阅读说明：本技术 一种化学链制备氧气方法 (A kind of chemical chain prepares oxygen method ) 是由 陶进峰 于 2019-07-30 设计创作，主要内容包括：本发明提供一种化学链制备氧气方法,将Mn<Sub>2</Sub>O<Sub>3</Sub>/Mn<Sub>3</Sub>O<Sub>4</Sub>、BaO<Sub>2</Sub>/BaO、Co<Sub>3</Sub>O<Sub>4</Sub>/CoO、CUO/CU<Sub>2</Sub>O等固体载氧体活性成分浸没在熔盐内,使载氧体活性成分的放氧过程在熔盐环境下进行,进而促进载氧体活性成分分解生成氧气,显著提高化学链直接制备氧气的收集气中氧气纯度。(The present invention provides a kind of chemical chain and prepares oxygen method, by Mn 2 O 3 /Mn 3 O 4 、BaO 2 /BaO、Co 3 O 4 /CoO、CUO/CU 2 The solids oxygen carrier active constituent such as O is immersed in fused salt, carries out the oxygen process of putting of oxygen carrier active constituent under fused salt environment, and then oxygen carrier active ingredient breaks down is promoted to generate oxygen, is significantly improved chemical chain and is directly prepared oxygen purity in the collection gas of oxygen.)

1. the present invention provides a kind of chemical chain and prepares oxygen method, including puts oxygen process and oxygen uptake process, which is characterized in that oxygen carrier The oxygen process of putting of body active constituent carries out under fused salt environment；The oxygen carrier active constituent is selected from manganese, barium, cobalt, copper Metal oxide and its composite oxides and perovskite composite oxide, preferably Mn₂O₃/Mn₃O₄、BaO₂/BaO、Co₃O₄/ CoO or CUO/CU₂O, the temperature of molten salt is 400 ~ 1200 DEG C, preferably 550 ~ 950 DEG C at this time；The oxygen carrier active constituent is SrO₂/SrO、MnO₂/Mn₂O₃、Sb₂O₅/SbO₂Or Pb₃O₄/ PbO, at this time the temperature of molten salt be 150 ~ 600 DEG C, preferably 200 ~ 500℃。

2. chemical chain according to claim 1 prepares oxygen method, which is characterized in that the suction of the oxygen carrier active constituent Oxygen process carries out under fused salt environment；The oxygen carrier active constituent, which is under fused salt environment, refers to that the oxygen carrier is living Property ingredient dissolution or be immersed in fused salt.

3. chemical chain according to claim 1 prepares oxygen method, which is characterized in that the concentration of oxygen gas S of the fused salt Meet: 0mol/m³< S≤1000mol/m³, preferably 0mol/m³< S≤100mol/m³, more preferable 0mol/m³< S≤10mol/ m³。

4. chemical chain according to claim 1 prepares oxygen method, which is characterized in that the fused salt is to described in reduction-state The solubility of oxygen carrier active constituent is 0.1% ~ 100%, preferably 1% ~ 50%.

5. chemical chain according to claim 1 prepares oxygen method, which is characterized in that the fused salt includes melting halogenation Or mixtures thereof object, fused carbonate, molten silicate, molten nitrate, molten sulfate, preferably CaCl₂、KCl 、 Na₂CO₃、K₂CO₃、Na₂SiO₃、K₂SiO₃、CaCl₂-NaCl、CaCl₂-CaF₂、NaCl-KCl 、LiF-Li₂CO₃、Na₂CO₃- K₂CO₃、Na₂CO₃-Na₂SiO₃、K₂CO₃-K₂SiO₃、Na₂CO₃-Li₂CO₃、K₂CO₃-Li₂CO₃、CaCl₂-NaCl-CaF₂、NaCl- KCl-NaF、LiF-NaF-KF、Na₂CO₃-K₂CO₃-Na₂SiO₃Or Na₂CO₃-K₂CO₃-K₂SiO₃, more preferable CaCl₂、CaCl₂- NaCl、Na₂CO₃-K₂CO₃-Na₂SiO₃Or Na₂CO₃-K₂CO₃-K₂SiO₃；The halide includes KF, CaF₂、NaF、LiF、KCl、 CaCl₂、NaCl、MgCl₂、KBr、CaBr₂Or NaBr, preferably CaCl₂Or NaCl；The carbonate includes Na₂CO₃、K₂CO₃Or Li₂CO₃；The silicate includes Na₂SiO₃Or K₂SiO₃。

6. chemical chain according to claim 1 prepares oxygen method, which is characterized in that the oxygen carrier active constituent and institute The mass ratio for stating fused salt is 1:1000 ~ 20:1, preferably 1:100 ~ 1:1, more preferable 1:100 ~ 1:2.

7. chemical chain according to claim 1 prepares oxygen method, which is characterized in that the oxygen carrier active constituent is CUO/CU₂When O, the temperature of molten salt for putting oxygen process is 795 ~ 1200 DEG C, and preferably 800 ~ 1000 DEG C, the oxygen uptake process melts Salt temperature is 400 ~ 950 DEG C, preferably 600 ~ 850 DEG C.

8. chemical chain according to claim 1 prepares oxygen method, which is characterized in that the absolute pressure for putting oxygen process For 0.6 ~ 1.1atm, preferably 0.9 ~ 1atm；The absolute pressure of the oxygen uptake process is 1 ~ 10atm, preferably 1 ~ 2atm.

9. chemical chain according to claim 1 prepares oxygen method, which is characterized in that oxygen carrier is living during the oxygen uptake Property ingredient draws oxygen sources in oxygenous gas, the oxygenous gas includes that air, flue gas, flue gas and air are mixed Close gas；The temperature of the oxygenous gas is 10 ~ 1200 DEG C, preferably 10 ~ 800 DEG C during the oxygen uptake.

10. chemical chain according to claim 1 prepares oxygen method, which is characterized in that the gas-liquid of the oxygen uptake process connects The ratio between the phase contact area of touching and liquid phase volume > 50m²/m³, preferably > 100m²/m³, further put the gas-liquid contact of oxygen process Phase contact area and the ratio between liquid phase volume < 50m²/m³, preferably < 20m²/m³。

Technical field

The invention belongs to prepare oxygen technical field more particularly to chemical chain to prepare oxygen method.

Background technique

Chemical chain prepare oxygen technology basic principle be made by control temperature, the conditions such as pressure oxygen carrier carry out oxygen uptake, Oxygen reaction is put, to realize the purpose for separating oxygen from air, energy consumption, cost separate air oxygenerating technology than Deep Cooling Method It is low.

The oxygen carrier that chemical chain prepares oxygen is usually made of active constituent and carrier, and active constituent is to participate in reaction transmitting The substance of oxygen, active constituent mainly include that manganese, barium, strontium, cobalt, copper metal oxide and its composite oxides and Ca-Ti ore type are multiple Close oxide；Carrier is then the substance for carrying active constituent, and common vector includes Al₂O₃、SiO₂、TiO₂、ZrO₂、 MgAl₂O₄, sepiolite, kaolin and bentonite.

It includes putting oxygen process and oxygen uptake process that chemical chain, which prepares oxygen, with CUO/CU₂For O oxygen carrier, Fig. 1 is seen, firstly, It is put in oxygen reactor in 900 DEG C of normal pressures, oxidation state oxygen carrier active constituent CUO resolves into reduction-state oxygen carrier active constituent CU₂O And oxygen, this sees formula 1 to put oxygen process；Then, reduction-state oxygen carrier active constituent CU₂It is anti-that O is sent to 700 DEG C of normal pressure oxygen uptakes It answers in device, the air oxidation being passed into oxygen-absorbing reaction device is oxidation state oxygen carrier active constituent CUO, this is oxygen uptake process, is seen Formula 2.

CUO→CU₂O + O₂Formula 1

CU₂O + O₂→ CUO formula 2

Comprehensively consider the factors such as the anti-sintering property of oxygen carrier, oxygen carrier reaction temperature should control in OK range.And at this In temperature range, the oxygen equilibrium partial pressure of oxygen carrier is lower, causes maximum oxygen concentration in collection gas low, collection gas utility value is not It is high.With CUO/CU₂For O oxygen carrier, to avoid oxygen carrier from being sintered, CUO/CU₂O oxygen carrier reaction temperature general control is 1000 Within DEG C, and the CUO/CU under 1000 DEG C of condition of normal pressure₂The maximum oxygen equilibrium partial pressure of O oxygen carrier is less than 0.21atm, to promote Oxygen generation can be passed through vapor, final to collect the gaseous mixture that gas is oxygen and vapor, and wherein oxygen percentage by volume is not Foot 20%.Therefore, how improving chemical chain and directly preparing in the collection gas of oxygen oxygen purity becomes urgent problem to be solved.

Summary of the invention

The present invention provides a kind of chemical chain and prepares oxygen method, and solid oxygen carrier active constituent is immersed in fused salt, is made The oxygen process of putting of oxygen carrier active constituent carries out under fused salt environment, and then oxygen carrier active ingredient breaks down is promoted to generate oxygen, It significantly improves chemical chain and directly prepares oxygen purity in the collection gas of oxygen.

The present invention provides a kind of chemical chain and prepares oxygen method, and the oxygen process of putting of oxygen carrier active constituent is place in this method It is carried out under fused salt environment, the specific steps are as follows:

In putting oxygen reactor, oxygen carrier active constituent is immersed in fused salt, puts oxygen condition, oxygen when oxygen carrier active constituent reaches Changing state oxygen carrier active ingredient breaks down is reduction-state oxygen carrier active constituent and oxygen, this is to put oxygen process；

In oxygen-absorbing reaction device, oxygen carrier active constituent is immersed in fused salt, is passed through air into oxygen-absorbing reaction device, air and molten Oxygen carrier active ingredient contacts in salt, when oxygen carrier active constituent reaches oxygen uptake condition, reduction-state oxygen carrier active constituent is empty Gas is oxidized to oxidation state oxygen carrier active constituent, this is oxygen uptake process, which can also carry out under non-fused salt environment, described Air can be replaced by other oxygenous gases, as flue gas, flue gas mix with air gas；

Oxygen carrier active constituent put oxygen, circulation puts oxygen, oxygen uptake process in oxygen-absorbing reaction device, realize that chemical chain prepares oxygen mesh 's.

The oxygen carrier active constituent is selected from manganese, barium, cobalt, copper metal oxide and its composite oxides and Ca-Ti ore type Composite oxides, preferably Mn₂O₃/Mn₃O₄、BaO₂/BaO、Co₃O₄/ CoO or CUO/CU₂O, the temperature of molten salt are 400 ~ 1200 DEG C, preferably 550 ~ 950 DEG C.

The oxygen carrier active constituent is SrO₂/SrO、MnO₂/Mn₂O₃、Sb₂O₅/SbO₂Or Pb₃O₄/ PbO, the fused salt temperature Degree is 150 ~ 600 DEG C, preferably 200 ~ 500 DEG C.

The oxygen carrier active constituent, which is under fused salt environment, to be referred to the oxygen carrier active constituent dissolution or is immersed in molten In salt.

The oxygen uptake process of the oxygen carrier active constituent carries out under fused salt environment.

The concentration of oxygen gas S of the fused salt meets: 0mol/m³< S≤1000mol/m³, preferably 0mol/m³< S≤ 100mol/m³, more preferable 0mol/m³< S≤10mol/m³。

The fused salt is 0.1% ~ 100%, preferably 1% ~ 50% to the solubility of the oxygen carrier active constituent of reduction-state.

The fused salt include melting halide, fused carbonate, molten silicate, molten nitrate, molten sulfate or Its mixture, preferably CaCl₂、KCl 、Na₂CO₃、K₂CO₃、Na₂SiO₃、K₂SiO₃、CaCl₂-NaCl、CaCl₂-CaF₂、NaCl- KCl 、LiF-Li₂CO₃、Na₂CO₃-K₂CO₃、Na₂CO₃-Na₂SiO₃、K₂CO₃-K₂SiO₃、Na₂CO₃-Li₂CO₃、K₂CO₃-Li₂CO₃、 CaCl₂-NaCl-CaF₂、NaCl-KCl-NaF、LiF-NaF-KF、Na₂CO₃-K₂CO₃-Na₂SiO₃Or Na₂CO₃-K₂CO₃-K₂SiO₃, More preferable CaCl₂、CaCl₂-NaCl、Na₂CO₃-K₂CO₃-Na₂SiO₃Or Na₂CO₃-K₂CO₃-K₂SiO₃；The halide include KF, CaF₂、NaF、LiF、KCl、CaCl₂、NaCl、MgCl₂、KBr、CaBr₂Or NaBr, preferably CaCl₂Or NaCl；The carbonate packet Include Na₂CO₃、K₂CO₃Or Li₂CO₃；The silicate includes Na₂SiO₃Or K₂SiO₃。

The mass ratio of the oxygen carrier active constituent and the fused salt is 1:1000 ~ 20:1, preferably 1:100 ~ 1:1, more excellent Select 1:100 ~ 1:2.

The oxygen carrier active constituent is powdered or liquid in the fused salt.

The oxygen process of putting is carried out in putting oxygen reactor；The oxygen uptake process is carried out in oxygen-absorbing reaction device 's；It is described to put oxygen reactor and the oxygen-absorbing reaction device can be same reactor.

The oxygen carrier active constituent is CUO/CU₂When O, the temperature of molten salt for putting oxygen process is 795 ~ 1200 DEG C, excellent 800 ~ 1000 DEG C are selected, the temperature of molten salt of the oxygen uptake process is 400 ~ 950 DEG C, preferably 600 ~ 850 DEG C.

The absolute pressure for putting oxygen process is 0.6 ~ 1.1atm, preferably 0.9 ~ 1atm；The absolute pressure of the oxygen uptake process Power is 1 ~ 10atm, preferably 1 ~ 2atm.

The oxygen sources of oxygen carrier active ingredient draws are described oxygenous in oxygenous gas during the oxygen uptake Gas includes that air, flue gas, flue gas mix with air gas；During the oxygen uptake the oxygenous gas temperature be 10 ~ 1200 DEG C, preferably 10 ~ 800 DEG C.

The gas-liquid contact form of the oxygen uptake process is that gas phase is dispersed in fused salt with bubble shape, fused salt is with droplet-like point It dissipates in the gas phase or fused salt is contacted with membranaceous with gas phase；The phase contact area of the gas-liquid contact of the oxygen uptake process and liquid phase volume it Than > 50m²/m³, preferably > 100m²/m³, further put the ratio between phase contact area and liquid phase volume of the gas-liquid contact of oxygen process < 50m²/m³, preferably < 20m²/m³。

Beneficial effects of the present invention: it significantly improves chemical chain and directly prepares oxygen purity in the collection gas of oxygen, at 900 DEG C Under condition of normal pressure, using CUO/ CU₂O directly prepares oxygen volume basis in the collection gas of oxygen as oxygen carrier active constituent Than up to 60% or more.

Detailed description of the invention

Fig. 1 is that chemical chain prepares oxygen schematic diagram.

Specific embodiment

Summary of the invention of the invention is described in further detail With reference to embodiment.It should be understood that this hair It is bright that the embodiments are used only to illustrate the invention is not intended to limit the present invention, in the case where not departing from technical thought of the invention, according to Ordinary skill knowledge and customary means, the various replacements and change made, should all be included within the scope of the invention.