CN213172233U - Natural gas hydrogen production desulfurization system - Google Patents
Natural gas hydrogen production desulfurization system Download PDFInfo
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- CN213172233U CN213172233U CN202022094565.4U CN202022094565U CN213172233U CN 213172233 U CN213172233 U CN 213172233U CN 202022094565 U CN202022094565 U CN 202022094565U CN 213172233 U CN213172233 U CN 213172233U
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Abstract
The utility model discloses a natural gas hydrogen manufacturing desulfurization system, including air feed unit, hydrodesulfurization unit, steam generation unit, steam conversion unit, medium temperature transform unit, carry hydrogen unit and purification unit, the feed gas input section of hydrodesulfurization unit and steam generation unit's convection current section heat exchange setting, the hydrogen input of hydrodesulfurization unit is connected through tail hydrogen compressor to the tail hydrogen output of purification unit. The utility model discloses in, the produced tail hydrogen impurity content of purification unit is less, can carry out hydrogenation, supplies hydrogen to the hydrogenation ware through the tail hydrogen buffer tank, has not only saved the hydrogen buffer tank of hydrogenation ware, has saved the technology and the equipment of further purifying tail hydrogen moreover.
Description
Technical Field
The utility model relates to a hydrogen manufacturing field, concretely relates to natural gas hydrogen manufacturing desulfurization system.
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.
Currently, a hydrogen buffer tank is usually arranged in a hydrodesulfurization system to supply hydrogen to a hydrogenation reactor, a tail hydrogen buffer tank is also arranged in a pressure swing adsorption tower B to receive reverse exhaust gas of a purification unit, and tail hydrogen cannot be directly discharged into the atmosphere. How to further simplify the process and reduce the equipment is the problem to be solved by the present application.
Disclosure of Invention
The utility model aims at providing a natural gas hydrogen production desulfurization system which simplifies the process and reduces the equipment.
In order to achieve the above purpose, the utility model adopts the technical scheme that: the utility model provides a natural gas hydrogen manufacturing desulfurization system, includes air feed unit, hydrodesulfurization unit, steam generation unit, steam conversion unit, medium temperature transform unit, carries hydrogen unit and purification unit, the hydrodesulfurization unit is equipped with the feed gas input section, the steam conversion unit is equipped with the convection current section, the feed gas input section with convection current section heat exchange sets up, the tail hydrogen output of purification unit is connected through tail hydrogen compressor the hydrogen input of hydrodesulfurization unit.
Among the above-mentioned technical scheme, the hydrodesulfurization unit includes feed gas preheating coil, cobalt molybdenum hydrogenation ware and zinc oxide desulfurization groove, cobalt molybdenum hydrogenation ware's feed inlet is connected the feed gas preheating coil's discharge gate, the feed inlet of zinc oxide desulfurization groove is connected the discharge gate of cobalt molybdenum hydrogenation ware, the feed gas preheating coil does the feed gas input section of hydrodesulfurization unit, the hydrogenation mouth of cobalt molybdenum hydrogenation ware does the hydrogen input of hydrodesulfurization unit, the feed inlet of feed gas preheating coil does the raw materials input of hydrodesulfurization unit, the discharge gate of zinc oxide desulfurization groove does the desulfurization gas output of hydrodesulfurization unit.
In the above technical scheme, the steam reforming unit includes a reformer, the reformer is provided with a convection chamber and a radiation chamber, a mixed gas preheating coil is arranged in the convection chamber, the convection chamber is a convection section of the steam reforming unit, a feed inlet of the mixed gas preheating coil is a desulfurized gas steam input end of the steam reforming unit, a reforming tube and a burner are arranged in the radiation chamber, the feed inlet of the reforming tube is connected with a discharge outlet of the mixed gas preheating coil, the discharge outlet of the reforming tube is a reformed gas output end of the steam reforming unit, and an air inlet of the burner is a fuel input end of the steam reforming unit.
In the technical scheme, the purification unit comprises a pressure swing adsorption tower B, a high-purity hydrogen buffer tank and a tail hydrogen buffer tank, wherein a feed inlet of the pressure swing adsorption tower B is a common hydrogen input end of the purification unit, a feed inlet of the high-purity hydrogen buffer tank is connected with a discharge outlet of the pressure swing adsorption tower B, a discharge outlet of the high-purity hydrogen buffer tank is a high-purity hydrogen output end of the purification unit, a feed inlet of the tail hydrogen buffer tank is connected with a reverse gas discharge outlet of the pressure swing adsorption tower B, and a discharge outlet of the tail hydrogen buffer tank is a tail hydrogen output end of the purification unit.
In the technical scheme, the purification unit comprises 6 pressure swing adsorption towers B which are arranged in parallel, and each pressure swing adsorption tower B is provided with a common hydrogen feeding program control valve, a high-purity hydrogen discharging program control valve and a tail hydrogen discharging program control valve.
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:
1) the utility model discloses a natural gas hydrogen production desulfurization system, the produced tail hydrogen impurity content of purification unit is less, can carry out hydrogenation, supplies hydrogen to the hydrogenation ware through tail hydrogen buffer tank, has not only saved the hydrogen buffer tank of hydrogenation ware, has saved the technology and the equipment of further purification to tail hydrogen moreover;
2) the utility model discloses a natural gas hydrogen manufacturing desulfurization system sets up 6 pressure swing adsorption towers B, staggers each other in time, makes pressure swing adsorption process can constantly purify the feed gas, reduces the fluctuation of output product gas, is applicable to hydrogenation ware's application.
Drawings
Fig. 1 is a schematic diagram of the composition of the natural gas hydrogen production and desulfurization 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 is used for carrying out desulfurization treatment on natural gas to obtain desulfurized gas, and comprises a feed gas preheating coil 21, a cobalt-molybdenum hydrogenation reactor 22 and a zinc oxide desulfurization tank 23, wherein a feed inlet of the cobalt-molybdenum hydrogenation reactor 22 is connected with a discharge outlet of the feed gas preheating coil 21, a feed inlet of the zinc oxide desulfurization tank 23 is connected with a discharge outlet of the cobalt-molybdenum hydrogenation reactor 22, a hydrogenation port of the cobalt-molybdenum hydrogenation reactor 22 is a hydrogen input end of the hydrodesulfurization unit, a feed inlet of the feed gas preheating coil 21 is a raw material input end of the hydrodesulfurization unit, a discharge outlet of the zinc oxide desulfurization tank 23 is a desulfurized gas output end of the hydrodesulfurization unit, and a raw material input end is connected with a raw material output end;
a steam generating unit 30 for providing steam, the steam generating unit having a steam output;
a steam conversion unit for converting the desulfurization gas and the steam to obtain converted gas, the steam conversion unit comprises a converter, the converter is provided with a convection chamber 41 and a radiation chamber 42, a mixed gas preheating coil 43 is arranged in the convection chamber 41, a feed inlet of the mixed gas preheating coil 43 is a desulfurization gas steam input end of the steam conversion unit, a conversion pipe 44 and a burner 45 are arranged in the radiation chamber 42, a feed inlet of the conversion pipe 44 is connected with a discharge outlet of the mixed gas preheating coil 43, a discharge outlet of the conversion pipe 44 is a converted gas output end of the steam conversion unit, a gas inlet of the burner 45 is a fuel input end of the steam conversion unit, the desulfurization gas steam input end is connected with a desulfurization gas output end and a steam output end, the fuel input end is connected with the fuel output end
The medium temperature conversion unit 50 is used for converting the converted gas to obtain converted gas, and the medium temperature conversion unit is provided with a converted gas input end and a converted gas output end, and the converted gas input end is connected with the converted gas output end;
a hydrogen extraction unit 60 for purifying the converted gas to obtain common hydrogen, the hydrogen extraction unit having a converted gas input end and a common hydrogen output end, the converted gas input end being connected with the converted gas output end
The purification unit is used for obtaining high-purity hydrogen after the purification treatment of the common hydrogen, and comprises a pressure swing adsorption tower B71, a high-purity hydrogen buffer tank 72 and a tail hydrogen buffer tank 73, wherein a feed inlet of the pressure swing adsorption tower B71 is a common hydrogen input end of the purification unit, a feed inlet of the high-purity hydrogen buffer tank 72 is connected with a discharge outlet of the pressure swing adsorption tower B71, a discharge outlet of the high-purity hydrogen buffer tank 72 is a high-purity hydrogen output end of the purification unit, a feed inlet of the tail hydrogen buffer tank 73 is connected with a reverse gas outlet of the pressure swing adsorption tower B71, and a discharge outlet of the tail hydrogen buffer tank 73 is a tail hydrogen output end of the purification unit.
Wherein, the feed gas preheating disk 21 is arranged in the convection chamber 41;
a discharge hole of the tail hydrogen buffer tank 73 is connected with a hydrogenation hole of the cobalt-molybdenum hydrogenation reactor 22 through a tail hydrogen compressor 74;
the reverse gas outlet of the pressure swing adsorption tower B is also connected with the feed inlet of a second desorption gas buffer tank (not shown in the figure);
the tail hydrogen buffer tank is provided with a pressure detection device, the tail hydrogen buffer tank is provided with a feed inlet program control valve A, a feed inlet program control valve B is arranged between a reverse gas outlet of the pressure swing adsorption tower B and the second analysis gas buffer tank, a control system controls the switch of the program control valve A and the program control valve B according to detection information of the pressure detection device, and specifically, when the pressure of the tail hydrogen buffer tank reaches a set requirement, the program control valve A is closed, and the program control valve B is opened.
The purification unit comprises 6 pressure swing adsorption towers B71 arranged in parallel, and each pressure swing adsorption tower B71 is provided with a common hydrogen feeding program control valve, a high-purity hydrogen discharging program control valve and a tail hydrogen discharging program control valve.
The specific process flow is briefly described as follows:
1. hydrodesulfurization process of natural gas
Compressed Natural Gas (CNG) is transported to a production site from a 4.0MPa medium-pressure tank car, enters a first natural gas buffer tank, is discharged from the buffer tank and decompressed to 2.0MPa, is buffered by a second natural gas buffer tank, enters a raw material gas preheating coil pipe positioned in a convection chamber of a reformer, is preheated to 360 ℃, enters a cobalt-molybdenum hydrogenation reactor, and is subjected to hydrogenation reaction with circulating hydrogen (PSA desorption gas) from a tail hydrogen compressor under the action of a hydrogenation catalyst; then enters a zinc oxide desulfurization tank, and organic sulfur in the natural gas is removed by using a desulfurizing agent.
Under the action of the hydroconversion catalyst, organic sulfur in the feed gas is converted into H2S, and is absorbed by the following desulfurization reaction under the action of the zinc oxide catalyst. 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 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 tail gas produced by washing the adsorbent saturated in adsorption with pure hydrogen is partially used for the hydrodesulfurization of the feed gas. The Pressure Swing Adsorption (PSA) purification method has the characteristics of simple process, high automation degree, high product hydrogen purity and the like. The whole PSA adsorption unit is divided into an 8-tower hydrogen extraction section and a 6-tower purification section, and can respectively produce common hydrogen and high-purity hydrogen.
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 (6)
1. The utility model provides a natural gas hydrogen manufacturing desulfurization system, its characterized in that includes air feed unit, hydrodesulfurization unit, steam conversion unit, medium temperature transform unit, carries hydrogen unit and purification unit, the hydrodesulfurization unit is equipped with feed gas input section, the steam conversion unit is equipped with the convection current section, the feed gas input section with convection current section heat exchange sets up, the tail hydrogen output of purification unit is connected through tail hydrogen compressor the hydrogen input of hydrodesulfurization unit.
2. The natural gas hydrogen production desulfurization system according to claim 1, wherein the hydrodesulfurization unit comprises a feed gas preheating coil, a cobalt-molybdenum hydrogenation reactor and a zinc oxide desulfurization tank, a feed inlet of the cobalt-molybdenum hydrogenation reactor is connected with a discharge outlet of the feed gas preheating coil, a feed inlet of the zinc oxide desulfurization tank is connected with a discharge outlet of the cobalt-molybdenum hydrogenation reactor, the feed gas preheating coil is a feed gas input section of the hydrodesulfurization unit, a hydrogenation port of the cobalt-molybdenum hydrogenation reactor is a hydrogen input end of the hydrodesulfurization unit, a feed inlet of the feed gas preheating coil is a raw material input end of the hydrodesulfurization unit, and a discharge outlet of the zinc oxide desulfurization tank is a desulfurization gas output end of the hydrodesulfurization unit.
3. The natural gas hydrogen production and desulfurization system of claim 1, wherein the steam reforming unit comprises a reformer, the reformer is provided with a convection chamber and a radiation chamber, the convection chamber is provided with a mixed gas preheating coil therein, the convection chamber is a convection section of the steam reforming unit, a feed inlet of the mixed gas preheating coil is a desulfurized gas steam input end of the steam reforming unit, the radiation chamber is provided with a reforming tube and a burner therein, the feed inlet of the reforming tube is connected with a discharge outlet of the mixed gas preheating coil, the discharge outlet of the reforming tube is a reformed gas output end of the steam reforming unit, and a gas inlet of the burner is a fuel input end of the steam reforming unit.
4. The natural gas hydrogen production and desulfurization system according to claim 1, wherein the purification unit comprises a pressure swing adsorption tower B, a high purity hydrogen buffer tank and a tail hydrogen buffer tank, the feed inlet of the pressure swing adsorption tower B is the common hydrogen input end of the purification unit, the feed inlet of the high purity hydrogen buffer tank is connected with the discharge outlet of the pressure swing adsorption tower B, the discharge outlet of the high purity hydrogen buffer tank is the high purity hydrogen output end of the purification unit, the feed inlet of the tail hydrogen buffer tank is connected with the reverse gas discharge outlet of the pressure swing adsorption tower B, and the discharge outlet of the tail hydrogen buffer tank is the tail hydrogen output end of the purification unit.
5. The natural gas hydrogen production and desulfurization system of claim 4, wherein the purification unit comprises 6 pressure swing adsorption towers B arranged in parallel, and each pressure swing adsorption tower B is provided with a common hydrogen feeding program control valve, a high-purity hydrogen discharging program control valve and an exhaust hydrogen outlet program control valve.
6. The natural gas hydrogen production and desulfurization 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 the feed inlet of the first natural gas buffer tank is connected with the medium-pressure tank wagon, the feed inlet of the second natural gas buffer tank and the feed inlet of the third natural gas buffer tank are connected in parallel with the discharge outlet of the first natural gas buffer tank, the discharge outlet of the second natural gas buffer tank is the raw material output end of the gas supply unit, and the discharge outlet of the third natural gas buffer tank is the fuel output end of the gas supply unit.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113955717A (en) * | 2021-10-21 | 2022-01-21 | 福州大学 | System and method for producing hydrogen by desulfurizing tail gas generated in iron-making and steel-making |
| CN114955996A (en) * | 2022-04-21 | 2022-08-30 | 陕西液化天然气投资发展有限公司 | Hydrogen energy recovery and purification device in natural gas liquefaction process |
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2020
- 2020-09-22 CN CN202022094565.4U patent/CN213172233U/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113955717A (en) * | 2021-10-21 | 2022-01-21 | 福州大学 | System and method for producing hydrogen by desulfurizing tail gas generated in iron-making and steel-making |
| CN113955717B (en) * | 2021-10-21 | 2023-12-22 | 中琉科技有限公司 | System and method for producing hydrogen by desulfurizing tail gas from iron making and steel making |
| CN114955996A (en) * | 2022-04-21 | 2022-08-30 | 陕西液化天然气投资发展有限公司 | Hydrogen energy recovery and purification device in natural gas liquefaction process |
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