CN113501497A

CN113501497A - Method for purifying hydrogen

Info

Publication number: CN113501497A
Application number: CN202110760581.9A
Authority: CN
Inventors: 张东来
Original assignee: Hubei Lituo Energy Chemical Equipment Co ltd
Current assignee: Hubei Lituo Energy Chemical Equipment Co ltd
Priority date: 2021-07-06
Filing date: 2021-07-06
Publication date: 2021-10-15

Abstract

The invention relates to the technical field of gas treatment, in particular to a method for purifying hydrogen. The method provided by the invention comprises the following steps: adding an adsorption catalyst material to the reactor; introducing hydrogen containing impurity gas into a reactor under the conditions of the temperature of 100-300 ℃ and the pressure of 0.1-10MPa, wherein the impurity gas contained in the hydrogen is absorbed and removed by the absorption catalytic material. The method for purifying hydrogen provided by the invention has the advantages of simple process, simple and convenient operation and mild conditions, and can effectively adsorb and remove oxygen, carbon dioxide and carbon monoxide in hydrogen.

Description

Method for purifying hydrogen

Technical Field

The invention relates to the technical field of gas treatment, in particular to a method for purifying hydrogen.

Background

Hydrogen (H)₂) The hydrogen energy can be used as clean energy for transportation and power production, and the demand of hydrogen energy is continuously increased along with the increasing strictness of environmental protection laws and regulations around the world and the attention of society to clean energy. The hydrogen can be used as a raw material for producing clean oil products, the requirements on the quality of the oil products are stricter and stricter along with the improvement of the fuel oil standard, and the deterioration degree of the crude oil is higher and higher, so that deep processing technologies such as hydrofining, hydrocracking and the like become important processing technologies of oil refineries, and the demand of the oil refining industry on the hydrogen is rapidly increased.

PSA hydrogen production is commonly used in the hydrogen production process, the PSA hydrogen production process is simple in process and stable in operation, and impurities can be removed once for mixed gas containing various impurities to obtain a high-purity product, so that the PSA hydrogen production process is developed rapidly in recent years and widely applied to purification of hydrogen in hydrogen-containing gas, preparation of carbon monoxide, carbon dioxide, oxygen, nitrogen, argon and hydrocarbons in the mixed gas, athermal drying of various gases and the like.

However, in special cases such as where the hydrogen purity is high and only small amounts of oxygen and carbon oxides need to be removed, the PSA hydrogen production process does not address the purity of the hydrogen. Therefore, it is necessary to provide a hydrogen purification method which is simple in operation, energy-saving and environment-friendly.

Disclosure of Invention

In view of the above, the invention provides a method for purifying hydrogen, which is simple to operate, energy-saving and environment-friendly.

The invention provides a method for purifying hydrogen, which comprises the following steps: adding an adsorption catalyst material to the reactor; under the conditions of the temperature of 100-300 ℃ and the pressure of 0.1-10MPa, hydrogen containing impurity gas is introduced into a reactor, the impurity gas contained in the hydrogen is adsorbed by the adsorption catalytic material and removed by reaction, and under the normal conditions, the volume ratio of the volume of the hydrogen containing impurity gas introduced per minute to the volume of the adsorption catalytic material is 10-100.

Further, the impurity gas is a mixture of oxygen, carbon dioxide and carbon monoxide, and in the impurity gas, the volume content of oxygen is less than 0.5 vol%, the volume content of carbon monoxide is less than 3.0 vol%, and the volume content of carbon dioxide is less than 1.0 vol%. Furthermore, in the impurity gas, the volume content of oxygen is less than 0.05 vol%, the volume content of carbon monoxide is less than 1.0 vol%, and the volume content of carbon dioxide is less than 0.5 vol%.

Further, after purification, the volume content of impurity gas in the hydrogen is less than 0.001 vol%.

Further, the adsorption catalytic material is formed by mixing porous oxide, porous carbon and metal salt.

Further, the content of the metal element in the adsorption catalysis material is 5-80 wt%. Furthermore, the content of the metal element in the adsorption catalysis material is 20-60 wt%.

Further, the content of the porous carbon in the adsorption catalytic material is 1-50 wt%. Further, the content of the porous carbon in the adsorption catalyst material is 3-15 wt%.

Further, the porous oxide is any one of alumina, silica or molecular sieve.

Furthermore, the porous carbon is coconut shell activated carbon.

Further, the metal salt is any one or more of copper chloride, copper sulfate, copper nitrate, nickel chloride, nickel nitrate, nickel sulfate, cobalt chloride, cobalt nitrate or cobalt sulfate.

Further, the preparation process of the adsorption catalysis material comprises the following steps: uniformly mixing porous oxide and porous carbon, performing ball milling and tabletting to obtain a granular solid compound; dissolving a metal salt in water to obtain a metal salt solution; spraying a metal salt solution on the surface of the solid compound under a vacuum condition, drying, and calcining for 1-24 hours at the temperature of 300-1000 ℃ in the atmosphere of mixed gas of nitrogen and hydrogen to obtain the porous adsorption catalytic material.

Further, the mass ratio of the porous oxide to the porous carbon is 2:8-8: 2.

Further, the mass ratio of the metal salt solution to the solid compound is 1:5-2: 1.

Further, the particle size of the solid composite is 1-20 mm. Further, the solid composite has a particle size of 5 to 12 mm.

Further, the temperature condition of the calcination is 400-600 ℃, and the time is 2-8 hours.

Furthermore, the porous oxide is alumina with the average pore diameter of 20-30nm, and the porous carbon is coconut shell activated carbon with the average pore diameter of 2-4 nm.

The technical scheme provided by the invention has the beneficial effects that:

1. the method for purifying hydrogen provided by the invention has the advantages of simple process, simple and convenient operation and mild conditions, and can effectively adsorb and remove oxygen, carbon dioxide and carbon monoxide in hydrogen by using the method provided by the invention;

2. the adsorption catalysis material is prepared from porous oxide, porous carbon and metal salt, has surface properties and a micro-pore structure of the porous oxide and the porous carbon, and has strong adsorption performance and activity; and the adsorption catalytic material can be repeatedly used, and does not need to be regenerated within 1 year generally.

Drawings

FIG. 1 is a schematic flow diagram of a method of purifying hydrogen gas according to the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be further described with reference to the accompanying drawings.

Referring to fig. 1, an embodiment of the present invention provides a method for purifying hydrogen, including the following steps:

(1) adding an adsorption catalysis material into a fixed bed reactor;

(2) introducing hydrogen containing impurity gas into a fixed bed reactor under the conditions that the temperature is 100-300 ℃ and the pressure is 0.1-10MPa, wherein the impurity gas contained in the hydrogen is absorbed and removed by an absorption catalytic material, and the purified hydrogen flows out of the fixed bed reactor; the impurity gas is a mixture of oxygen, carbon dioxide and carbon monoxide, and in the impurity gas, the volume content of oxygen is less than 0.5 vol%, the volume content of carbon monoxide is less than 3.0 vol%, and the volume content of carbon dioxide is less than 1.0 vol%.

Wherein, the adsorption catalysis material is prepared by the following processes: uniformly mixing porous oxide and porous carbon, ball-milling, tabletting and forming to obtain a granular solid compound with the grain diameter of 1-20 mm; dissolving a metal salt in water to obtain a metal salt solution; spraying a metal salt solution on the surface of the solid compound under a vacuum condition, drying, and calcining for 1-24 hours at the temperature of 300-1000 ℃ in the atmosphere of nitrogen-hydrogen mixed gas to obtain the porous adsorption catalytic material; wherein, the porous oxide is any one of alumina, silicon oxide or molecular sieve; porous carbon is coconut shell activated carbon; the metal salt is any one of copper chloride, copper sulfate, copper nitrate, nickel chloride, nickel nitrate, nickel sulfate, cobalt chloride, cobalt nitrate or cobalt sulfate; in the porous adsorption catalytic material, the content of nickel, copper or cobalt is 5-80 wt%, and the content of porous carbon is 1-50 wt%.

In some preferred embodiments, the porous oxide is alumina with a mean pore size of 20-30nm, and the porous carbon is coconut shell activated carbon with a mean pore size of 2-4 nm.

The method for purifying hydrogen provided by the present invention will be described in detail below with reference to examples and comparative examples.

The preparation process of the adsorption catalyst material CAT-1 used in the following examples 1 to 3 is as follows:

weighing 50 kg of alumina powder and 15 kg of coconut shell activated carbon, putting the alumina powder and the coconut shell activated carbon into a high-speed ball mill, operating for 10 minutes, fully and uniformly mixing, taking out, adding a small amount of deionized water and graphite, uniformly mixing, and tabletting and forming by using a tablet press to obtain a cylindrical granular solid compound with the particle size of 3-8 mm; the specific surface area of the used alumina powder is 280 square meters per gram, and the average pore diameter is 25 nanometers; the average pore diameter of the coconut shell activated carbon is 3 nanometers;

adding nickel nitrate into water to dissolve to obtain a nickel nitrate solution with the nickel content of 15 wt%;

weighing 20 kg of solid compound, putting the solid compound into a sealed stainless steel container with heating and rotating functions, vacuumizing the stainless steel container, spraying 28 kg of nickel nitrate solution on the surface of the solid compound SU-1, rotating for 30 minutes, starting the heating function, rotating and heating to 110 ℃ to remove moisture, and finally calcining for 6 hours at 500 ℃ in a high-temperature furnace in the atmosphere of mixed gas containing 50% of nitrogen and 50% of hydrogen to obtain the adsorption catalytic material marked as CAT-1.

In comparative examples 1 to 3, the procedure for preparing the catalytic material CAT-2 used was:

weighing 50 kg of alumina powder, putting the alumina powder into a high-speed ball mill, operating for 10 minutes, fully and uniformly mixing, taking out, adding a small amount of deionized water and graphite, uniformly mixing, and tabletting by using a tabletting machine to obtain cylindrical granular alumina particles with the particle size of 3-8 mm; the specific surface area of the used alumina powder is 280 square meters per gram, and the average pore diameter is 20 nanometers;

weighing 20 kg of alumina particles SU-2, putting the alumina particles SU-2 into a sealed stainless steel container with heating and rotating functions, vacuumizing the stainless steel container, spraying 28 kg of nickel nitrate solution on the surface of the alumina particles SU-2, rotating for 30 min, starting the heating function, rotating and heating to 110 ℃ to remove moisture, and finally calcining for 6 hours at 500 ℃ in a high-temperature furnace in a mixed gas atmosphere containing 50% of nitrogen and 50% of hydrogen to obtain a catalytic material, which is marked as CAT-2.

Example 1:

embodiment 1 of the present invention provides a method of purifying hydrogen gas, including the steps of:

(1) adding 10 g of adsorption catalysis material CAT-1 into a fixed bed reactor;

(2) under the conditions of 130 ℃ of temperature and 5.0MPa of hydrogen atmosphere pressure, the composition is as follows: carbon monoxide 1.5 vol%, carbon dioxide 0.5 vol%, oxygen 0.2 vol%, and hydrogen in balance 0.3m³The flow rate of/hour is introduced into the fixed bed reactor, and after 1 hour of stabilization, sampling, chromatographic analysis and detector FID are carried out, the reaction aims at judging the comprehensive performance of hydrogen purification, and the indexes are the concentrations of residual oxygen, carbon dioxide and carbon monoxide after flowing through the fixed bed reactor.

Comparative example 1:

comparative example 1 differs from example 1 only in that: in comparative example 1, catalytic material CAT-2 was added to the fixed bed reactor; the rest is basically the same as the embodiment 1.

The reaction results of example 1 and comparative example 1 are shown in table 1.

Table 1: reaction results of example 1 and comparative example 1

	Residual oxygen	Residual carbon dioxide	Residual carbon monoxide
				Example 1	＜0.0005vol％	＜0.05vol％	＜0.01vol％
Comparative example 1	＜0.0005vol％	＜0.20vol％	＜0.05vol％

Example 2:

example 2 differs from example 1 only in that: the reaction temperature is 200 ℃; the rest is basically the same as the embodiment 1.

Comparative example 2:

comparative example 2 differs from example 2 only in that: in comparative example 2, catalytic material CAT-2 was added to the fixed bed reactor; the rest is basically the same as the embodiment 2.

The reaction results of example 2 and comparative example 2 are shown in table 2.

Table 2: reaction results of example 2 and comparative example 2

	Residual oxygen	Residual carbon dioxide	Residual carbon monoxide
				Example 2	＜0.0005vol％	＜0.0003vol％	＜0.0001vol％
Comparative example 2	＜0.0005vol％	＜0.001vol％	＜0.0005vol％

Example 3:

example 3 differs from example 1 only in that: the reaction temperature is 270 ℃; the rest is basically the same as the embodiment 1.

Comparative example 3:

comparative example 3 differs from example 3 only in that: in comparative example 3, catalytic material CAT-2 was added to the fixed bed reactor; the rest is basically the same as the embodiment 3.

The reaction results of example 3 and comparative example 3 are shown in table 3.

Table 3: reaction results of example 3 and comparative example 3

	Residual oxygen	Residual carbon dioxide	Residual carbon monoxide
				Example 3	＜0.0005vol％	＜0.0001vol％	＜0.0001vol％
Comparative example 3	＜0.0005vol％	＜0.0005vol％	＜0.0001vol％

Example 4:

embodiment 4 of the present invention provides a method of purifying hydrogen gas, including the steps of:

(2) under the conditions of 130 ℃ of temperature and 5.0MPa of hydrogen atmosphere pressure, the composition is as follows: carbon monoxide 0.05 vol%, carbon dioxide 0.05 vol%, oxygen 0.1 vol%, and hydrogen in balance 0.3m³The flow rate of/hour is introduced into the fixed bed reactor, and after 1 hour of stabilization, sampling, chromatographic analysis and detector FID are carried out, the reaction aims at judging the comprehensive performance of hydrogen purification, and the indexes are the concentrations of residual oxygen, carbon dioxide and carbon monoxide after flowing through the fixed bed reactor.

Comparative example 4:

comparative example 4 differs from example 4 only in that: in comparative example 4, catalytic material CAT-2 was added to the fixed bed reactor; the rest is basically the same as the embodiment 4.

The reaction results of example 4 and comparative example 4 are shown in Table 4.

Table 4: reaction results of example 4 and comparative example 4

	Residual oxygen	Residual carbon dioxide	Residual carbon monoxide
				Example 4	＜0.0005vol％	＜0.001vol％	＜0.001vol％
Comparative example 4	＜0.0005vol％	＜0.01vol％	＜0.01vol％

Example 5:

example 5 differs from example 4 only in that: the reaction temperature is 200 ℃; the rest is basically the same as the embodiment 4.

Comparative example 5:

comparative example 5 differs from example 5 only in that: in comparative example 5, catalytic material CAT-2 was added to the fixed bed reactor; the rest is basically the same as the embodiment 5.

The reaction results of example 5 and comparative example 5 are shown in Table 2.

Table 5: reaction results of example 5 and comparative example 5

	Residual oxygen	Residual carbon dioxide	Residual carbon monoxide
				Example 5	＜0.0005vol％	＜0.0001vol％	＜0.0001vol％
Comparative example 5	＜0.0005vol％	＜0.001vol％	＜0.0005vol％

Example 6:

example 6 differs from example 4 only in that: the reaction temperature is 270 ℃; the rest is basically the same as the embodiment 4.

Comparative example 6:

comparative example 6 differs from example 6 only in that: in comparative example 6, catalytic material CAT-2 was added to the fixed bed reactor; the rest is basically the same as the embodiment 6.

The reaction results of example 6 and comparative example 6 are shown in Table 6.

Table 6: reaction results of example 6 and comparative example 6

	Residual oxygen	Residual carbon dioxide	Residual carbon monoxide
				Example 6	＜0.0005vol％	＜0.0001vol％	＜0.0001vol％
Comparative example 6	＜0.0005vol％	＜0.0005vol％	＜0.0001vol％

Example 7:

embodiment 7 of the present invention provides a method of purifying hydrogen gas, including the steps of:

(2) under the conditions of temperature of 120 ℃ and hydrogen atmosphere pressure of 5.0MPa, the composition is as follows: carbon monoxide 0.01 vol%, carbon dioxide 0.01 vol%, and hydrogen in balance 0.3m³The flow of the reaction is measured by the fixed bed reactor, the sample is taken after 1 hour of stabilization, the reaction is analyzed by chromatography and the detector FID, the reaction is aimed at judging the comprehensive performance of hydrogen purification, and the index is that the hydrogen flows through the fixed bedThe residual carbon dioxide and carbon monoxide concentrations after the reactor.

Comparative example 7:

comparative example 7 differs from example 7 only in that: in comparative example 7, catalytic material CAT-2 was added to the fixed bed reactor; the rest is basically the same as that of example 7.

The reaction results of example 7 and comparative example 7 are shown in Table 7.

Table 7: reaction results of example 7 and comparative example 7

	Residual carbon dioxide	Residual carbon monoxide
			Example 7	＜0.0001vol％	＜0.0001vol％
Comparative example 7	＜0.001vol％	＜0.001vol％

Example 8:

example 8 differs from example 7 only in that: the reaction temperature is 150 ℃; the rest is basically the same as that of example 7.

Comparative example 8:

comparative example 8 differs from example 8 only in that: in comparative example 8, catalytic material CAT-2 was added to the fixed bed reactor; the rest is basically the same as the embodiment 8.

The reaction results of example 8 and comparative example 8 are shown in Table 8.

Table 8: reaction results of example 8 and comparative example 8

	Residual carbon dioxide	Residual carbon monoxide
			Example 8	＜0.0001vol％	＜0.0001vol％
Comparative example 8	＜0.0005vol％	＜0.0005vol％

Example 9:

example 9 differs from example 7 only in that: the reaction temperature is 180 ℃; the rest is basically the same as that of example 7.

Comparative example 9:

comparative example 9 differs from example 9 only in that: in comparative example 9, catalytic material CAT-2 was added to the fixed bed reactor; the rest is basically the same as that of example 9.

The reaction results of example 9 and comparative example 9 are shown in Table 9.

Table 9: reaction results of example 9 and comparative example 9

	Residual carbon dioxide	Residual carbon monoxide
			Example 9	＜0.0001vol％	＜0.0001vol％
Comparative example 9	＜0.0005vol％	＜0.0005vol％

As can be seen from the results in tables 1 to 9, after the adsorption and removal of the catalytic material CAT-1, the contents of carbon dioxide, carbon monoxide and oxygen in hydrogen are obviously reduced, and the method provided by the invention is proved to have excellent hydrogen purification performance.

The features of the embodiments and embodiments described herein above may be combined with each other without conflict.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims

1. A method of purifying hydrogen gas, comprising the steps of: adding an adsorption catalyst material to the reactor; introducing hydrogen containing impurity gas into a reactor under the conditions of the temperature of 100-300 ℃ and the pressure of 0.1-10MPa, wherein the impurity gas contained in the hydrogen is absorbed and removed by the absorption catalytic material.

2. A method for purifying hydrogen as claimed in claim 1, wherein the impure gas is a mixture of oxygen, carbon dioxide and carbon monoxide, and the impure gas has a volume content of oxygen of less than 0.5 vol%, a volume content of carbon monoxide of less than 3.0 vol% and a volume content of carbon dioxide of less than 1.0 vol%.

3. A method for purifying hydrogen as claimed in claim 2, characterized in that the impurity gas contains less than 0.05 vol% of oxygen, less than 1.0 vol% of carbon monoxide and less than 0.5 vol% of carbon dioxide.

4. A method of purifying hydrogen as claimed in claim 1, characterized in that the content of impurity gases in the hydrogen gas after purification is less than 0.001 vol%.

5. A method for purifying hydrogen as claimed in claim 1, characterized in that said adsorption catalytic material is composed of a mixture of porous oxides, porous carbon and metal salts.

6. A method for purifying hydrogen as claimed in claim 5, characterized in that the content of metallic elements in the adsorption catalyst material is 5-80 wt%.

7. A method for purifying hydrogen as claimed in claim 5, characterized in that the content of porous carbon in the adsorptive catalytic material is 1-50 wt%.

8. A method for purifying hydrogen as claimed in claim 5, characterized in that the porous oxide is alumina with a mean pore size of 20-30nm, and the porous carbon is coconut shell activated carbon with a mean pore size of 2-4 nm.