CN213231512U - Natural gas hydrogen production medium temperature shift system - Google Patents
Natural gas hydrogen production medium temperature shift system Download PDFInfo
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- CN213231512U CN213231512U CN202021935257.3U CN202021935257U CN213231512U CN 213231512 U CN213231512 U CN 213231512U CN 202021935257 U CN202021935257 U CN 202021935257U CN 213231512 U CN213231512 U CN 213231512U
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Abstract
The utility model discloses a natural gas hydrogen manufacturing medium temperature transform system, including air feed unit, hydrodesulfurization unit, steam generation unit, steam conversion unit, medium temperature transform unit, carry hydrogen unit and purification unit, medium temperature transform unit with carry and be equipped with first transform gas in proper order between the hydrogen unit and carry section and second transform gas transport section, steam generation unit is equipped with the first water supply section and the second water supply section that set gradually along the water supply flow direction, first transform gas transport section with the second is given water the section heat exchange and is set up, the second transform gas transport section with first water supply section heat exchange sets up. The utility model discloses a medium temperature transform unit of natural gas hydrogen manufacturing, transform gas divide twice to cool down boiler feed water as the preheating heat source of boiler feed water, and abundant rational utilization waste heat can cool down transform gas, the heat that the make full use of system produced simultaneously.
Description
Technical Field
The utility model relates to a natural gas hydrogen manufacturing field, concretely relates to medium temperature shift system of natural gas hydrogen manufacturing.
Background
As energy consumption has increased, finding new energy sources has become an important task at present. As an energy source with the most development potential, hydrogen has wide sources, hardly generates pollution, has high conversion efficiency and wide application prospect.
The natural gas is used for preparing the hydrogen, so that the energy crisis of China can be relieved to a certain extent, and the transformation of the energy utilization structure of China is further promoted. The principle of the natural gas hydrogen production process is to pretreat natural gas, then convert methane and water vapor into carbon monoxide, hydrogen and the like in a converter, and after waste heat is recovered, convert carbon monoxide into carbon dioxide and hydrogen in a conversion tower. In the shift tower, in the presence of catalyst, the reaction temperature is controlled, and the carbon monoxide in the converted gas reacts with water to produce hydrogen and carbon dioxide.
Alkane in natural gas can generate a series of chemical reactions to generate converted gas under proper pressure and temperature, the converted gas passes through a PAS device filled with various adsorbents under automatic control through processes of heat exchange, condensation and the like, impurities such as carbon monoxide, carbon dioxide and the like are adsorbed by an adsorption tower, hydrogen is sent to a gas unit, the adsorbents with the impurities are adsorbed, after desorption, the desorbed gas can be sent to a shift converter as fuel, and the adsorbents also complete regeneration.
The main reaction formula is as follows:
reacting natural gas and water at the high temperature of 800-900 ℃ under the condition of a nickel oxide catalyst to generate carbon monoxide and hydrogen. The reaction formula is as follows: CH4+ H2O → CO + H2-Q
Carbon monoxide and water react at the temperature of 300-400 ℃ and under the condition of ferric oxide catalyst to generate carbon dioxide and hydrogen. The reaction formula is as follows: CO + H2O → CO2+ H2+ Q
In addition, the technical index requirements related to the preparation process are as follows:
the pressure is generally 1.5-2.5 MPa, and the unit consumption of natural gas is 0.4-0.5 m3/m3 hydrogen; operating time: 8000 h; on an industrial scale: 1000m 3/h-100000 m 3/h.
The hydrogen preparation process of natural gas mainly comprises four steps: raw material gas pretreatment, natural gas steam conversion, carbon monoxide conversion and hydrogen purification.
Firstly, a raw material pretreatment step is carried out, wherein the pretreatment mainly refers to the desulfurization of raw material gas, and in the actual process operation, natural gas cobalt molybdenum hydrogenation series zinc oxide is generally adopted as a desulfurizing agent to convert organic sulfur in natural gas into inorganic sulfur and then remove the inorganic sulfur.
Secondly, the step of natural gas steam conversion is carried out, and the alkane in the natural gas is converted into the raw material gas of which the main components are carbon monoxide and hydrogen by adopting a nickel catalyst in a conversion furnace.
Then, carbon monoxide is shifted to react with steam in the presence of a catalyst, thereby generating hydrogen and carbon dioxide, and a shifted gas containing hydrogen and carbon dioxide as main components is obtained. The shift conversion process of carbon monoxide can be divided into two types according to the difference of shift conversion temperature: medium temperature shift and high temperature shift. Wherein the temperature of high-temperature transformation is about 360 ℃, and the process of medium-temperature transformation is about 320 ℃. With the development of technical countermeasures, two-stage process setting of carbon monoxide high-temperature conversion and low-temperature conversion is started to be adopted in recent years, so that the consumption of resources can be further saved, but for the condition that the content of carbon monoxide in converted gas is not high, only medium-temperature conversion can be adopted.
The last step is to purify hydrogen, and the most common hydrogen purification system at present is a PAS system, which is also called a pressure swing adsorption purification separation system, and the system has low energy consumption, simple flow and high purity of prepared hydrogen, and the highest purity of the hydrogen can reach 99.99 percent.
The temperature of the converted gas after medium temperature conversion is high, hydrogen extraction and purification are carried out after cooling, and how to fully utilize the waste heat generated after medium temperature conversion is the problem to be solved by the application.
Disclosure of Invention
The utility model aims at providing a natural gas hydrogen manufacturing medium temperature transform system of abundant rational utilization waste heat.
In order to achieve the above purpose, the utility model adopts the technical scheme that: the utility model provides a natural gas hydrogen manufacturing medium temperature transform system, includes air feed unit, hydrodesulfurization unit, steam generation unit, steam conversion unit, medium temperature transform unit, carries hydrogen unit and purification unit, medium temperature transform unit with carry and be equipped with first transform gas between the hydrogen unit and carry section and second transform gas transport section in proper order, steam generation unit is equipped with the first water feeding section and the second water feeding section that set gradually along feedwater flow direction, first transform gas transport section with the heat exchange setting of second water feeding section, second transform gas transport section with first water feeding section heat exchange setting.
In the above technical scheme, the medium temperature shift unit includes a medium temperature shift converter, a shift gas water cooler, a shift gas water separator and a shift gas buffer tank, a feed inlet of the medium temperature shift converter is used as a shift gas input end of the medium temperature shift unit, a discharge outlet of the shift gas buffer tank is used as a shift gas output end of the medium temperature shift unit, and the first shift gas conveying section and the second shift gas conveying section are sequentially arranged between the medium temperature shift converter and the shift gas water cooler.
Among the above-mentioned technical scheme, the steam generation unit includes demineralized water supply installation, demineralized water preheater, oxygen-eliminating device, phosphate charge device, feedwater preheater, steam pocket, boiler and steam-water separator, the tube side water inlet of demineralized water preheater with the delivery port of demineralized water supply installation is connected, the water inlet of oxygen-eliminating device with the tube side delivery port of demineralized water preheater is connected, the tube side water inlet of feedwater preheater is connected the delivery port of oxygen-eliminating device with phosphate charge device, the shell side water inlet and the shell side steam outlet of boiler are connected the steam pocket, the steam pocket is connected respectively the tube side export of feedwater preheater with the steam inlet of steam-water separator, the steam outlet of steam-water separator does the steam output of steam generation unit, the tube side entry of boiler with the conversion gas output of steam conversion unit is connected,
the discharge port of the medium-temperature shift converter is connected with the shell pass inlet of the feed water preheater, the shell pass inlet of the desalted water heat exchanger is connected with the shell pass outlet of the feed water preheater, the shell pass of the shift gas water cooler is connected with the shell pass outlet of the desalted water heat exchanger, the shell pass inlet of the shift gas water separator is connected with the shell pass outlet of the shift gas water cooler, and the feed port of the shift gas buffer tank is connected with the shell pass outlet of the shift gas water separator;
the shell pass of the desalted water preheater is the second conversion gas conveying section, the shell pass of the feed water preheater is the first conversion gas conveying section, the tube pass of the desalted water preheater is the first feed water section, and the tube pass of the feed water preheater is the second feed water section.
Among the above-mentioned technical scheme, the air feed unit includes middling pressure tank wagon, first natural gas buffer tank, second natural gas buffer tank and third natural gas buffer tank, the feed inlet of first natural gas buffer tank is connected the middling pressure tank wagon, the feed inlet of second natural gas buffer tank with the feed inlet parallel connection of third natural gas buffer tank the discharge gate of first natural gas buffer tank, the discharge gate of second natural gas buffer tank does the feedstock output end of air feed unit, the discharge gate of third natural gas buffer tank does the fuel output end of air feed unit.
Because of the application of the technical scheme, compared with the prior art, the utility model has the following advantages: the utility model discloses a medium temperature transform unit of natural gas hydrogen manufacturing, transform gas divide twice to cool down boiler feed water as the preheating heat source of boiler feed water, and abundant rational utilization waste heat can cool down transform gas, the heat that the make full use of system produced simultaneously.
Drawings
Fig. 1 is a schematic diagram of the composition of the natural gas hydrogen production medium temperature shift system disclosed by the utility model.
Detailed Description
The invention will be further described with reference to the accompanying drawings and examples:
referring to fig. 1, as shown in the illustration therein, a natural gas hydrogen production system includes:
the natural gas supply unit is used for providing natural gas and comprises a medium-pressure tank car 11, a first natural gas buffer tank 12, a second natural gas buffer tank 13 and a third natural gas buffer tank 14, wherein a feed inlet of the first natural gas buffer tank 12 is connected with the medium-pressure tank car 11, a feed inlet of the second natural gas buffer tank 13 and a feed inlet of the third natural gas buffer tank 14 are connected with a discharge outlet of the first natural gas buffer tank 12 in parallel, a discharge outlet of the second natural gas buffer tank 13 is a raw material output end of the gas supply unit, and a discharge outlet of the third natural gas buffer tank 14 is a fuel output end of the gas supply unit;
the desulfurization unit 20 is used for performing desulfurization treatment on the natural gas to obtain a desulfurization gas, and the hydrodesulfurization unit is provided with a hydrogen input end, a raw material input end and a desulfurization gas output end, wherein the raw material input end is connected with the raw material output end;
the steam generation unit is used for providing steam and comprises a desalted water supply device 31, a desalted water preheater 32, a deaerator 33, a phosphate dosing device 34, a feed water preheater 35, a steam drum 36, a boiler 37 and a steam-water separator 38, wherein a tube pass water inlet of the desalted water preheater 32 is connected with a water outlet of the desalted water supply device 31, a water inlet of the deaerator 33 is connected with a tube pass water outlet of the desalted water preheater 32, a tube pass water inlet of the feed water preheater 35 is connected with a water outlet of the deaerator 33 and the phosphate device 34, a shell pass water inlet and a shell pass steam outlet of the boiler 37 are connected with the steam drum 36, the steam drum 36 is respectively connected with a tube pass outlet of the feed water preheater 35 and a steam inlet of the steam-water separator 38, and a steam outlet of the steam-water separator 38 is a steam output end of the;
the steam conversion unit 40 is used for converting the desulfurized gas and the steam to obtain converted gas, and comprises a converter, wherein the converter is provided with a desulfurized gas steam input end, a fuel input end and a converted gas output end, the desulfurized gas steam input end is connected with the desulfurized gas output end and the steam output end, and the fuel input end is connected with the fuel output end;
the medium temperature conversion unit is used for carrying out conversion treatment on the converted gas to obtain converted gas, and comprises a medium temperature conversion furnace 51, a converted gas water cooler 52, a converted gas-gas water separator 53 and a converted gas buffer tank 54 which are sequentially connected, wherein a feed inlet of the medium temperature conversion furnace 51 is used as a converted gas input end of the medium temperature conversion unit, a discharge outlet of the converted gas buffer tank 54 is used as a converted gas output end of the medium temperature conversion unit, and the converted gas input end is connected with the converted gas output end;
the hydrogen extraction unit 60 is used for purifying the conversion gas to obtain common hydrogen, and is provided with a conversion gas input end and a common hydrogen output end, and the conversion gas input end is connected with the conversion gas output end;
and the purification unit 70 is used for purifying the common hydrogen to obtain high-purity hydrogen, and the purification unit is provided with a common hydrogen input end and a high-purity hydrogen output end, and the common hydrogen input end is connected with the common hydrogen output end.
The discharge port of the medium temperature shift converter 51 is connected with the shell pass inlet of the feed water preheater 35, the shell pass inlet of the desalted water heat exchanger 32 is connected with the shell pass outlet of the feed water preheater 35, the shell pass inlet of the shift gas water cooler 52 is connected with the shell pass outlet of the desalted water heat exchanger 32, the shell pass inlet of the shift gas water separator 53 is connected with the shell pass outlet of the shift gas water cooler 52, and the feed port of the shift gas buffer tank 54 is connected with the shell pass outlet of the shift gas water separator 53.
The specific process flow is briefly described as follows:
1. hydrodesulfurization process of natural gas
Under the action of the hydroconversion catalyst, organic sulfur in the feed gas is converted into H2S, and desulfurization reaction is carried out under the action of the zinc oxide catalyst to be absorbed. Under a certain temperature and pressure, the raw material gas passes through a manganese oxide and zinc oxide desulfurizer to remove organic sulfur and H2S in the raw material gas to be below 0.1PPm so as to meet the requirement of a steam conversion catalyst on sulfur.
2. Steam reforming process
Mixing desulfurized raw natural gas with pressure of about 2.0MPa with process steam with pressure of 2.3MPa from a steam generation unit according to the ratio of water to carbon of 3.5, preheating the mixture to about 580 ℃ through a mixed gas preheating coil of a convection chamber of a reformer, entering a reformer tube of a radiation chamber of the reformer, and carrying out conversion reaction on the natural gas and the steam to generate hydrogen and carbon monoxide under the conditions of temperature and pressure of 830 ℃, pressure of about 2.0MPa and the action of a catalyst; the reformed gas enters the medium temperature conversion unit after being subjected to heat exchange and temperature reduction to be 360 ℃.
3. Intermediate temperature conversion step
The 1.8MP converted gas from the steam conversion unit enters a medium-temperature shift converter, and carbon monoxide in the converted gas and water vapor are subjected to shift reaction to generate hydrogen and carbon dioxide under the action of a catalyst. The temperature of the waste heat is about 400-430 ℃ after the waste heat is discharged from the medium-temperature shift converter, the waste heat is recovered through a feed water preheater and a desalted water preheater of the steam generation unit, the waste heat is cooled to 40 ℃ through water of a shift gas water cooler, and the waste heat is sent to a PSA adsorption unit through a shift gas water separator and a shift gas buffer tank. The reformed gas sent from the reformer contains about 13% of CO, and the shift reaction is to make CO react with water vapor under the action of a catalyst to generate CO2 and H2. Thus, the amount of hydrogen required is increased.
4. Product purification procedure
The conversion gas from the medium-temperature conversion unit enters a hydrogen extraction unit and a purification unit for adsorption, carbon dioxide and other easily adsorbed impurities are adsorbed, the hydrogen concentration is improved, and the purity can reach 99.999%. The high-purity hydrogen is taken as a product and sent out of the device. The Pressure Swing Adsorption (PSA) purification method has the characteristics of simple process, high automation degree, high product hydrogen purity and the like.
5. Compression charging process
The common hydrogen and the high-purity hydrogen enter a compressor unit consisting of 5 hydrogen compressors in two paths, and a compression medium is selected by switching. The outlet of the compressor unit is divided into 4 paths to be respectively filled with a common hydrogen tube bundle type container, a pure hydrogen tube bundle type container, a packaging grid and a bulk bottle (containing a bulk bottle group). The filling pressure of the tube bundle type container is 2.0MPa, and the filling pressure of the steel cylinder is 1.5 MPa.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. The natural gas hydrogen production medium-temperature conversion system comprises a gas supply unit, a hydrodesulfurization unit, a steam generation unit, a steam conversion unit, a medium-temperature conversion unit, a hydrogen extraction unit and a purification unit, and is characterized in that the medium-temperature conversion unit and the hydrogen extraction unit are sequentially provided with a first conversion gas conveying section and a second conversion gas conveying section, the steam generation unit is provided with a first water supply section and a second water supply section which are sequentially arranged along a water supply flow direction, the first conversion gas conveying section is in heat exchange with the second water supply section, and the second conversion gas conveying section is in heat exchange with the first water supply section.
2. A medium temperature shift system for hydrogen production from natural gas according to claim 1, wherein the medium temperature shift unit comprises a medium temperature shift converter, a shift gas water cooler, a shift gas water separator and a shift gas buffer tank, a feed inlet of the medium temperature shift converter is used as a shift gas input end of the medium temperature shift unit, a discharge outlet of the shift gas buffer tank is used as a shift gas output end of the medium temperature shift unit, and the first shift gas conveying section and the second shift gas conveying section are sequentially arranged between the medium temperature shift converter and the shift gas water cooler.
3. The natural gas hydrogen production medium temperature shift system of claim 2, wherein the steam generation unit comprises a desalted water supply device, a desalted water preheater, a deaerator, a phosphate dosing device, a feed water preheater, a drum, a boiler and a steam-water separator, wherein a tube pass water inlet of the desalted water preheater is connected with a water outlet of the desalted water supply device, a water inlet of the deaerator is connected with a tube pass water outlet of the desalted water preheater, a tube pass water inlet of the feed water preheater is connected with a water outlet of the deaerator and the phosphate device, a shell pass water inlet and a shell pass steam outlet of the boiler are connected with the drum, the drum is respectively connected with a tube pass outlet of the feed water preheater and a steam inlet of the steam-water separator, and a steam outlet of the steam-water separator is a steam output end of the steam generation unit, the discharge port of the medium-temperature shift converter is connected with the shell pass inlet of the feed water preheater, the shell pass inlet of the desalted water heat exchanger is connected with the shell pass outlet of the feed water preheater, the shell pass of the shift gas water cooler is connected with the shell pass outlet of the desalted water heat exchanger, the shell pass inlet of the shift gas water separator is connected with the shell pass outlet of the shift gas water cooler, and the feed port of the shift gas buffer tank is connected with the shell pass outlet of the shift gas water separator;
the shell pass of the desalted water preheater is the second conversion gas conveying section, the shell pass of the feed water preheater is the first conversion gas conveying section, the tube pass of the desalted water preheater is the first feed water section, and the tube pass of the feed water preheater is the second feed water section.
4. The natural gas hydrogen production medium-temperature shift system according to claim 1, wherein the gas supply unit comprises a medium-pressure tank wagon, a first natural gas buffer tank, a second natural gas buffer tank and a third natural gas buffer tank, wherein a feed inlet of the first natural gas buffer tank is connected with the medium-pressure tank wagon, a feed inlet of the second natural gas buffer tank and a feed inlet of the third natural gas buffer tank are connected in parallel with a discharge outlet of the first natural gas buffer tank, a discharge outlet of the second natural gas buffer tank is a raw material output end of the gas supply unit, and a discharge outlet of the third natural gas buffer tank is a fuel output end of the gas supply unit.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115159458A (en) * | 2022-07-29 | 2022-10-11 | 四川金星清洁能源装备股份有限公司 | Natural gas hydrogen production system and hydrogen production method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115159458A (en) * | 2022-07-29 | 2022-10-11 | 四川金星清洁能源装备股份有限公司 | Natural gas hydrogen production system and hydrogen production method |
| CN115159458B (en) * | 2022-07-29 | 2024-01-16 | 四川金星清洁能源装备股份有限公司 | Natural gas hydrogen production system and hydrogen production method |
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