and method for measuring carbon deposition rate of catalytic reforming catalyst Download PDFInfo
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
A device and a method for measuring the carbon deposition rate of a catalytic reforming catalyst belong to the field of hydrogen production by reforming tar and steam. In the device, a nitrogen steel cylinder is communicated with a feed inlet of a quartz tube reactor through a gas flowmeter; the double-channel micro-injection pump is communicated with a feed inlet of the quartz tube reactor; the middle part of the quartz tube reactor is provided with a distribution net, the periphery of the quartz tube reactor is provided with a heat preservation tube, a discharge port of the quartz tube reactor is sequentially connected with a condensation tube and a liquid collector, and a gas outlet of the liquid collector is respectively connected with a soap bubble flowmeter and a gas chromatograph; an electric heating pipe is arranged between the heat preservation pipe and the quartz tube reactor and is connected with an electric heating temperature controller. The device is adopted to deposit carbon on the catalytic reforming catalyst, the temperature programming oxidation is adopted to measure and calculate the carbon deposition rate of the catalytic reforming catalyst, the method is used for researching the carbon deposition rate of the steam reforming hydrogen production catalyst, the data is accurate, and the effect of the carbon deposition rate can be truly reflected.
Description
Technical Field
The invention relates to the technical field of hydrogen production by reforming tar and steam, in particular to a device and a method for measuring carbon deposition rate of a catalytic reforming catalyst.
Background
The technology has a great development prospect by combining environmental protection technologies such as renewable energy, clean energy and the like, and hydrogen is produced by biomass gasification2、CO2、CO、CH4The main product gas is subjected to steam reforming, water-gas conversion, PSA hydrogen separation and compression and other processes to prepare high-purity hydrogen. However, tar, which is a byproduct, is inevitably generated in the pyrolysis gasification process. It is a black brown viscous liquid, and its main chemical composition includes twoClass (c): the first is aromatic compound mainly comprising benzene, toluene, xylene, phenol, naphthalene, styrene and indene; the second is a small amount of oxygen, nitrogen and sulfur containing compounds. The presence of tar presents a great hazard to the entire gasification system: (1) reducing the hydrogen yield; (2) after condensation, the condensed tar affects the normal operation of the system device; (3) harm human health and environment; (4) preventing further utilization of the hydrogen product.
In order to reduce the harm of tar, the existing methods for removing tar mainly comprise two main types: the first is a physical purification method divided into a wet method and a dry method, and the second is a thermochemical purification method divided into thermal cracking and catalytic reforming.
The physical purification method is to remove tar by physical means, but the dry method or the wet method only converts tar from gas phase into liquid phase or solid phase, and the tar is converted into phase state rather than being really removed.
The thermochemical cleaning law refers to a series of chemical reactions of tar under a certain temperature condition to convert macromolecular tar into micromolecular gaseous products. The method can not only reduce the tar content and recycle the energy contained in the tar, but also fundamentally eliminate the influence of the tar.
The thermal cracking method is to directly pyrolyze tar at a high temperature, and the process can convert macromolecular tar into micromolecular gaseous compounds through reactions such as bond breaking dehydrogenation, dealkylation and the like. However, the temperature required by the method is very high, and the good effect can be achieved generally at 1000-. However, in practical production applications, this temperature is difficult to achieve and is not economically justified.
The catalytic reforming is to reduce the reaction temperature to 700-900 ℃ under the action of a catalyst so as to obtain better tar conversion efficiency. The reaction temperature of catalytic reforming is within the tolerance range of some reactor materials and the energy consumption is greatly improved compared to thermal cracking, and is therefore considered to be the most economical method for tar removal. In this process, the steam plays an important role in catalytically reforming tar and the catalyst plays an important role in cracking tar. The catalyst can reduce the temperature of pyrolysis gasification reaction, reduce energy consumption, reduce the using amount of gasification medium, promote reaction balance and obtain more products. However, in the catalytic reforming process, tar is easily deposited on the catalytic reforming catalyst, thereby causing carbon deposition deactivation of the catalytic reforming catalyst. When the problem of carbon deposition inactivation of a reforming catalyst in a biomass gasification and re-catalytic reforming hydrogen production process is researched, accurate measurement of the carbon deposition rate of the catalyst is basic and important work. However, the existing equipment for producing hydrogen by gasifying, re-catalytically reforming and continuously feeding biomass can realize the continuous feeding of biomass, the scale of a gasification device and a catalytic reforming device in laboratory scale is large, the data fluctuation is very large in the test process, and the carbon deposition rate of the catalyst measured under the same test condition is very different, so that whether the implemented solution can really realize the reduction of the carbon deposition rate of the catalytic reforming catalyst cannot be judged.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a device and a method for measuring the carbon deposition rate of a catalytic reforming catalyst.
The invention discloses a device for measuring the carbon deposition rate of a catalytic reforming catalyst, which comprises a gas supply system, a feeding system, a reaction system, a product analysis system and an electric heating control system, wherein the gas supply system is connected with the feeding system;
the gas supply system comprises a nitrogen gas steel cylinder and a gas flowmeter;
the feeding system comprises a double-channel micro-injection pump; in the double-channel micro-injection pump, tar is injected into a first channel, and a liquid substance is injected into a second channel;
when researching whether the added liquid substance can reduce the carbon deposition rate of the catalytic reforming catalyst, the liquid substance is added into a channel of the liquid substance, and the liquid substance is water or a mixture of water and hydrogen peroxide.
The reaction system comprises a quartz tube reactor, a distribution net, a heat preservation tube, a condensation tube and a liquid collector;
the product analysis system comprises a soap bubble flow meter and a gas chromatograph;
the electric heating control system comprises an electric heating pipe and an electric heating temperature controller;
the nitrogen steel cylinder is communicated with a feed inlet of the quartz tube reactor through a gas flowmeter; the channel outlet of the double-channel micro-injection pump is communicated with the feed inlet of the quartz tube reactor through a pipeline;
the middle part of a pipeline of the quartz tube reactor is provided with a distribution net, the periphery of the quartz tube reactor is provided with a heat preservation tube, a discharge port of the quartz tube reactor is sequentially connected with a condensation tube and a liquid collector, and a gas outlet of the liquid collector is respectively connected with a soap bubble flowmeter and a gas chromatograph through a three-way valve;
an electric heating pipe is arranged between the heat preservation pipe and the quartz tube reactor and is connected with an electric heating temperature controller; the electric heating temperature controller is connected with a thermocouple, and the thermocouple is arranged inside the quartz tube reactor and used for monitoring the temperature in the quartz tube reactor in real time.
The soap bubble flow meter is used for measuring the flow of the non-condensable gas, and the gas chromatograph is used for analyzing the components of the non-condensable gas and determining the product composition of the non-condensable gas.
The liquid collector is arranged in an environment at the temperature of-5-0 ℃.
The invention discloses a method for measuring carbon deposition rate of a catalytic reforming catalyst, which adopts the device and comprises the following steps:
(1) placing the activated catalytic reforming catalyst on a distribution net in a quartz tube reactor;
(2) opening a nitrogen steel cylinder, and purging the whole device for measuring the carbon deposition rate of the catalytic reforming catalyst to change the environment into inert atmosphere;
(3) setting the electric heating temperature controller as a reaction temperature according to the reaction temperature in the catalytic reforming process, and adjusting the nitrogen flow to 1/2-1/15 of the flow in the blowing process after the electric heating tube heats the quartz tube reactor to the reaction temperature;
(4) according to the catalytic reforming process, the ratio of tar to liquid substances is adjusted, the flow of the tar and the liquid substances is adjusted, the tar and the liquid substances are added into a quartz tube reactor by a double-channel micro-injection pump, and the catalytic reforming is carried out on the activated catalyst, wherein the ratio of water in the liquid substances is as follows according to the mol ratio: medium carbon in tar (2-3): 1;
(5) after reaction in the quartz tube reactor, condensing a reaction product through a condensing tube, collecting a liquid product in a liquid collector, allowing non-condensable gas to flow through a soap bubble flowmeter and a gas chromatograph respectively, measuring the flow of the non-condensable gas through the soap bubble flowmeter, measuring the components of the non-condensable gas through the gas chromatograph, and determining the components of the non-condensable gas;
(6) after the reaction was completed, the amount of CO produced and CO were measured by a catalytic reforming catalyst2And (4) calculating the generation amount to obtain the carbon deposition rate of the catalytic reforming catalyst.
The carbon deposition rate of the catalytic reforming catalyst is measured by adopting a temperature programming oxidation method, and the specific method comprises the following steps:
taking out the catalytic reforming catalyst after the reaction, placing the catalytic reforming catalyst in another quartz tube reactor, and introducing a nitrogen-oxygen mixture of 40-80 mL/h into the quartz tube reactor, wherein O in the nitrogen-oxygen mixture2Account for N2The molar percentage of the carbon dioxide is 5-25%, the temperature of the quartz tube reactor is increased from room temperature to 900 ℃ at the speed of 5-30 ℃/min, the produced tail gas is introduced into an online mass spectrometer for online continuous analysis, and the CO generation amount m is obtained1、CO2Amount of formation m2Calculating the carbon deposition rate v of the catalytic reforming catalyst according to the following formula;
the mass M of the carbon source C is as follows: m ═ M1/28+m2/44)×12；
Wherein M is the mass of carbon and has the unit of g, M1Is the amount of CO produced in g, m2Is CO2The amount of product produced is in g.
According to the mass of carbon, calculating the carbon deposition rate v of the catalytic reforming catalyst as follows:
v＝M÷m÷t；
wherein v is the carbon deposition rate of the catalytic reforming catalyst, and the unit is g/g/min; m is the mass of carbon in g, M is the mass of the catalytic reforming catalyst in g, and t is the catalytic reforming time in min.
In the step (1), the filling height is determined according to the use amount of the catalytic reforming catalyst and the diameter of the distribution net.
In the step (2), in the purging process, according to the specification of a pipeline in the device for measuring the carbon deposition rate of the catalytic reforming catalyst, the nitrogen flow rate is 10-25 m/s, preferably, in the device for measuring the carbon deposition rate of the catalytic reforming catalyst, 1-10L/min is preferred.
In the step (3), the flow rate of nitrogen gas after adjustment is preferably 0.2 to 0.5L/min.
In the step (3), the set reaction temperature is preferably 650-950 ℃.
In the step (4), when a liquid substance is added into water for research, the liquid substance is added into the water and enters the quartz tube reactor together with the water.
The device and the method for measuring the carbon deposition rate of the catalytic reforming catalyst have the beneficial effects that:
the device can accurately measure the carbon deposition rate of the catalytic reforming catalyst, and is very beneficial to research on a method for reducing carbon deposition inactivation of the catalytic reforming catalyst. In addition, in the biomass gasification and re-catalytic reforming hydrogen production process, tar is the main factor causing the carbon deposition inactivation of the reforming catalyst, tar by-products generated in the previous biomass gasification are collected, and catalytic reforming is carried out in the device, so that the influence of experimental fluctuation of a gasification device on carbon deposition rate measurement is reduced, the size of a catalytic reforming reactor can be greatly reduced (a spiral rod is required to be designed for feeding because biomass is required to be continuously and uniformly fed in the biomass gasification, a certain continuous groove is required for the spiral rod, therefore, the spiral rod needs to be designed thicker, the spiral rod is generally introduced from the side wall of the gasification reactor, so that the design diameter of the fluidized bed reactor cannot be too small, a gasification product is required to achieve the catalytic reforming effect in the reforming reactor, and the catalytic reforming reactor is required to be matched with the spiral rod, namely, so that the carbon deposition rate measurement result of the catalyst is more accurate, and has great reference significance for guiding the research of the method for reducing the carbon deposition rate of the catalytic reforming catalyst in a large laboratory device and even an industrial device for preparing hydrogen by gasifying and re-catalytically reforming biomass.
Drawings
Fig. 1 is a schematic structural diagram of an apparatus for measuring the carbon deposition rate of a catalytic reforming catalyst in the present invention, wherein: 1: a nitrogen cylinder; 2: a dual channel micro-syringe pump; 3: a gas flow meter; 4: a quartz tube reactor; 5: a heat preservation pipe; 6: an electric heating tube; 7: electrically heating a temperature controller; 8: a thermocouple; 9: a distribution net; 10: a condenser tube; 11: a liquid collector; 12: an ice-water mixture; 13: a soap bubble flow meter; 14: a gas chromatograph.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited thereto.
In the following examples, the in-line mass spectrometer used was a Max 300-LG model in-line mass spectrometer manufactured by Extrel, USA.
In the following examples, the biomass catalytic reforming catalyst used was a Z409 catalytic reforming catalyst purchased from ziru.
Example 1
In order to investigate whether the hydrogen deposition rate of the catalytic reforming catalyst can be reduced by adding hydrogen peroxide to the reforming reactant steam in the hydrogen production process by steam reforming of tar, the embodiment adopts a device for determining the carbon deposition rate of the catalytic reforming catalyst, and the schematic structural diagram of the device is shown in fig. 1, and includes: the system comprises a gas supply system, a feeding system, a reaction system, a product analysis system and an electric heating control system;
the gas supply system comprises a nitrogen gas steel cylinder 1 and a gas flowmeter 3;
the feeding system comprises a double-channel micro-injection pump 2; in the double-channel micro-injection pump 2, biomass tar is injected into a first channel, and a mixture of water and hydrogen peroxide is injected into a second channel; wherein the mass percentage of the hydrogen peroxide in the mixture of water and hydrogen peroxide is 3%.
The reaction system comprises a quartz tube reactor 4, a distribution net 9, a heat preservation tube 5, a condensation tube 10 and a liquid collector 11;
the product analysis system comprises a soap bubble flow meter 13 and a gas chromatograph 14;
the electric heating control system comprises an electric heating pipe 6 and an electric heating temperature controller 7;
the nitrogen steel cylinder 1 is communicated with a feed inlet of the quartz tube reactor 4 through a gas flowmeter 3; the channel outlet of the double-channel micro-injection pump 2 is communicated with the feed inlet of the quartz tube reactor 4 through a pipeline;
a distribution net 9 is arranged in the middle of a pipeline of the quartz tube reactor 4, heat preservation tubes 5 are arranged around the quartz tube reactor 4, a discharge port of the quartz tube reactor 4 is sequentially connected with a condensation tube 10 and a liquid collector 11, and a gas outlet of the liquid collector 11 is respectively connected with a soap bubble flow meter 13 and a gas chromatograph 14 through a three-way valve;
an electric heating pipe 6 is arranged between the heat preservation pipe 5 and the quartz tube reactor 4, and the electric heating pipe 6 is connected with an electric heating temperature controller 7; the electric heating temperature controller 7 is connected with a thermocouple 8, and the thermocouple 8 is arranged inside the quartz tube reactor 4 and is used for monitoring the temperature in the quartz tube reactor 4 in real time.
The liquid collector 11 is arranged in the ice-water mixture.
In this example, water containing 1% H2O2The structure of the adopted device is schematically shown in figure 1.
The method for measuring the carbon deposition rate of the catalytic reforming catalyst by adopting the device comprises the following steps:
(1) crushing the Z409 catalytic reforming catalyst into catalytic reforming catalyst powder with the particle size of 0.18-0.25 mm; before the Z409 catalytic reforming catalyst is used each time, reducing for 5 hours by using a mixed gas flow of hydrogen and nitrogen at the reduction temperature of 500 ℃ to obtain an activated Z409 catalytic reforming catalyst, wherein in the mixed gas flow of hydrogen and nitrogen, the molar percentage of hydrogen: 15 parts of nitrogen: 85.
(2) the catalyst with the grain diameter of 0.18-0.25mmZ409 is loaded on the distribution net 9 in the middle of the quartz tube reactor 4, and the loading height is 6 cm. The reaction apparatus was then connected intact. Then, the reaction system was purged with high-purity nitrogen gas at 2L/min for 30 minutes to change the reaction system to an inert atmosphere.
(3) Then the electric heating temperature controller 7 is set to the reaction temperature of 900 ℃, so that the temperature of the quartz tube reactor 4 starts to rise under the action of the electric heating tube 6.
(4) When the quartz tube reactors 6 all reach the set temperature, the flow rate of the nitrogen flow meter 3 is set to 0.3L/min.
(5) The flow rates of tar and water of the two-channel micro-injection pump 2 were set to 10mL/h (tar) and 20mL/h (mixture of deionized water and hydrogen peroxide containing 1% by mass of hydrogen peroxide), respectively, and then feeding was started.
The biomass raw material selected in this example was wood chips, the gasification temperature was 750 ℃, and the components of the obtained tar as biomass tar are shown in table 1.
TABLE 1 chemical composition of Biomass Tar
(6) After catalytic reforming in a quartz tube reactor, the whole reaction temperature is 900 ℃, the whole reaction time is 12 hours, and after a reaction product is condensed by a condensing tube, a liquid product is collected in a liquid collector; the temperature of the liquid collector is 0 ℃;
(7) the non-condensable gas in the liquid collector flows through a soap bubble flow meter and a gas chromatograph respectively, the soap bubble flow meter measures the flow of the non-condensable gas, and the gas chromatograph analyzes the components of the non-condensable gas to determine the product composition of the non-condensable gas.
(8) After the reaction is finished, cooling the reactor to room temperature in 3L/min of nitrogen, removing the Z409 catalytic reforming catalyst out of the reactor, and measuring the carbon deposition rate by adopting temperature programming oxidation, wherein the method comprises the following specific steps:
placing the reacted catalytic reforming catalyst in another quartz tube reactor, and introducing 60mL/h of nitrogen-oxygen mixture into the quartz tube reactor, wherein O in the nitrogen-oxygen mixture2Account for N2The molar percentage of the carbon dioxide is 15 percent, the quartz tube reactor is heated from room temperature to 900 ℃ at the speed of 10 ℃/min, the produced tail gas is introduced into an online mass spectrometer for online continuous analysis, and the CO generation amount m is obtained1、CO2Amount of formation m2Calculating the carbon deposition rate v of the catalytic reforming catalyst according to the following formula;
the mass M of the carbon source C is as follows: m ═ M1/28+21m2/44)×12；
Wherein M is the mass of carbon and has the unit of g, M1Is the amount of CO produced in g, m2Is CO2The amount of product produced is in g.
According to the mass of carbon, calculating the carbon deposition rate v of the catalytic reforming catalyst as follows:
v＝M÷m÷t；
wherein v is the carbon deposition rate of the catalytic reforming catalyst, and the unit is g/g/min; m is the mass of carbon in g, M is the mass of the catalytic reforming catalyst in g, and t is the catalytic reforming time in min.
Analysis tests show that the content of hydrogen in the non-condensable gas after the reaction is 58.45%, the hydrogen yield is 97.82%, and the carbon deposition rate of the catalyst is 1.2 multiplied by 10-6g/g catalyst/min。
Example 2
An apparatus for measuring the carbon deposition rate of a catalytic reforming catalyst was the same as in experimental example 1.
The method for measuring the carbon deposition rate of the catalytic reforming catalyst by adopting the device comprises the following steps:
(1) loading a catalytic reforming catalyst on a distribution net 9 in the quartz tube reactor 4;
(2) opening a nitrogen steel cylinder 1, controlling the flow of nitrogen gas to be 1-10L/min through a gas flowmeter 3, and purging until the internal environment of a quartz tube reactor 4 is changed into inert atmosphere;
(3) setting the electric heating temperature controller 7 to be the reaction temperature, heating the quartz tube reactor 4 by the electric heating tube 6, and adjusting the nitrogen gas flow by the gas flowmeter 3 to be 0.2-0.5L/min when the temperature of the quartz tube reactor 4 reaches the reaction temperature;
(4) adjusting tar and water of the double-channel micro-injection pump 2 according to the reaction flow ratio, introducing the tar and the water into a quartz tube reactor 4, and reacting at 850 ℃ to obtain a reaction product; wherein, the molar ratio of water: medium carbon in tar (2-3): 1; in water, the mass of the hydrogen peroxide is 3% of that of the mixture of the water and the hydrogen peroxide;
(5) after the reaction product is condensed by a condensing tube 10, collecting the liquid product in a liquid collector 11, wherein the temperature of the liquid collector 11 is 0 ℃;
(6) the non-condensable gas in the liquid collector 11 respectively flows through a soap bubble flow meter 13 and a gas chromatograph 14, the soap bubble flow meter 13 measures the flow rate of the gas prepared after catalytic reforming, and the gas chromatograph 14 measures and measures the components of the gas prepared after catalytic reforming to determine the product composition;
(7) the device for measuring the carbon deposition rate of the catalytic reforming catalyst is cooled by adopting nitrogen in a nitrogen steel cylinder, the catalytic reforming catalyst after reaction on a distribution network is subjected to carbon deposition measurement of the catalytic reforming catalyst, and temperature programming oxidation is adopted for analysis, and the method comprises the following specific steps:
placing the reacted catalytic reforming catalyst in another quartz tube reactor, and introducing 60mL/h of nitrogen-oxygen mixture into the quartz tube reactor, wherein O in the nitrogen-oxygen mixture2Account for N2The molar percentage of the carbon dioxide is 15 percent, the quartz tube reactor is heated from room temperature to 900 ℃ at the speed of 10 ℃/min, the produced tail gas is introduced into an online mass spectrometer for online continuous analysis according to CO and CO2The amount of formation was calculated as the carbon deposition rate of the catalytic reforming catalyst.
In this example, the carbon deposition rate of the catalytic reforming catalyst was calculated to be 1.5X 10-6g/g catalyst/min. The hydrogen content of the non-condensable gas after the reaction was 56.78%, the hydrogen yield was 95.37%.
Comparative example
An apparatus for determining the carbon deposition rate of a catalytic reforming catalyst was the same as in example 2.
A method for determining the carbon deposition rate of a catalytic reforming catalyst, which is the same as that in example 2, except that: hydrogen peroxide is not added into the water of the double-channel micro-injection pump, and the determination result is as follows: the carbon deposition rate of the catalytic reforming catalyst was 2.3X 10-6g/g catalyst/min. The hydrogen content in the non-condensable gas after the reaction was 56.84%, and the hydrogen yield was 94.15%.
Through the comparison, the carbon deposition rate of the catalytic reforming catalyst is reduced by 34.78 percent after hydrogen peroxide is added, the hydrogen concentration is basically unchanged, and the hydrogen yield is slightly increased.
Claims (10)
1. A device for measuring the carbon deposition rate of a catalytic reforming catalyst is characterized by comprising a gas supply system, a feeding system, a reaction system, a product analysis system and an electric heating control system;
the gas supply system comprises a nitrogen gas steel cylinder and a gas flowmeter;
the feeding system comprises a double-channel micro-injection pump; in the double-channel micro-injection pump, tar is injected into a first channel, and a liquid substance is injected into a second channel; the liquid substance is water or a mixture of water and hydrogen peroxide;
the reaction system comprises a quartz tube reactor, a distribution net, a heat preservation tube, a condensation tube and a liquid collector;
the product analysis system comprises a soap bubble flow meter and a gas chromatograph;
the electric heating control system comprises an electric heating pipe and an electric heating temperature controller;
the nitrogen steel cylinder is communicated with a feed inlet of the quartz tube reactor through a gas flowmeter; the channel outlet of the double-channel micro-injection pump is communicated with the feed inlet of the quartz tube reactor through a pipeline;
the middle part of a pipeline of the quartz tube reactor is provided with a distribution net, the periphery of the quartz tube reactor is provided with a heat preservation tube, a discharge port of the quartz tube reactor is sequentially connected with a condensation tube and a liquid collector, and a gas outlet of the liquid collector is respectively connected with a soap bubble flowmeter and a gas chromatograph through a three-way valve;
an electric heating pipe is arranged between the heat preservation pipe and the quartz tube reactor and is connected with an electric heating temperature controller; the electric heating temperature controller is connected with a thermocouple, and the thermocouple is arranged inside the quartz tube reactor and used for monitoring the temperature in the quartz tube reactor in real time.
2. The apparatus of claim 1, wherein the soap bubble flow meter is configured to measure the flow rate of the non-condensable gas, and the gas chromatograph is configured to analyze the composition of the non-condensable gas to determine the composition of the non-condensable gas.
3. The device for measuring the carbon deposition rate of the catalytic reforming catalyst as claimed in claim 1, wherein the liquid collector is arranged in an environment of-5 to 0 ℃.
4. A method for measuring the carbon deposition rate of a catalytic reforming catalyst, which is characterized in that the device for measuring the carbon deposition rate of the catalytic reforming catalyst, which is disclosed by any one of claims 1 to 3, is adopted, and comprises the following steps:
(1) placing the activated catalytic reforming catalyst on a distribution net in a quartz tube reactor;
(2) opening a nitrogen steel cylinder, and purging the whole device for measuring the carbon deposition rate of the catalytic reforming catalyst to change the environment into inert atmosphere;
(3) setting the electric heating temperature controller as a reaction temperature according to the reaction temperature in the catalytic reforming process, and adjusting the nitrogen flow to 1/2-1/15 of the flow in the blowing process after the electric heating tube heats the quartz tube reactor to the reaction temperature;
(4) according to the catalytic reforming process, the ratio of tar to liquid substances is adjusted, the flow of the tar and the liquid substances is adjusted, the tar and the liquid substances are added into a quartz tube reactor by a double-channel micro-injection pump, and the catalytic reforming is carried out on the activated catalyst, wherein the ratio of water in the liquid substances is as follows according to the mol ratio: carbon in tar = (2-3): 1;
(5) after reaction in the quartz tube reactor, condensing a reaction product through a condensing tube, collecting a liquid product in a liquid collector, allowing non-condensable gas to flow through a soap bubble flowmeter and a gas chromatograph respectively, measuring the flow of the non-condensable gas through the soap bubble flowmeter, measuring the components of the non-condensable gas through the gas chromatograph, and determining the components of the non-condensable gas;
(6) after the reaction was completed, the amount of CO produced and CO were measured by a catalytic reforming catalyst2And (4) calculating the generation amount to obtain the carbon deposition rate of the catalytic reforming catalyst.
5. The method for determining the carbon deposition rate of the catalytic reforming catalyst according to claim 4, wherein the carbon deposition rate of the catalytic reforming catalyst is determined by a temperature programmed oxidation method, and the specific method comprises the following steps:
taking out the catalytic reforming catalyst after the reaction, placing the catalytic reforming catalyst in another quartz tube reactor, and introducing a nitrogen-oxygen mixture of 40-80 mL/h into the quartz tube reactor, wherein O in the nitrogen-oxygen mixture2Account for N2The molar percentage of the carbon dioxide is 5-25%, the temperature of the quartz tube reactor is increased from room temperature to 900 ℃ at the speed of 5-30 ℃/min, the produced tail gas is introduced into an online mass spectrometer for online continuous analysis, and the CO generation amount m is obtained1、CO2Amount of formation m2The carbon deposition rate of the catalytic reforming catalyst was calculated according to the following formulav；
The mass M of the carbon source C is as follows: m = (M)1/28+m2/44)×12；
Wherein M is the mass of carbon and has the unit of g, M1Is the amount of CO produced in g, m2Is CO2The amount of production in g;
calculating the carbon deposition rate of the catalytic reforming catalyst according to the mass of the carbonvComprises the following steps:
v=M÷m÷t；
wherein the content of the first and second substances,vthe carbon deposition rate of the catalytic reforming catalyst is expressed in g/g/min; m is the mass of carbon in g, M is the catalytic reforming catalystThe mass is given in g, t is the catalytic reforming time in min.
6. The method for determining carbon deposition rate of a catalytic reforming catalyst according to claim 4, wherein in the step (1), the filling height is determined according to the use amount of the catalytic reforming catalyst and the diameter of the distribution net.
7. The method for measuring the carbon deposition rate of the catalytic reforming catalyst according to claim 4, wherein in the step (2), the nitrogen flow rate in the purging process is 10-25 m/s.
8. The method for measuring the carbon deposition rate of the catalytic reforming catalyst according to claim 7, wherein the nitrogen flow rate is 1-10L/min.
9. The method for determining the carbon deposition rate of a catalytic reforming catalyst according to claim 4, wherein in the step (3), the adjusted nitrogen flow rate is 0.2-0.5L/min.
10. The method for determining the carbon deposition rate of the catalytic reforming catalyst as set forth in claim 4, wherein the reaction temperature in the step (3) is set to 650-950 ℃.
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