CN111977612B - Catalytic heating coupled methanol hydrogen production process - Google Patents
Catalytic heating coupled methanol hydrogen production process Download PDFInfo
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Abstract
The invention discloses a catalytic heating coupling methanol hydrogen production process, belongs to the field of hydrogen production, and particularly relates to the technical field of methanol hydrogen production, aiming at solving the problems that the existing methanol hydrogen production process needs external heating for starting, needs additional equipment, has high energy consumption and large occupied area, and comprises a catalytic oxidation reactor and a methanol hydrogen production system, wherein in the catalytic oxidation reactor, methanol and air in raw materials are subjected to catalytic oxidation reaction under the condition of more than 10 ℃, under the action of a catalyst layer at a normal temperature, and the generated heat provides heat energy for starting the methanol hydrogen production system. Under the condition of no heat source, the raw materials of methanol and air are subjected to catalytic oxidation reaction in the catalytic oxidation reactor under the action of the combined catalyst layer, and the generated heat provides heat energy for the starting of the methanol hydrogen production system, so that the whole methanol hydrogen production process is started at normal temperature without external heating, and external heat source equipment is not required to be additionally added, so that the equipment has small floor area and low energy consumption.
Description
Technical Field
The invention discloses a catalytic heating coupling methanol hydrogen production process, belongs to the field of hydrogen production, and particularly relates to the technical field of methanol hydrogen production.
Background
The reformed gas of the traditional methanol steam reforming hydrogen production process is subjected to pressure swing adsorption or membrane hydrogen extraction to obtain the required product H2In addition, the rest is the analytic gas, H in the analytic gas2The content is 30-40%; product H of the currently common direct methanol cracking process2CO, exhaust gas H after use2The content is more than 95 percent. The method has two treatment modes, one is that the waste gas is sent into a boiler combustion system for boiler combustion, and because the gas source is unstable, obvious potential safety hazard is caused to the boiler combustion system; in addition, the device is directly emptied, a large amount of combustible gas is emptied, the potential safety hazard is great, and clean energy waste is also caused. The treatment of the combustible tail gas becomes a difficult problem for the safe production of the methanol hydrogen production device.
Domestic combustible tail gas treatment aspectMany exploratory tasks are done, but the prior processing technology has many limitations: for example, chinese patent application No. 200910311040.7 is directed to a process for supplying heat by catalytic combustion of hydrogen contained in methanol hydrogen production tail gas, but does not describe the mixture ratio and mixing manner of air and combustible gas, and has uncontrollable operation safety, easy explosion and low operability. The Chinese patent application No. 201710497756.5 relates to a temperature-controlled safety type catalytic oxidation VOCSIn the method, the reaction mixture gas is preheated to carry out the oxidation reaction, and the energy consumption is additionally increased. The Chinese patent application No. 201810019696.0 is only suitable for tail gas containing hydrogen, does not effectively control the oxygen content after mixing, is easy to explode, requires a pressure of more than or equal to 0.1MPa for processing gas, needs additional pressurizing equipment in the actual operation process, and has various limitations on safety and economy.
Disclosure of Invention
The invention aims to: the catalytic heating coupled methanol hydrogen production process is provided, and aims to solve the problems that the conventional methanol hydrogen production process needs external heating for starting, needs additional equipment, is high in energy consumption and large in occupied area, and can also solve the defects that the conventional methanol hydrogen production process needs combustible tail gas emission, and is unsafe and environmentally-friendly.
The technical scheme adopted by the invention is as follows:
a catalytic heating coupling methanol hydrogen production process comprises a catalytic oxidation reactor and a methanol hydrogen production system, wherein in the catalytic oxidation reactor, methanol and air in raw materials are subjected to catalytic oxidation reaction under the action of a catalyst layer at a normal temperature at a temperature of more than 10 ℃, and the generated heat provides heat energy for starting the methanol hydrogen production system.
According to the technical scheme, under the condition of no heat source, the catalytic oxidation reaction is generated in the catalytic oxidation reactor under the condition that the temperature of raw materials of methanol and air is higher than 10 ℃, and the effect of the combined catalyst layer is utilized, so that the generated heat provides heat energy for the starting of the methanol hydrogen production system, the whole methanol hydrogen production process is started at normal temperature, no external source heating is needed for starting, no external heat source equipment is additionally added, the occupied area of the equipment is small, and the energy consumption is low; in the normal operation process of the methanol hydrogen production system, the combustible tail gas of the system does not contain combustible gas after being treated by catalytic oxidation reaction, and is safe and environment-friendly to discharge.
Preferably, the catalytic oxidation reactor comprises a reactor cylinder body with two closed ends and connected with a plurality of inlet and outlet pipes, a central pipe is arranged in the reactor cylinder body, the central pipe extends to the outer side of the top of the reactor cylinder body, a mixer is arranged at the upper part of the central pipe in the reactor cylinder body, a plurality of reaction tubes are uniformly arranged on the periphery of the central pipe, a combined catalyst layer is arranged in each reaction tube, the combined catalyst layer comprises a normal-temperature oxidation catalyst layer at the lower part and a medium-temperature oxidation catalyst layer positioned at the upper part of the normal-temperature oxidation catalyst layer, the central pipe and the reaction tubes are both open, a heat-conducting medium outlet and a heat-conducting medium inlet are arranged on the cylinder wall of the reactor cylinder body between the two ends of the reaction tubes, and a desorption gas inlet is arranged on the central pipe outside the reactor cylinder body, the reactor comprises an air inlet, a methanol inlet is further formed in the outer side of the reactor barrel, the methanol inlet is communicated with the central pipe above the mixer in the reactor barrel, a high-temperature flue gas outlet is formed in the side wall of the reactor barrel above the reaction tube array, and a high-speed fan is arranged at the bottom of the reactor barrel.
Preferably, each reaction tube is wound with fins on the outer periphery. The fin is used for improving the heat transfer efficiency.
Preferably, the normal-temperature oxidation catalyst layer includes a first catalyst, the first catalyst is spherical and/or honeycomb-cylindrical in shape, the medium-temperature oxidation catalyst layer includes a second catalyst, and the second catalyst is spherical and/or honeycomb-cylindrical in shape.
Preferably, the volume ratio of the first catalyst to the second catalyst is 1:1 to 1: 5.
Preferably, the normal-temperature oxidation catalyst layer includes a honeycomb cylindrical first catalyst and a spherical first catalyst located on the honeycomb cylindrical first catalyst; the medium-temperature oxidation catalyst layer comprises a honeycomb cylindrical second catalyst and a spherical second catalyst positioned on the upper part of the honeycomb cylindrical second catalyst;
preferably, the volume ratio of the spherical first catalyst to the honeycomb cylindrical first catalyst is 1:4-1: 10; the volume ratio of the spherical second catalyst to the honeycomb cylindrical second catalyst is 1:4-1: 10.
Preferably, the volume ratio of the spherical first catalyst to the honeycomb cylindrical first catalyst is 1: 5; the volume ratio of the spherical second catalyst to the honeycomb cylindrical second catalyst is 1: 5.
Preferably, the preparation method of the first catalyst is as follows:
Preferably, in step 2, La2O3Accounting for 1-2% of the total mass of the modified carrier.
Preferably, the surfactant comprises one of CTAB, LAS, AES or TX-10.
Preferably, the preparation method of the second catalyst is as follows: soaking the alumina spherical or honeycomb cylindrical ceramic carrier in a chloroplatinic acid solution with the concentration of 0.005-0.01 mol/L for 60-120min, and then calcining for 2h at the temperature of 400-600 ℃ to obtain a semi-finished product second catalyst; finally activating for 4 hours at the temperature of 400-600 ℃ to obtain the finished product of the second catalyst. Wherein the alumina spherical or honeycomb cylindrical ceramic carrier is commercially available and has a specific surface area of 150m2More than g. The second catalyst can make methanol and air produce catalytic oxidation reaction at 100 deg.c and over to produce heat.
Preferably, an energy saver is arranged on one side of the catalytic oxidation reactor, a high-temperature flue gas part discharged from the high-temperature flue gas outlet enters the catalytic oxidation reactor from the air inlet through a return pipe to be used as a protective gas, the rest part is cooled by the energy saver and then is exhausted through a chimney, and the air inlet and the analysis gas inlet are respectively communicated with the energy saver through pipelines.
Preferably, the hydrogen is produced by methanol cracking: the methanol cracking hydrogen production system comprises a methanol cracking reactor, a vaporization superheater, an oil-gas separator, an air cooler and a pressure swing adsorber, wherein methanol is heated by a heat exchanger and then enters the methanol cracking reactor after being vaporized by the vaporization superheater, the generated cracked gas passes through the heat exchanger and then enters the air cooler, a part of cracked gas is then prepared into product gas by the pressure swing adsorber, the rest of cracked gas and the analyzed gas discharged from the pressure swing adsorber are preheated by an energy saver and are mixed with air and part of standard-reaching tail gas after catalytic oxidation to generate catalytic oxidation reaction and heat transfer, the rest of cracked gas and the analyzed gas discharged from the pressure swing adsorber form combustible gas, and the volume ratio of the combustible gas, the air and the standard-reaching tail gas after the part of catalytic oxidation is 1-5:1-5: 2-8;the heat is absorbed by the heat-conducting medium and supplies heat to the methanol reforming hydrogen production reactor, and the heat-conducting medium after heat supply enters the catalytic oxidation reactor from the heat-conducting medium inlet after passing through the vaporization superheater and the oil-gas separator. The product gas comprises CO and/or H2。
Preferably, the hydrogen production by methanol steam reforming: the methanol steam reforming hydrogen production system comprises a methanol reforming hydrogen production reactor, a vaporization superheater, an oil-gas separator, an air cooler and a pressure swing absorber or a membrane separator, wherein methanol and steam are heated by a heat exchanger and enter the methanol reforming hydrogen production reactor after being vaporized by the vaporization superheater, and H is generated2The hydrogen is produced through a pressure swing absorber or a membrane separator after passing through a heat exchanger and then entering an air cooler, and simultaneously, the hydrogen is produced into analysis gas, the analysis gas is preheated through an energy saver in sequence, is mixed with air and the standard-reaching tail gas after partial catalytic oxidation, and is subjected to catalytic oxidation reaction and heat transfer, wherein the volume ratio of the analysis gas to the air to the standard-reaching tail gas after the partial catalytic oxidation is 1-5:1-5: 2-8; the heat is absorbed by the heat-conducting medium and supplies heat to the methanol reforming hydrogen production reactor, and the heat-conducting medium after heat supply enters the catalytic oxidation reactor from the heat-conducting medium inlet after passing through the vaporization superheater and the oil-gas separator.
Preferably, the heat-conducting medium comprises heat-conducting oil or heat-conducting oil gas, the pressure of the heat-conducting oil or the heat-conducting oil gas is 0.01-0.5MPa, and the heating temperature is 200-350 ℃.
Preferably, a first oxygen online analyzer is arranged at the high-temperature flue gas outlet.
Preferably, a second oxygen online analyzer is arranged at the inlet of the reaction tube array.
The utility model provides a technical scheme in the lower part of vaporization over heater be the heat exchanger, and upper portion is the vaporization over heater, and integral type equipment takes up an area of for a short time, practices thrift the space.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. in the invention, under the condition of no heat source, the raw materials of methanol and air are subjected to catalytic oxidation reaction in the catalytic oxidation reactor under the condition of more than 10 ℃ and under the action of the combined catalyst layer, and the generated heat provides heat energy for the starting of the methanol hydrogen production system, so that the whole methanol hydrogen production process is started at normal temperature without external heating and external heat source equipment, the equipment occupies small area and consumes low energy; in the normal operation process of the methanol hydrogen production system, the combustible tail gas of the system does not contain combustible gas after being treated by catalytic oxidation reaction, and is safe and environment-friendly to discharge;
2. according to the invention, only one catalytic oxidation reactor is needed in the catalytic heating coupling methanol hydrogen production process, catalytic oxidation raw material gas is mixed by the upper mixer in the central tube and then flows to the lower part through the central tube and enters the high-speed fan, the mixed gas is mixed under the action of the high-speed fan under the pressure of 3-8 KPa, so that the mixed gas entering the catalytic oxidation system is uniform, the uniformly mixed raw material gas can be completely reacted in the catalytic oxidation heating reactor and then discharged, and the tail gas discharged by the whole device system does not contain combustible gas, so that the process is safe and environment-friendly;
3. in the invention, a normal-temperature oxidation catalyst layer at the lower part in each reaction tube and a medium-temperature oxidation catalyst layer positioned at the upper part of the normal-temperature oxidation catalyst layer are arranged, wherein the normal-temperature oxidation catalyst layer comprises a honeycomb cylindrical first catalyst and a spherical first catalyst positioned at the upper part of the honeycomb cylindrical first catalyst; the medium-temperature oxidation catalyst layer comprises a honeycomb cylindrical second catalyst and a spherical second catalyst positioned on the upper part of the honeycomb cylindrical second catalyst, and the catalysts are reasonably matched in front, so that the air flow resistance is small and the reaction efficiency is high;
4. in the invention, the tail gas from the catalytic oxidation reactor is partially recycled without additionally using inert gas for explosion suppression, and a second oxygen online analyzer is arranged at the inlet of a reaction tube of the catalytic oxidation reactor, so that the feed gas for catalytic oxidation can be automatically adjusted in a proper proportion, and the complete catalytic oxidation of the reaction gas is ensured;
5. in the invention, a first oxygen online analyzer detects the oxygen content in high-temperature flue gas at an outlet and judges whether the reaction is complete;
6. in the invention, the heat-conducting medium of the hydrogen production system for the catalytic heating coupling methanol hydrogen production process can be heat-conducting oil or heat-conducting oil gas, and the heat-conducting oil gas is selected to be more beneficial to energy conservation without using a heat-conducting oil circulating pump;
7. in the invention, the high-speed fan is a high-temperature resistant centrifugal fan without a fan shell, so that the air quantity entering the catalytic oxidation reactor is uniform and stable;
8. the invention relates to the application field of a methanol steam reforming hydrogen production process or a methanol cracking CO and H preparation process in the catalytic heating coupling methanol hydrogen production process2And (5) processing.
Drawings
FIG. 1 is a flow diagram of a process for producing hydrogen by reforming methanol steam according to the present invention;
FIG. 2 is a flow chart of the process for producing hydrogen by cracking methanol according to the present invention;
FIG. 3 is a transverse cross-sectional view of a catalytic oxidation reactor of the present invention;
fig. 4 is a schematic structural view of a center tube and fins.
The labels in the figure are: 1-an energy saver, 2-a catalytic oxidation reactor, 3-a high-temperature flue gas outlet, 4-a central tube, 5-a reaction tube array, 6-a mixing fan, 7-a methanol inlet, 8-a heat-conducting medium outlet, 9-a heat-conducting medium inlet, 10-a methanol reforming hydrogen production reactor, 11-a return pipe, 12-a vaporization superheater, 13-an oil-gas separator, 14-an air cooler, 15-a pressure swing absorber, 16-a first oxygen online analyzer, 17-a second oxygen online analyzer, 18-a methanol cracking reactor, 19-a mixer, 20-a fin, 21-a desorption gas inlet and 22-an air inlet.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Referring to fig. 1-2, a catalytic heating coupled methanol hydrogen production process comprises a catalytic oxidation reactor 2 and a methanol hydrogen production system, wherein in the catalytic oxidation reactor 2, methanol in raw materials and air are subjected to catalytic oxidation reaction under the action of a normal temperature oxidation catalyst layer at a temperature of more than 10 ℃, and the generated heat provides heat energy for starting the methanol hydrogen production system.
Example 2
On the basis of the embodiment 1, as shown in fig. 1 to 3, the catalytic oxidation reactor 2 includes a reactor cylinder with two closed ends and connected with a plurality of inlet and outlet pipes, a central pipe 4 is disposed in the reactor cylinder, the central pipe 4 extends to the outside of the top of the reactor cylinder, a mixer 19 is disposed on the upper portion of the central pipe 4 in the reactor cylinder, a plurality of reaction tubes 5 are uniformly disposed on the periphery of the central pipe 4, a composite catalyst layer is disposed in each reaction tube 5, the composite catalyst layer includes a normal temperature oxidation catalyst layer on the lower portion and a medium temperature oxidation catalyst layer on the upper portion of the normal temperature oxidation catalyst layer, both ends of the central pipe 4 and the reaction tubes 5 are open, a heat conducting medium outlet 8 and a heat conducting medium inlet 9 are disposed on the cylinder wall of the reactor cylinder between both ends of the reaction tubes 5, a desorption gas inlet 21 and an air inlet 22 are formed in the central tube 4 on the outer side of the reactor cylinder, a methanol inlet 7 is further formed in the outer side of the reactor cylinder, the methanol inlet 7 is communicated with the central tube 4 above the mixer 19 in the reactor cylinder, a high-temperature flue gas outlet 3 is formed in the side wall of the reactor cylinder above the reaction tube array 5, and a mixing fan 6 is arranged at the bottom of the reactor cylinder; a first oxygen online analyzer 16 is arranged at the high-temperature flue gas outlet 3, and a second oxygen online analyzer 17 is arranged at the inlet of the reaction tube array 5.
Example 3
On the basis of embodiment 2, the normal-temperature oxidation catalyst layer includes a first catalyst, the first catalyst is spherical and/or honeycomb-cylindrical in shape, the medium-temperature oxidation catalyst layer includes a second catalyst, and the second catalyst is spherical and/or honeycomb-cylindrical in shape; the volume ratio of the first catalyst to the second catalyst is 1:1-1: 5.
Example 4
On the basis of example 3, the normal-temperature oxidation catalyst layer includes the first catalyst having a honeycomb cylindrical shape and the spherical first catalyst located on the upper portion of the first catalyst having a honeycomb cylindrical shape; the medium-temperature oxidation catalyst layer comprises a honeycomb cylindrical second catalyst and a spherical second catalyst positioned on the upper part of the honeycomb cylindrical second catalyst.
Example 5
On the basis of example 4, the volume ratio of the spherical first catalyst to the honeycomb cylindrical first catalyst is 1:4-1: 10; the volume ratio of the spherical second catalyst to the honeycomb cylindrical second catalyst is 1:4-1: 10; the volume ratio of the spherical first catalyst to the honeycomb cylindrical first catalyst is 1: 5; the volume ratio of the spherical second catalyst to the honeycomb cylindrical second catalyst is 1: 5.
Example 6
On the basis of example 3, the first catalyst was prepared as follows:
Example 7
On the basis of example 3, the second catalyst was prepared as follows: soaking the alumina spherical or honeycomb cylindrical ceramic carrier in a chloroplatinic acid solution with the concentration of 0.005-0.01 mol/L for 60-120min, and then calcining for 2h at the temperature of 400-600 ℃ to obtain a semi-finished product second catalyst; finally, the catalyst is activated for 4 hours at the temperature of 400-600 ℃, and the finished product of the second catalyst is obtained.
Example 8
As shown in fig. 1-2, on the basis of embodiment 2, an economizer 1 is disposed at one side of the catalytic oxidation reactor 2, a high-temperature flue gas portion discharged from the high-temperature flue gas outlet 3 enters the catalytic oxidation reactor 2 from the air inlet 22 through a return pipe 11 to be used as a shielding gas, a remaining portion is cooled by the economizer 1 and then exhausted through a chimney, and the air inlet 22 and the desorption gas inlet 21 are respectively communicated with the economizer 1 through a pipeline.
Example 9
As shown in fig. 2, on the basis of example 8, hydrogen is produced by methanol cracking: the methanol hydrogen production system comprises a methanol cracking reactor 18, a vaporization superheater 12, an oil-gas separator 13, an air cooler 14 and a pressure swing adsorber 15, wherein methanol is heated by a heat exchanger and enters the methanol cracking reactor 18 after being vaporized by the vaporization superheater 12, the generated pyrolysis gas passes through the heat exchanger and then enters the air cooler 14, part of the pyrolysis gas passes through the pressure swing adsorber 15 to prepare product gas, the rest pyrolysis gas and the analysis gas discharged from the pressure swing adsorber 15 are sequentially preheated by the energy saver 1 and mixed with air and part of the standard-reaching tail gas after catalytic oxidation to generate catalytic oxidation reaction and heat transfer, the rest pyrolysis gas and the analysis gas discharged from the pressure swing adsorber 15 form combustible gas, and the volume ratio of the combustible gas to the air to the standard-reaching tail gas after the partial catalytic oxidation is 1-5:1-5: 2-8; the heat is absorbed by the heat-conducting medium and supplies heat to the methanol reforming hydrogen production reactor 10, and the heat-conducting medium after heat supply enters the catalytic oxidation reactor 2 from the heat-conducting medium inlet 9 after passing through the vaporization superheater 12 and the oil-gas separator 13. Combustible gas enters the catalytic oxidation reactor 2 from a combustible gas inlet in the attached drawing 2, and the combustible gas inlet in the attached drawing 2 is arranged at the same position as the desorption gas inlet 21 in the attached drawing 1.
Example 10
As shown in fig. 1, hydrogen is produced by methanol steam reforming based on example 8: the methanol hydrogen production system comprises a methanol reforming hydrogen production reactor 10, a vaporization superheater 12, an oil-gas separator 13, an air cooler 14 and a pressure swing adsorber 15 or a membrane separator, methanol and steam are heated by a heat exchanger and enter the methanol reforming hydrogen production reactor 10 after being vaporized by the vaporization superheater 12, generated H2 passes through the heat exchanger and then enters the air cooler 14, then the hydrogen is produced by the pressure swing adsorber 15 or the membrane separator, meanwhile, desorption gas is generated, the desorption gas is preheated by the energy saver 1 in sequence and is mixed with air and partial standard tail gas after catalytic oxidation, catalytic oxidation reaction and heat transfer are carried out, and the volume ratio of the desorption gas to the air to the standard tail gas after partial catalytic oxidation is 1-5:1-5: 2-8; the heat is absorbed by the heat-conducting medium and supplies heat to the methanol reforming hydrogen production reactor 10, and the heat-conducting medium after heat supply enters the catalytic oxidation reactor 2 from the heat-conducting medium inlet 9 after passing through the vaporization superheater 12 and the oil-gas separator 13.
Example 11
As shown in fig. 4, on the basis of example 2, each of the reaction tubes 5 has fins 20 wound around the outer periphery thereof. The fins 20 function to improve heat transfer efficiency.
Test example 1
1000 Nm as shown in FIG. 13The hydrogen production device by reforming methanol steam adopts a process flow of taking catalytic oxidation as a heat source, and the size of a catalytic oxidation reactor is as follows: the diameter is 1500 mm, the height is 3000 mm, wherein the filling volume of the normal-temperature catalytic oxidant is 0.16 m3The loading of the medium-temperature catalytic oxidation catalyst is 0.8m3(ii) a Wherein the volume ratio of the spherical catalyst to the honeycomb catalyst is 1: 5; at the time of starting at normal temperature, the amount of methanol consumed was controlled to 300 kg/h, and the amount of air charged was 5200 Nm3H, heating the heat conducting oil to over 250 DEG CThen, starting reaction by a methanol hydrogen production conversion reactor with a light load of 20-30%; after the methanol hydrogen production reaction is started, the load of the methanol hydrogen production reaction system is gradually adjusted to 100 percent according to the heat, and the analysis gas (wherein H) is controlled238-40% by volume of + CO) in 680 Nm3H, air amount of 640 Nm3The amount of recovered tail gas is 1720 Nm3And h enters a catalytic oxidation reactor, so that the system can normally produce. The tail gas discharged by the whole device system meets the discharge requirement of GB31571-2015, and reaches the standard.
Test example 2
1000 Nm as shown in FIG. 23The hydrogen production device by methanol cracking adopts a process flow of taking catalytic oxidation as a heat source, and the size of a catalytic oxidation reactor is as follows: the diameter is 1500 mm, the height is 3000 mm, wherein the filling volume of the normal-temperature catalytic oxidant is 0.16 m3The loading of the medium-temperature catalytic oxidation catalyst is 0.8m3(ii) a Wherein the volume ratio of the spherical catalyst to the honeycomb catalyst is 1: 5; at the time of starting at normal temperature, the amount of methanol consumed was controlled to 300 kg/h, and the amount of air charged was 5200 Nm3Heating the heat conducting oil to more than 250 ℃, and then starting the reaction of the methanol hydrogen production conversion reactor with a light load of 20-30%; after the methanol hydrogen production reaction is started, the load of the methanol hydrogen production reaction system is gradually adjusted to 100 percent according to the heat, and the cracking gas amount is controlled to be 300 Nm3H (wherein H)2+ CO volume fraction of 95% or more), and an air amount of 680 Nm3The amount of recovered tail gas is 1700 Nm3And h enters a catalytic oxidation reactor, so that the system can normally produce. The tail gas discharged by the whole device system meets the discharge requirement of GB31571-2015, and reaches the standard.
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 and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A catalytic heating coupling methanol hydrogen production process is characterized in that: the methanol hydrogen production system comprises a catalytic oxidation reactor (2) and a methanol hydrogen production system, wherein in the catalytic oxidation reactor (2), under the condition of no heat source, the raw material methanol and air are subjected to catalytic oxidation reaction under the action of a combined catalyst layer at the temperature of more than 10 ℃, and the generated heat provides heat energy for the start of the methanol hydrogen production system, so that the whole methanol hydrogen production process is started at normal temperature without external heating; the combined catalyst layer comprises a normal-temperature oxidation catalyst layer at the lower part and a medium-temperature oxidation catalyst layer positioned at the upper part of the normal-temperature oxidation catalyst layer.
2. The catalytic heating coupled methanol hydrogen production process according to claim 1, characterized in that: the catalytic oxidation reactor (2) comprises a reactor barrel body with two closed ends and connected with a plurality of inlet and outlet pipes, a central pipe (4) is arranged in the reactor barrel body, the central pipe (4) extends to the outer side of the top of the reactor barrel body, a mixer (19) is arranged on the upper portion of the central pipe (4) in the reactor barrel body, a plurality of reaction tubes (5) are uniformly arranged on the periphery of the central pipe (4), the combined catalyst layer is arranged in each reaction tube (5), the combined catalyst layer comprises a normal-temperature oxidation catalyst layer on the lower portion and a medium-temperature oxidation catalyst layer on the upper portion of the normal-temperature oxidation catalyst layer, two ends of the central pipe (4) and the reaction tubes (5) are both open, and a heat-conducting medium outlet (8) and a heat-conducting medium inlet (9) are arranged on the wall of the reactor barrel body between two ends of the reaction tubes (5), a desorption gas inlet (21) and an air inlet (22) are formed in the central tube (4) on the outer side of the reactor barrel, a methanol inlet (7) is further formed in the outer side of the reactor barrel, the methanol inlet (7) is communicated with the central tube (4) above the mixer (19) in the reactor barrel, a high-temperature flue gas outlet (3) is formed in the side wall of the reactor barrel above the reaction tube array (5), and a mixing fan (6) is arranged at the bottom of the reactor barrel; a first oxygen online analyzer (16) is arranged at the high-temperature flue gas outlet (3), and a second oxygen online analyzer (17) is arranged at the inlet of the reaction tube array (5).
3. The catalytic heating coupled methanol hydrogen production process according to claim 2, characterized in that: the normal-temperature oxidation catalyst layer comprises a first catalyst, the first catalyst is spherical and/or honeycomb cylindrical in shape, the medium-temperature oxidation catalyst layer comprises a second catalyst, and the second catalyst is spherical and/or honeycomb cylindrical in shape; the volume ratio of the first catalyst to the second catalyst is 1:1-1: 5.
4. The catalytic heating coupled methanol-to-hydrogen process according to claim 3, characterized in that: the normal-temperature oxidation catalyst layer comprises a honeycomb cylindrical first catalyst and a spherical first catalyst positioned on the upper part of the honeycomb cylindrical first catalyst; the medium-temperature oxidation catalyst layer comprises a honeycomb cylindrical second catalyst and a spherical second catalyst positioned on the upper part of the honeycomb cylindrical second catalyst.
5. The catalytic heating coupled methanol hydrogen production process according to claim 4, characterized in that: the volume ratio of the spherical first catalyst to the honeycomb cylindrical first catalyst is 1:4-1: 10; the volume ratio of the spherical second catalyst to the honeycomb cylindrical second catalyst is 1:4-1: 10.
6. The catalytic heating coupled methanol-to-hydrogen production process according to claim 3, wherein the first catalyst is prepared by the following method:
step 1, mixing and ball-milling pseudo-boehmite, magnesium oxide and cellulose with the mass ratio of 93-96.5:2-4:1.5-3, adding water after ball-milling until the granularity is less than 320 meshes, uniformly mixing, then preparing a spherical carrier with phi 2-5 mm or preparing a honeycomb cylindrical carrier with phi 40mm in a slip casting mode, curing the spherical carrier or the honeycomb cylindrical carrier with steam, and calcining to obtain spherical or honeycomb cylindrical MgO/Al2O3Carrier with specific surface area not less than 200m2The strength reaches more than 100N per grain;
step 2, dissolving lanthanum nitrate in deionized water to prepare a metal nitrate solution with the concentration of 0.05-0.2mol/L, and dissolving lanthanum nitrate in the deionized water at the temperature of 50-90 DEG CSpherical or honeycomb cylinder MgO/Al2O3Soaking the carrier in a metal nitrate solution for 30-60min, drying at 120-200 deg.C for 2-6h after soaking, calcining at 400-500 deg.C for 3-10h, cooling, and adding La2O3Accounting for 0.5-2 percent of the total mass of the modified carrier to obtain the La2O3Modified spherical or honeycomb cylindrical support, La2O3The specific surface area of the modified spherical or honeycomb cylindrical carrier is more than or equal to 280m2G, strength of more than 100N, La2O3Accounting for 1-2% of the total mass of the modified carrier;
step 3, uniformly mixing a surfactant with the concentration of 0.10 mol/L and chloroplatinic acid with the concentration of 0.05-0.2mol/L to obtain a mixed solution, and carrying out La treatment at the temperature of 20-60 DEG C2O3The modified spherical or honeycomb cylindrical carrier is soaked in the mixed solution for 60-120min and then activated for 4h at the temperature of 400-600 ℃, thus obtaining the finished product first catalyst.
7. The catalytic heating coupled methanol-to-hydrogen process according to claim 3, wherein the second catalyst is prepared by the following method: soaking the alumina spherical or honeycomb cylindrical ceramic carrier in a chloroplatinic acid solution with the concentration of 0.005-0.01 mol/L for 60-120min, and then calcining for 2h at the temperature of 400-600 ℃ to obtain a semi-finished product second catalyst; finally, the catalyst is activated for 4 hours at the temperature of 400-600 ℃, and the finished product of the second catalyst is obtained.
8. The catalytic heating coupled methanol hydrogen production process according to claim 2, characterized in that: one side of catalytic oxidation reactor (2) is provided with economizer (1), high temperature exhanst gas part of high temperature exhanst gas outlet (3) exhaust is followed through back flow (11) air intlet (22) get into catalytic oxidation reactor (2) are the guard gas and use, and remaining part is through economizer (1) cooling back chimney evacuation, air intlet (22) with analysis gas import (21) respectively through the pipeline with economizer (1) intercommunication.
9. The catalytic heating coupling methanol hydrogen production process according to claim 8, wherein the methanol hydrogen production system comprises a methanol cracking reactor (18), a vaporization superheater (12), an oil-gas separator (13), an air cooler (14) and a pressure swing adsorber (15), methanol is heated by a heat exchanger, enters the methanol cracking reactor (18) after being vaporized by the vaporization superheater (12), produced cracked gas passes through the heat exchanger and then enters the air cooler (14), product gas is produced by a pressure swing adsorber (15) after partial cracked gas passes through the heat exchanger, residual cracked gas and analyzed gas discharged from the pressure swing adsorber (15) are sequentially preheated by the energy saver (1), mixed with air and standard tail gas after partial catalytic oxidation to produce catalytic oxidation reaction and heat transfer, the residual cracked gas and the analyzed gas discharged from the pressure swing adsorber (15) form combustible gas, and the combustible gas, The volume ratio of air to the tail gas reaching the standard after partial catalytic oxidation is 1-5:1-5: 2-8; the heat is absorbed by the heat-conducting medium and supplies heat to the methanol cracking reactor (18), and the heat-conducting medium after heat supply enters the catalytic oxidation reactor (2) from the heat-conducting medium inlet (9) after passing through the vaporization superheater (12) and the oil-gas separator (13).
10. The catalytic heating coupling methanol hydrogen production process according to claim 8, wherein the methanol hydrogen production system comprises a methanol reforming hydrogen production reactor (10), a vaporization superheater (12), an oil-gas separator (13), an air cooler (14), a pressure swing adsorber (15) or a membrane separator, methanol and steam are heated by a heat exchanger, enter the methanol reforming hydrogen production reactor (10) after being vaporized by the vaporization superheater (12), and produce H2The hydrogen is sent to an air cooler (14) through a heat exchanger, then is made into a product hydrogen through a pressure swing absorber (15) or a membrane separator, and simultaneously generates a desorption gas, the desorption gas is preheated through the energy saver (1) in sequence, is mixed with air and the standard-reaching tail gas after partial catalytic oxidation, and generates catalytic oxidation reaction and heat transfer, and the volume ratio of the desorption gas to the air to the standard-reaching tail gas after partial catalytic oxidation is 1-5:1-5: 2-8; the heat is absorbed by the heat-conducting medium and supplies heat to the methanol reforming hydrogen production reactor (10), and the heat-conducting medium after supplying heat enters the catalytic oxidation reactor (2) from the heat-conducting medium inlet (9) after passing through the vaporization superheater (12) and the oil-gas separator (13).
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