CN111232920B - Method for producing hydrogen by coke oven coal chemical looping - Google Patents
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Abstract
The invention relates to a method for preparing hydrogen by coke oven coal chemical looping, belonging to the technical field of energy chemical industry. The invention uses oxygen carrier Ce 1‑x Fe x O 2‑δ Ce-Fe-X-O (X = Mn, cu or Ni), niO/MgO, la 1‑x Sr x FeO 3 、LaNi x Fe 1‑x O 3 Respectively react with the coke oven gas to convert the coke oven gas into CO in a reduction stage 2 And water or synthetic gas, and water vapor is introduced in the oxidation stage to generate pure hydrogen. The gas (hydrogen, methane and carbon monoxide) in the coke oven gas is fully utilized, the purity of the generated hydrogen is as high as 99.0 percent, the oxygen carrier can be recycled, and the economic and efficient utilization of the oxygen carrier and the coke oven gas is realized.
Description
Technical Field
The invention relates to a method for preparing hydrogen by coke oven coal chemical looping, belonging to the technical field of energy chemical industry.
Background
Coke oven gas is a by-product in the coking processSubstance mainly comprising H 2 (55～60vol％)、CO(5～8vol％)、CO 2 (3～6vol％)、CH 4 (23-27 vol%) and some impurities (e.g. N) 2 And H 2 S), the ignition point is 600-650 ℃, and the calorific value is about 17580KJ/m 3 ～18420KJ/m 3 . At present, the utilization of the coke oven gas is limited and still at a very low level, only 20-50% of the coke oven gas is generally used as fuel, most of the residual coke oven gas is burnt by a torch and even directly discharged into the air under certain conditions, which causes huge energy waste and serious environmental pollution.
Because the coke oven gas has higher hydrogen and methane contents, the coke oven gas can not be fully and efficiently utilized when being directly used as fuel, and greenhouse gas CO can be generated 2 . In recent years, coke oven gas is regarded as a potential low-cost hydrogen production raw material, and currently, methods for producing hydrogen by using coke oven gas mainly comprise a pressure swing adsorption method and a membrane separation method, but the two methods do not use other gases except hydrogen in coke oven gas, namely CH 4 CO and CO 2 Therefore, the overall utilization efficiency of the coke oven gas needs to be improved.
Disclosure of Invention
The invention provides a method for preparing hydrogen by coke oven coal chemical looping, aiming at the problem of resource utilization of coke oven gas in the prior art, and the method is based on Ce 1-x Fe x O 2-δ Ce-Fe-X-O (X = Mn, cu or Ni), niO/MgO, la 1-x Sr x FeO 3 、LaNi x Fe 1-x O 3 The method of adopting chemical chain on oxygen carrier can effectively utilize each component of coke oven gas to prepare pure hydrogen, ce 1-x Fe x O 2-δ Ce-Fe-X-O (X = Mn, cu or Ni), niO/MgO, la 1-x Sr x FeO 3 、LaNi x Fe 1-x O 3 The iso-oxygen carrier can be recycled, so that the cost is greatly saved, and the oxygen carrier and the coke oven gas are economically and efficiently utilized. The invention effectively overcomes the defects and shortcomings of the traditional coke oven gas component separation and hydrogen preparation.
A method for preparing hydrogen by coke oven coal chemical looping comprises the following specific steps:
(1) Placing an oxygen carrier in a reaction tube, and heating to 750-900 ℃ at a constant speed, wherein the oxygen carrier is Ce 1-x Fe x O 2-δ 、Ce-Fe-X-O、NiO/MgO、La 1-x Sr x FeO 3 、LaNi x Fe 1-x O 3 One or more oxygen carriers, wherein X in Ce-Fe-X-O is Mn, cu or Ni;
(2) Introducing the coke oven gas into the reaction tube in the step (1), reacting the coke oven gas with an oxygen carrier at the temperature of 750-900 ℃, reducing the oxygen carrier into an oxygen loss carrier, and oxidizing the coke oven gas into CO 2 And water or synthesis gas;
(3) Introducing water vapor into the reaction tube in the step (2), reacting with the oxygen loss carrier at the temperature of 750-900 ℃, oxidizing the oxygen loss carrier into an oxygen carrier by the water vapor, and simultaneously converting the water vapor into hydrogen because the water vapor is deprived of oxygen by the oxygen loss carrier;
(4) Condensing and separating the mixed gas of the excess water vapor and the hydrogen in the step (3), and purifying to obtain pure H 2 。
The step (1) Ce 1-x Fe x O 2-δ Wherein X is more than 0 and less than 1, the molar ratio of Ce, fe and X in Ce-Fe-X-O is 6 1-x Sr x FeO 3 Wherein x is more than 0 and less than 1 x Fe 1-x O 3 X is more than 0 and less than 0.1.
The main component of the coke oven gas in the step (2) is H 2 、CH 4 CO and CO 2 The flow rate of the coke oven gas is 100-200 mL/min.
Further, the preparation method of the oxygen carrier comprises the following steps
1) Dissolving oxygen carrier metal precursor salt in deionized water to obtain an oxygen carrier precursor salt mixed solution;
2) Placing the oxygen carrier precursor salt mixed solution obtained in the step 1) in a water bath at the temperature of 20-70 ℃ for stirring, simultaneously dropwise adding ammonia water into the oxygen carrier precursor salt mixed solution to adjust the pH value of the system to 9-10, continuously stirring for reaction for 0.5-3 h, standing for aging for 1-6 h, carrying out solid-liquid separation, and alternately washing the solid for 2-5 times by using deionized water and absolute ethyl alcohol;
3) Drying the solid washed in the step 2), then crushing the dried solid, and roasting the crushed solid in an air atmosphere at the temperature of 750-850 ℃ for 2-6 h to obtain the oxygen carrier.
The concentration of the oxygen carrier precursor salt mixed solution in the step 1) is 0.1-0.3 mol/L.
The mass concentration of the ammonia water in the step 2) is 5-25%, and the titration rate is 1-5 drops/s.
Said Ce 1-x Fe x O 2-δ In δ The values are much less than 2 to the point of being negligible.
The coke oven gas is a gas which is completely pretreated by tar removal, desulfurization, naphthalene removal, ammonia washing, light oil removal, benzene, toluene, xylene recovery and the like, and the main component of the coke oven gas is H 2 、CH 4 CO and CO 2 。
The reaction tube of the invention only needs to be filled with the primary oxygen carrier, the coke oven gas and the Ce 1-x Fe x O 2-δ Ce-Fe-X-O (X = Mn, cu or Ni), niO/MgO, la 1-x Sr x FeO 3 Or LaNi x Fe 1-x O 3 Oxygen carriers react to produce CO 2 And water or synthetic gas, wherein the oxygen carrier is reduced, then water vapor is introduced to react with the reduced oxygen loss carrier to generate hydrogen, and the reduced oxygen loss carrier is oxidized to return to the initial state of the oxygen carrier through the water vapor; ce of the invention 1-x Fe x O 2-δ Ce-Fe-X-O (X = Mn, cu or Ni), niO/MgO, la 1-x Sr x FeO 3 、LaNi x Fe 1-x O 3 The oxygen carrier can promote the partial oxidation of methane in the coke oven gas into synthesis gas or the complete oxidation into CO to different degrees 2 And H 2 O and Ce 1-x Fe x O 2-δ Ce-Fe-X-O (X = Mn, cu or Ni), niO/MgO, la 1-x Sr x FeO 3 、LaNi x Fe 1-x O 3 The oxygen carrier can be recycled. In the reaction process, the synthesis gas obtained by converting the coke oven gas in the reduction stage can be used as a chemical raw material, and if the coke oven gas is completely converted into CO in the reduction stage 2 And H 2 O, can better capture CO 2 To reduce CO 2 And (4) discharging. The high-purity hydrogen obtained in the oxidation stage can be used as fuel or chemical raw materials, and the like, and can also be used for smelting important metals by utilizing the reducibility of the hydrogen.
The invention has the beneficial effects that:
(1) The invention effectively overcomes the defects and shortcomings of the traditional coke oven gas component separation and hydrogen preparation, and is based on Ce 1-x Fe x O 2-δ Ce-Fe-X-O (X = Mn, cu or Ni), niO/MgO, la 1-x Sr x FeO 3 Or LaNi x Fe 1-x O 3 The components of the coke oven gas are efficiently utilized by a chemical chain method on an oxygen carrier to prepare pure hydrogen;
(2)Ce 1-x Fe x O 2-δ Ce-Fe-X-O (X = Mn, cu or Ni), niO/MgO, la 1-x Sr x FeO 3 Or LaNi x Fe 1-x O 3 The oxygen carrier can promote the partial oxidation of methane in the coke oven gas into synthesis gas or the complete oxidation into CO to different degrees 2 And H 2 O and Ce 1-x Fe x O 2-δ Ce-Fe-X-O (X = Mn, cu or Ni), niO/MgO, la 1-x Sr x FeO 3 Or LaNi x Fe 1-x O 3 The oxygen carrier can be recycled, so that the cost is greatly saved, and the oxygen carrier and the coke oven gas are economically and efficiently utilized.
Drawings
FIG. 1 is a diagram showing the change of each component in the coke oven gas reaction in example 1;
FIG. 2 is a graph of the steam hydrogen production of example 1;
FIG. 3 is a diagram showing the change of each component in the coke oven gas reaction in example 2;
FIG. 4 is a graph of the hydrogen production from steam in example 2;
FIG. 5 is a diagram showing the change of each component in the coke oven gas reaction in example 3;
FIG. 6 is a graph of the production of hydrogen from steam in example 3;
FIG. 7 is a diagram showing the change of each component in the coke oven gas reaction of example 4;
FIG. 8 is a graph of hydrogen production from steam for example 4;
FIG. 9 is a diagram showing changes in components of a coke oven gas reaction in example 5;
FIG. 10 is a graph of the production of hydrogen from steam in example 5.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: ce 6 Fe 4 O 2-δ The preparation method of the oxygen carrier comprises the following specific steps:
1) Adding Ce (NO) 3 ) 3 .6H 2 O、Fe(NO 3 ) 3 .9H 2 Dissolving O in deionized water to obtain an oxygen carrier precursor salt mixed solution; wherein Ce (NO) 3 ) 3 .6H 2 O、Fe(NO 3 ) 3 .9H 2 The molar ratio of O is 6;
2) Placing the oxygen carrier precursor salt mixed solution obtained in the step 1) in a water bath at the temperature of 70 ℃ for stirring, simultaneously dropwise adding ammonia water with the mass concentration of 15% into the oxygen carrier precursor salt mixed solution at the speed of 1 drop/s to adjust the pH value of the system to 9.5, continuously and rapidly stirring for reaction for 3 hours, standing and aging for 3 hours, carrying out solid-liquid separation, and then alternately washing the solid for 4 times by adopting deionized water and absolute ethyl alcohol;
3) Drying the solid washed in the step 2) at the temperature of 110 ℃ for 12h, then crushing the dried solid, and roasting the crushed solid in an air atmosphere at the temperature of 750 ℃ for 2h to obtain Ce 6 Fe 4 O 2-δ Oxygen carrier, wherein the temperature rising rate of roasting is 10 ℃/min, and the prepared Ce 6 Fe 4 O 2-δ Granulating the oxygen carrier into 20-40 meshes for preparing hydrogen by using a coke oven gas chemical chain;
a method for preparing hydrogen by coke oven coal chemical looping comprises the following specific steps:
(1) 2g of Ce 6 Fe 4 O 2-δ Placing the oxygen carrier in a reaction tube, and raising the temperature to 850 ℃ at a constant speed;
(2) Introducing coke oven gas into the reaction tube in the step (1), and introducing the coke oven gas and Ce at the temperature of 850 DEG C 6 Fe 4 O 2-δ Oxygen carrier reaction, ce 6 Fe 4 O 2-δ The oxygen carrier is reduced to oxygen loss carrier, and the coke oven gas is oxidized to CO 2 And water or synthesis gas; wherein the coke oven gas is completely pretreated gas, and the coke oven gas comprises the following components in percentage by volume: h 2 (6.0％)、CH 4 (2.8％)、CO(0.9％)、CO 2 (0.3%); the flow rate of coke oven gas is 120mL/min;
(3) Then introducing water vapor into the reaction tube in the step (2), wherein the flow rate of the water vapor is 150mL/min, reacting with the oxygen loss carrier at the temperature of 850 ℃, and oxidizing the oxygen loss carrier into Ce 6 Fe 4 O 2-δ Oxygen carrier, wherein the water vapor is deprived of oxygen by the oxygen loss carrier to become hydrogen;
(4) Condensing and separating the redundant water vapor in the step (3) and the mixed gas of the hydrogen, and purifying to obtain pure H 2 ；
The change diagram of each component of the coke oven gas reaction is shown in figure 1, and the hydrogen production curve diagram of water vapor is shown in figure 2; as can be seen from FIGS. 1 and 2, when coke oven gas reacts with oxygen carrier, CH 4 The overall conversion rate is lower, and CH is generated in the early stage of the reaction 4 And conversion of CO to CO 2 ，H 2 Conversion to water (peaks of water not detectable by mass spectrometry) resulting in CO 2 The content is increased, and a large amount of synthesis gas is generated in the later reaction stage, so that H 2 And overall CO content increases; water vapor introduction to produce H 2 The time is 20min, and almost no CO is generated, which indicates that the purity of the hydrogen is very high; the coke oven gas and the oxygen carrier are alternately reacted, and then the reduced oxygen loss carrier is oxidized by introducing water vapor to produce hydrogen, so that the recycling of the oxygen carrier can be realized.
Example 2: the preparation method of the Ce-Fe-Mn-O oxygen carrier comprises the following specific steps:
1) Ce (NO) 3 ) 3 .6H 2 O、Fe(NO 3 ) 3 .9H 2 O、MnN 2 O 6 .4H 2 Dissolving O in deionized water to obtain an oxygen carrier precursor salt mixed solution; wherein Ce (NO) 3 ) 3 .6H 2 O、Fe(NO 3 ) 3 .9H 2 O、MnN 2 O 6 .4H 2 The molar ratio of O to O is 6;
2) Placing the oxygen carrier precursor salt mixed solution obtained in the step 1) in a water bath at the temperature of 20 ℃ for stirring, dropwise adding ammonia water with the mass concentration of 5% into the oxygen carrier precursor salt mixed solution at the speed of 2 drops/s to adjust the pH value of the system to be 9.0, continuously and rapidly stirring for reaction for 1h, standing and aging for 6h, carrying out solid-liquid separation, and alternately washing the solid for 2 times by adopting deionized water-absolute ethyl alcohol;
3) Drying the solid washed in the step 2) at the temperature of 80 ℃ for 6h, then crushing the solid, and roasting the crushed solid in an air atmosphere at the temperature of 800 ℃ for 4h to obtain the Ce-Fe-Mn-O oxygen carrier, wherein the roasting heating rate is 5 ℃/min, and granulating the prepared Ce-Fe-Mn-O oxygen carrier into 20-40 meshes for hydrogen production by a coke oven gas chemical chain;
a method for producing hydrogen by coke oven coal chemical looping comprises the following specific steps:
(1) 0.5g of Ce-Fe-Mn-O oxygen carrier is placed in a reaction tube and heated to 800 ℃ at a constant speed;
(2) Introducing the coke oven gas into the reaction tube in the step (1), reacting the coke oven gas with the Ce-Fe-Mn-O oxygen carrier at the temperature of 800 ℃, reducing the Ce-Fe-Mn-O oxygen carrier into an oxygen loss carrier, and oxidizing the coke oven gas into CO 2 And water or synthesis gas; wherein the coke oven gas is completely pretreated gas, and the coke oven gas comprises the following components in percentage by volume: h 2 (6.0％)、CH 4 (2.8％)、CO(0.9％)、CO 2 (0.3%); the flow rate of coke oven gas is 100mL/min;
(3) Introducing water vapor into the reaction tube in the step (2), wherein the flow of the water vapor is 150mL/min, reacting with the oxygen loss carrier at the temperature of 800 ℃, oxidizing the oxygen loss carrier into a Ce-Fe-Mn-O oxygen carrier, and changing the water vapor into hydrogen because the water vapor is deprived of oxygen by the oxygen loss carrier;
(4) Condensing and separating the redundant water vapor in the step (3) and the mixed gas of the hydrogen, and purifying to obtain pure H 2 ；
The change diagram of each component of the coke oven gas reaction of the embodiment is shown in figure 3, and the hydrogen production curve diagram of water vapor is shown in figure 4; as can be seen from FIGS. 3 and 4, the coke oven gas and the oxygen carrierIn reaction, CH 4 The overall conversion rate is low, and CH is generated in the early stage of the reaction 4 And conversion of CO to CO 2 ，H 2 Conversion to water (peaks of water not detected by mass spectrometry) resulting in CO 2 The content is increased, and a small amount of synthesis gas, H, is generated in the later reaction stage 2 Is greater than the syngas produced, so H 2 The whole content is reduced; water vapor introduction to produce H 2 The time of (2) is 25min, and almost no CO is generated, which indicates that the purity of the hydrogen is very high; the coke oven gas and the oxygen carrier are alternately reacted, and then the reduced oxygen loss carrier is oxidized by introducing water vapor to produce hydrogen, so that the recycling of the oxygen carrier can be realized.
Example 3: the preparation method of the NiO/MgO oxygen carrier comprises the following specific steps:
1) Mixing Ni (NO) 3 ) 2 .6H 2 O、Mg(NO 3 ) 2 .6H 2 Dissolving O in deionized water to obtain an oxygen carrier precursor salt mixed solution; wherein Ni (NO) 3 ) 2 .6H 2 O、Mg(NO 3 ) 2 .6H 2 The molar ratio of O is 1;
2) Placing the oxygen carrier precursor salt mixed solution obtained in the step 1) in a water bath at the temperature of 50 ℃ for stirring, dropwise adding ammonia water with the mass concentration of 20% into the oxygen carrier precursor salt mixed solution at the speed of 3 drops/s to adjust the pH value of the system to 9.3, continuously and rapidly stirring for reaction for 1h, standing and aging for 4h, carrying out solid-liquid separation, and alternately washing the solid for 2 times by adopting deionized water-absolute ethyl alcohol;
3) Drying the solid washed in the step 2) at 100 ℃ for 18h, then crushing and roasting in an air atmosphere at 800 ℃ for 4h to obtain a NiO/MgO oxygen carrier, wherein the roasting heating rate is 5 ℃/min, and granulating the prepared NiO/MgO oxygen carrier into 20-40 meshes for hydrogen production by a coke oven gas chemical looping;
a method for producing hydrogen by coke oven coal chemical looping comprises the following specific steps:
(1) 1.0g of NiO/MgO oxygen carrier is placed in a reaction tube and heated to 850 ℃ at a constant speed;
(2) Introducing coke oven gas into the reaction tube in the step (1) at the temperatureThe coke oven gas reacts with the NiO/MgO oxygen carrier at 850 ℃, the NiO/MgO oxygen carrier is reduced into an oxygen loss carrier, and the coke oven gas is oxidized into CO 2 And water or synthesis gas; wherein the coke oven gas is completely pretreated gas, and the coke oven gas comprises the following components in percentage by volume: h 2 (6.0％)、CH 4 (2.8％)、CO(0.9％)、CO 2 (0.3%); the flow rate of coke oven gas is 150mL/min;
(3) Introducing water vapor into the reaction tube in the step (2), wherein the flow rate of the water vapor is 150mL/min, reacting with an oxygen loss carrier at the temperature of 850 ℃, oxidizing the oxygen loss carrier into a NiO/MgO oxygen carrier, and changing the water vapor into hydrogen gas because the water vapor is deprived of oxygen by the oxygen loss carrier;
(4) Condensing and separating the redundant water vapor in the step (3) and the mixed gas of the hydrogen, and purifying to obtain pure H 2 ；
The change diagram of each component of the coke oven gas reaction of the embodiment is shown in figure 5, and the hydrogen production curve diagram of water vapor is shown in figure 6; as can be seen from FIGS. 5 and 6, CH is present when coke oven gas reacts with oxygen carrier 4 The overall conversion is higher, but the second step is fed with steam to produce H 2 The content of the NiO/MgO oxygen carrier is very low, which indicates that the NiO/MgO oxygen carrier is not suitable for producing hydrogen by using coke oven gas.
Example 4: la 0.5 Sr 0.5 FeO 3 The preparation method of the oxygen carrier comprises the following specific steps:
1) Mixing La (NO) 3 ) 3 .6H 2 O、Sr(NO 3 ) 2 、Fe(NO 3 ) 3 .9H 2 Dissolving O in deionized water to obtain an oxygen carrier precursor salt mixed solution; wherein La (NO) 3 ) 3 .6H 2 O、Sr(NO 3 ) 2 、Fe(NO 3 ) 3 .9H 2 The molar ratio of O is 0.5;
2) Placing the oxygen carrier precursor salt mixed solution obtained in the step 1) in a water bath at the temperature of 60 ℃ for stirring, dropwise adding ammonia water with the mass concentration of 10% into the oxygen carrier precursor salt mixed solution at the speed of 5 drops/s to adjust the pH value of the system to 9.7, continuously and rapidly stirring for reaction for 2 hours, standing and aging for 6 hours, carrying out solid-liquid separation, and alternately washing the solid for 4 times by adopting deionized water-absolute ethyl alcohol;
3) Drying the solid washed in the step 2) at the temperature of 90 ℃ for 24h, then crushing the dried solid, and roasting the crushed solid in an air atmosphere at the temperature of 850 ℃ for 6h to obtain La 0.5 Sr 0.5 FeO 3 Oxygen carrier, wherein the temperature rise rate of roasting is 7 ℃/min, and the prepared La 0.5 Sr 0.5 FeO 3 Granulating the oxygen carrier into 20-40 meshes for preparing hydrogen by a coke oven gas chemical chain;
a method for preparing hydrogen by coke oven coal chemical looping comprises the following specific steps:
(1) 1.5g of La 0.5 Sr 0.5 FeO 3 Placing the oxygen carrier in a reaction tube, and raising the temperature to 900 ℃ at a constant speed;
(2) Introducing coke oven gas into the reaction tube in the step (1), and reacting the coke oven gas and La at 900 DEG C 0.5 Sr 0.5 FeO 3 Oxygen carrier reaction, la 0.5 Sr 0.5 FeO 3 The oxygen carrier is reduced to oxygen loss carrier, and the coke oven gas is oxidized to CO 2 And water or syngas; wherein the coke oven gas is completely pretreated gas, and the coke oven gas comprises the following components in percentage by volume: h 2 (6.0％)、CH 4 (2.8％)、CO(0.9％)、CO 2 (0.3%); the flow rate of coke oven gas is 200mL/min;
(3) Then introducing water vapor into the reaction tube in the step (2), wherein the flow of the water vapor is 150mL/min, reacting with an oxygen loss carrier at the temperature of 900 ℃, and oxidizing the oxygen loss carrier into La 0.5 Sr 0.5 FeO 3 Oxygen carrier, wherein the water vapor is deprived of oxygen by the oxygen loss carrier to become hydrogen;
(4) Condensing and separating the redundant water vapor in the step (3) and the mixed gas of the hydrogen, and purifying to obtain pure H 2 ；
The change diagram of each component of the coke oven gas reaction of the embodiment is shown in figure 7, and the hydrogen production curve diagram of water vapor is shown in figure 8; as can be seen from FIGS. 7 and 8, when coke oven gas reacts with oxygen carrier, CH 4 The overall conversion rate is higher, and CH is generated in the early stage of the reaction 4 And CO conversion to CO 2 ，H 2 Conversion to water (peaks of water not detectable by mass spectrometry) resulting in CO 2 The content of the sodium chloride is increased, and the sodium chloride is dissolved in the water,a small amount of synthesis gas, H, is produced in the later stage of the reaction 2 Is greater than the syngas produced, so H 2 The whole content is reduced; water vapor introduction to produce H 2 The time of (2) is 60min, and a small amount of CO is detected, which indicates that a small amount of cracking of methane occurs during the reaction with the coke oven gas in the first step, and carbon deposition is generated. The purity of hydrogen is also higher; the coke oven gas and the oxygen carrier are alternately reacted, and then the reduced oxygen loss carrier is oxidized by introducing water vapor to produce hydrogen, so that the recycling of the oxygen carrier can be realized.
Example 5: laNi 0.07 Fe 0.93 O 3 The preparation method of the oxygen carrier comprises the following specific steps:
1) Mixing La (NO) 3 ) 3 .6H 2 O、Ni(NO 3 ) 2 .6H 2 O、Fe(NO 3 ) 3 .9H 2 Dissolving O in deionized water to obtain an oxygen carrier precursor salt mixed solution; wherein La (NO) 3 ) 3 .6H 2 O、Ni(NO 3 ) 2 .6H 2 O、Fe(NO 3 ) 3 .9H 2 The molar ratio of O is 1;
2) Placing the oxygen carrier precursor salt mixed solution obtained in the step 1) in a water bath at the temperature of 70 ℃ for stirring, dropwise adding ammonia water with the mass concentration of 25% into the oxygen carrier precursor salt mixed solution at the speed of 5 drops/s to adjust the pH value of the system to 10, continuously and rapidly stirring for reaction for 3 hours, standing and aging for 6 hours, carrying out solid-liquid separation, and alternately washing the solid for 4 times by adopting deionized water-absolute ethyl alcohol;
3) Drying the solid washed in the step 2) at the temperature of 120 ℃ for 24h, then crushing the dried solid, and roasting the crushed solid in an air atmosphere at the temperature of 800 ℃ for 6h to obtain LaNi 0.07 Fe 0.93 O 3 Oxygen carrier, wherein the temperature rising rate of roasting is 10 ℃/min, and the prepared LaNi 0.07 Fe 0.93 O 3 Granulating the oxygen carrier into 20-40 meshes for preparing hydrogen by a coke oven gas chemical chain;
a method for producing hydrogen by coke oven coal chemical looping comprises the following specific steps:
(1) 2.0g of LaNi 0.07 Fe 0.93 O 3 Placing the oxygen carrier in a reaction tube, and raising the temperature to 800 ℃ at a constant speed;
(2) Introducing coke oven gas into the reaction tube in the step (1), and introducing the coke oven gas and LaNi at the temperature of 800 DEG C 0.07 Fe 0.93 O 3 Oxygen carrier reaction, laNi 0.07 Fe 0.93 O 3 The oxygen carrier is reduced to oxygen loss carrier, and the coke oven gas is oxidized to CO 2 And water or syngas; wherein the coke oven gas is completely pretreated gas, and the coke oven gas comprises the following components in percentage by volume: h 2 (6.0％)、CH 4 (2.8％)、CO(0.9％)、CO 2 (0.3%); the flow rate of coke oven gas is 200mL/min;
(3) Then introducing water vapor into the reaction tube in the step (2), wherein the flow rate of the water vapor is 150mL/min, reacting with an oxygen loss carrier at the temperature of 800 ℃, and oxidizing the oxygen loss carrier into LaNi 0.07 Fe 0.93 O 3 Oxygen carrier, wherein the water vapor is deprived of oxygen by the oxygen loss carrier to become hydrogen;
(4) Condensing and separating the redundant water vapor in the step (3) and the mixed gas of the hydrogen, and purifying to obtain pure H 2 ；
The change diagram of each component of the coke oven gas reaction of the embodiment is shown in figure 9, and the hydrogen production curve diagram of water vapor is shown in figure 10; as can be seen from FIGS. 9 and 10, CH is present when coke oven gas reacts with oxygen carrier 4 Almost complete conversion to high H 2 Syngas of/CO; water vapor introduction to produce H 2 The time of (2) is 50min, and almost no CO is generated, which indicates that the purity of the hydrogen is very high; the coke oven gas and the oxygen carrier are alternately reacted, and then the reduced oxygen loss carrier is oxidized by introducing water vapor to produce hydrogen, so that the recycling of the oxygen carrier can be realized.
Claims (5)
1. A method for producing hydrogen by a coke oven coal chemical looping is characterized by comprising the following specific steps:
(1) Placing an oxygen carrier in a reaction tube, and heating to 750-900 ℃ at a constant speed, wherein the oxygen carrier is Ce 1-x Fe x O 2-δ 、Ce-Fe-X-O、La 1-x Sr x FeO 3 、LaNi x Fe 1-x O 3 One kind or more kinds of oxygen carriersIn Ce-Fe-X-O, X is Mn, cu or Ni; ce 1-x Fe x O 2-δ Wherein X is more than 0 and less than 1, the molar ratio of Ce, fe and X in the Ce-Fe-X-O is 6 1-x Sr x FeO 3 Wherein x is more than 0 and less than 1 x Fe 1-x O 3 X is more than 0 and less than 0.1;
(2) Introducing the coke oven gas into the reaction tube in the step (1), reacting the coke oven gas with an oxygen carrier at the temperature of 750-900 ℃, reducing the oxygen carrier into an oxygen loss carrier, and oxidizing the coke oven gas into CO at the early stage 2 And water, which is later oxidized to synthesis gas;
(3) Introducing water vapor into the reaction tube in the step (2), reacting with an oxygen loss carrier at the temperature of 750-900 ℃, oxidizing the oxygen loss carrier into an oxygen carrier by the water vapor, and simultaneously converting the water vapor into hydrogen because the water vapor is deprived of oxygen by the oxygen loss carrier;
(4) Condensing and separating the mixed gas of the redundant water vapor and the hydrogen in the step (3), and purifying to obtain pure H 2 。
2. The method for producing hydrogen by coke oven gas chemical looping according to claim 1, characterized in that: the main component of the coke oven gas in the step (2) is H 2 、CH 4 CO and CO 2 The flow of the coke oven gas is 100 to 200mL/min.
3. The method for producing hydrogen by coke oven gas chemical looping according to claim 1, characterized in that: the preparation method of the oxygen carrier comprises
1) Dissolving oxygen carrier metal precursor salt in deionized water to obtain an oxygen carrier precursor salt mixed solution;
2) Placing the oxygen carrier precursor salt mixed solution obtained in the step 1) in a water bath at the temperature of 20-70 ℃ for stirring, dropwise adding ammonia water into the oxygen carrier precursor salt mixed solution to adjust the pH value of the system to be 9-10, continuously stirring for reaction for 0.5-3h, standing for aging for 1-6h, carrying out solid-liquid separation, and alternately washing with deionized water and absolute ethyl alcohol for 2-5 times to obtain solid;
3) Drying the solid washed in the step 2), then crushing, and then baking in an air atmosphere at the temperature of 750-850 ℃ for 2-6 h to obtain the oxygen carrier.
4. The method for producing hydrogen by coke oven gas chemical looping according to claim 3, characterized in that: the total concentration of the oxygen carrier precursor salt mixed solution in the step 1) is 0.1 to 0.3mol/L.
5. The method for producing hydrogen by coke oven gas chemical looping according to claim 3, characterized in that: and 2) the mass concentration of ammonia water in the step 2) is 5-25%, and the titration rate is 1-5 drops/s.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2001292666A1 (en) * | 2000-09-18 | 2002-06-20 | Union Carbide Chemicals & Plastics Technology Corporation | Methods for manufacturing olefins from lower alkanes by oxidative dehydrogenation |
| EP1419814A1 (en) * | 2002-11-15 | 2004-05-19 | L'AIR LIQUIDE, Société Anonyme à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des | Perovskite catalyst for the partial oxidation of natural gas |
| CN102585950A (en) * | 2012-02-27 | 2012-07-18 | 四川亚连科技有限责任公司 | Method for preparing synthetic natural gas by coke oven gas in combination with straw gas |
| CN102861582A (en) * | 2012-10-11 | 2013-01-09 | 江苏科技大学 | Solid solution catalyst for hydrogen production by partial oxidation reforming of methane in coke oven gas |
| CN102935998A (en) * | 2012-10-11 | 2013-02-20 | 江苏科技大学 | Application of NiO/MgO solid solution catalyst in coke oven coal gas steam reforming hydrogen production method at low water carbon ratio |
| CN107142125A (en) * | 2017-06-07 | 2017-09-08 | 中国科学院广州能源研究所 | A kind of sludge chemical chain gasification orientation produces synthetic gas method and realizes the device of this method |
| CN108855109A (en) * | 2018-07-02 | 2018-11-23 | 西北大学 | A kind of chemical chain partial oxidation methane preparing synthetic gas carrier of oxygen and its preparation method and application |
| CN109761192A (en) * | 2019-03-07 | 2019-05-17 | 浦江思欣通科技有限公司 | A kind of producing hydrogen by using chemical chain |
| CN109833877A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of chemical chain partial oxidation methane catalyst for preparing synthetic gas and its preparation and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6518476B1 (en) * | 2000-09-18 | 2003-02-11 | Union Carbide Chemicals & Plastics Technology Corporation | Methods for manufacturing olefins from lower alkans by oxidative dehydrogenation |
| US10670262B2 (en) * | 2014-02-26 | 2020-06-02 | University Of Connecticut | Reactor for chemical-looping combustion |
-
2020
- 2020-03-17 CN CN202010188478.7A patent/CN111232920B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2001292666A1 (en) * | 2000-09-18 | 2002-06-20 | Union Carbide Chemicals & Plastics Technology Corporation | Methods for manufacturing olefins from lower alkanes by oxidative dehydrogenation |
| EP1419814A1 (en) * | 2002-11-15 | 2004-05-19 | L'AIR LIQUIDE, Société Anonyme à Directoire et Conseil de Surveillance pour l'Etude et l'Exploitation des | Perovskite catalyst for the partial oxidation of natural gas |
| CN102585950A (en) * | 2012-02-27 | 2012-07-18 | 四川亚连科技有限责任公司 | Method for preparing synthetic natural gas by coke oven gas in combination with straw gas |
| CN102861582A (en) * | 2012-10-11 | 2013-01-09 | 江苏科技大学 | Solid solution catalyst for hydrogen production by partial oxidation reforming of methane in coke oven gas |
| CN102935998A (en) * | 2012-10-11 | 2013-02-20 | 江苏科技大学 | Application of NiO/MgO solid solution catalyst in coke oven coal gas steam reforming hydrogen production method at low water carbon ratio |
| CN107142125A (en) * | 2017-06-07 | 2017-09-08 | 中国科学院广州能源研究所 | A kind of sludge chemical chain gasification orientation produces synthetic gas method and realizes the device of this method |
| CN109833877A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of chemical chain partial oxidation methane catalyst for preparing synthetic gas and its preparation and application |
| CN108855109A (en) * | 2018-07-02 | 2018-11-23 | 西北大学 | A kind of chemical chain partial oxidation methane preparing synthetic gas carrier of oxygen and its preparation method and application |
| CN109761192A (en) * | 2019-03-07 | 2019-05-17 | 浦江思欣通科技有限公司 | A kind of producing hydrogen by using chemical chain |
Non-Patent Citations (4)
| Title |
|---|
| Highly flexible and energy-efficient process for converting coke-oven gas and pulverized coke into methanol and ammonia using chemical looping technology;Zhao,YX,et al;《Energy Conversion And Management》;20211031;第248卷;全文 * |
| 化学链蒸汽重整制氢与合成气的基础研究;祝星;《中国博士学位论文全文数据库 工程科技I辑》;20121031(第10期);全文 * |
| 焦炉煤气化学链制氢基础研究-氧载体选择与循环性能;杨坤;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20210515(第05期);全文 * |
| 焦炉煤气的能源应用新方式及能源利用效率研究;曾凡瑞;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20210515(第05期);全文 * |
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