CN110483228B - Method and device for simultaneously obtaining high-purity hydrogen and chemicals through reaction in proton conduction membrane reactor - Google Patents
Method and device for simultaneously obtaining high-purity hydrogen and chemicals through reaction in proton conduction membrane reactor Download PDFInfo
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Abstract
The invention relates to a method for preparing high-purity hydrogen and chemicals, in particular to a method and a device for simultaneously obtaining the high-purity hydrogen and the chemicals through reaction (low-carbon alkane high-temperature reforming or catalytic dehydrogenation reaction) in a proton-conducting membrane reactor. High-temperature reforming reaction or catalytic dehydrogenation reaction is carried out in the membrane reactor, hydrogen protons are transmitted in a compact proton conducting membrane of the membrane reactor by utilizing the hydrogen partial pressure gradient effect, hydrogen generated by the reaction is removed in situ, and then two naturally separated chemicals and high-purity hydrogen are obtained in the membrane reactor. The method of the invention utilizes the hydrogen partial pressure gradient effect to transmit hydrogen protons in oxide lattices of a proton conduction membrane, removes hydrogen generated by methane steam reforming or ethane dehydrogenation in situ, and prepares two naturally separated chemicals and hydrogen simultaneously in a membrane reactor. Because the selectivity of the proton conduction membrane to hydrogen is 100 percent, and any other gas can not permeate through the compact proton conduction membrane, the hydrogen prepared by the method has high purity, simple device and strong operation practicability, and can be applied to hydrogen-involved reactions such as methane aromatization, propane dehydrogenation and the like.
Description
Technical Field
The invention relates to a method for preparing high-purity hydrogen and chemicals, in particular to a method and a device for simultaneously obtaining the high-purity hydrogen and the chemicals through reaction (low-carbon alkane high-temperature reforming or catalytic dehydrogenation reaction) in a proton-conducting membrane reactor.
Background
Fischer-Tropsch synthesis is an important way for converting synthesis gas (a mixture of hydrogen and carbon monoxide) into liquid fuels and chemicals, and the volume ratio of the hydrogen to the carbon monoxide in the synthesis gas required by the Fischer-Tropsch synthesis is 2. At present, synthesis gas preparation mainly comes from natural gas, shale gas and biogas (main component methane). The conventional process for preparing synthesis gas is methane steam reforming reaction (Choudhary et al, angel. chem. int. ed.2008,47,1828-1847), and the volume ratio of hydrogen to carbon monoxide in the obtained synthesis gas is usually 3, which needs to be adjusted by a ratio adjusting unitA ratio of 2 (suitable for the subsequent fischer-tropsch synthesis reaction) would increase the fischer-tropsch synthesis gas preparation process and the investment costs. In addition, high-quality hydrogen can be prepared by steam reforming of methane (Malarod-Fjeld et al, nat. energy 2017,2,923-931), such as Wuxuefeng and Wusufang of the China petrochemical company Limited, which are used to prepare pure hydrogen (Chinese patent application Nos. 200910085584.6 and 200610155120.4). However, the hydrogen gas obtained by the water gas shift reaction often contains a small amount of carbon monoxide, which will poison the Pt electrocatalyst of the fuel cell, and a subsequent multi-step processing unit is usually required to remove the carbon monoxide contained in the hydrogen gas, which will greatly increase the production cost of pure hydrogen, and in addition, the production of pure hydrogen by the water gas shift reaction additionally adds greenhouse gas CO 2And (4) discharging.
At the same time, ethylene is an important industrial raw material for the production of higher value base chemicals. The current ethylene maturation process is thermal cracking or catalytic cracking, but the process is accompanied by side reactions, such as carbon deposition, and the reactor needs to be cleaned occasionally, and more seriously, the obtained product is complicated, and downstream separation units (Bhasin et al, applied. Catal. A2001, 221, 397-.
There are currently a lot of research on the separation of hydrogen from hydrogen-containing mixed gases based on membrane separation techniques, such as molecular sieves or microporous molecular sieve membranes made of silica (Gascon et al, chem. mater.2012,24,2829-2Selectivity to CO, hydrogen and carbon monoxide will permeate the microporous membrane simultaneously, and the resulting hydrogen will therefore contain a small amount of carbon monoxide, but CO will poison the Pt electrocatalyst in the Fuel cell (Kim et al, Energy Fuel 2013,27,4471-4480), requiring subsequent CO removal. In addition, Pd-based alloy membranes have been widely studied due to high hydrogen selectivity and high permeation flux, such as Yangweisu researchers and Androstris Goldbach, the institute of chemico-physical, university of Chinese academy of sciences (Chinese patent application No.: 201611057551.7; 201710219717.9). But expensive film material cost and film material pair C O and H2S low resistance limits its use (Ayturk et al, Energ. environ. Sci.2009,2, 430-. Recent studies have found that (Jiang et al, Angew. chem. int.Ed.2008,47, 9341-one 9344; Fang et al, Angew. chem. int.Ed.2016,55, 8648-one 8651) by coupling partial oxidation of methane and water splitting on both sides of an oxygen permeable membrane, partial oxidation of methane occurs on the surface of a nickel-based catalyst on one side of the membrane to produce syngas, while water on the other side of the membrane is split into hydrogen and oxygen, which can be removed in situ by the oxygen permeable membrane and consumed by partial oxidation of methane. Accordingly, high purity hydrogen and Fischer-Tropsch syngas are obtained simultaneously on both sides of the oxygen permeable membrane, however, the nickel-based catalyst on the methane side is prone to carbon deposition and eventual deactivation under anhydrous conditions (Lopez-Fonseca et al, appl. Catal. A2012,437, 53-62), and researchers in China are working on developing catalysts for hydrogen production by steam reforming of methane, such as Wang Xiang at Nanchang university (Chinese patent application No.: 201510340806. X; 201310745874.5), Sundao of China petrochemical Co., Ltd. (Chinese patent application No.: 201410732120.0); zhou Shi Ming (Chinese patent application No. 201310628252.4) of east China's university of science and technology. In addition, Yankee prudent researchers in the university of Chinese academy of sciences recently developed a method for preparing high-purity hydrogen by decomposing water in an oxygen-permeable membrane reactor (Li et al. energy environ. Sci.,2017,10,101-containing material 106; AIChE J.,2017,63,1278-containing material 1286; Chinese patent application No. 201611057557.4).
However, until now, there has been no research report on the simultaneous production of naturally separated high-purity hydrogen and chemicals by the reforming of low-carbon alkanes or catalytic dehydrogenation reactions in proton-conducting membrane reactors. It is therefore a significant challenge how to develop new technologies to produce high purity hydrogen and chemicals simultaneously.
Disclosure of Invention
In order to make up for the blank in the prior art, the invention aims to provide a method and a device for simultaneously obtaining high-purity hydrogen and chemicals by reaction (low-carbon alkane high-temperature reforming or catalytic dehydrogenation reaction) in a proton-conducting membrane reactor.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for obtaining high-purity hydrogen and chemicals simultaneously by reaction in a proton-conducting membrane reactor is characterized in that a high-temperature reforming reaction or a catalytic dehydrogenation reaction is carried out in the membrane reactor, hydrogen protons are transmitted in a proton-conducting membrane of the membrane reactor by utilizing the hydrogen partial pressure gradient effect, the hydrogen is removed in situ, and then the chemicals and the high-purity hydrogen which are naturally separated are obtained simultaneously in the membrane reactor.
Introducing raw material gas in the high-temperature reforming or catalytic dehydrogenation reaction into a feeding side I area in the membrane reactor, reacting the raw material gas at 700-950 ℃, introducing purge gas into a purging side II area of the membrane reactor during the reaction, so that hydrogen formed in the high-temperature reaction process of the raw material gas in the feeding side I area is transmitted and removed to the purging side in the form of hydrogen protons in oxide lattices of the proton-conducting membrane by utilizing the hydrogen partial pressure gradient effect, and hydrogen is desorbed on the membrane surface of the purging side II area to form hydrogen, so that high-purity hydrogen is obtained, and chemicals formed in the reaction process are obtained in the feeding side I area; a proton conduction membrane is arranged in the membrane reactor, and the reactor is divided into a feeding side I area and a blowing side II area.
The proton conducting membrane is a mixed conductor ceramic membrane, wherein the mixed conductor ceramic membrane is a material for simultaneously conducting protons and electrons, and the material for simultaneously conducting protons and electrons is a single-phase proton conducting membrane material, a metal-ceramic two-phase proton conducting membrane material or a ceramic-ceramic two-phase proton conducting membrane material.
The single-phase proton conduction membrane material is BaCeO3、SrCeO3Or La5.5WO11.25-δA single phase proton conducting membrane material; the metal-ceramic two-phase proton conduction membrane material is Ni-BaCeO3Or Ni-SrCeO3A base metal-ceramic biphasic proton conducting membrane material; the ceramic-ceramic two-phase proton conducting membrane material is BaCe0.65Zr0.20Y0.15O3-δ–Ce0.85Gd0.15O2-δ、La5.5WO11.25-δ–La0.87Sr0.13CrO3-δOr BaCe0.85Fe0.15O3-δ-BaCe0.15Fe0.85O3-δCeramic based-Ceramic two-phase proton conducting membrane material.
The structural form of the membrane is selected from a sheet membrane, a tubular membrane or a hollow fiber membrane.
The raw material gas is low-carbon alkane C1-C3Alkanes such as methane, ethane or propane;
the purge gas is an inert gas such as high-purity helium or argon, and the purity is 99.99%.
The feed gas introducing amount and the flow rate of the purge gas are related to the permeation flux of the proton-conducting membrane material; that is, when the permeation flux of the proton conducting membrane is high, the introduction amount of the raw material gas can be slightly larger, but the maximum hydrogen permeation flux of the proton conducting membrane material is not exceeded, otherwise, the concentration of hydrogen contained in the chemical is high, and the collected chemical needs to be separated and purified subsequently; when the permeation flux of the proton conduction membrane material is low, the permeation flux of the membrane can be further improved by adopting measures of increasing the flow rate of a sweeping side, increasing the permeation temperature and reducing the thickness of the membrane, namely adopting a tubular membrane or a hollow fiber membrane and the like, and the feed amount of feed gas and the flow rate of sweeping gas are dynamically adjusted to be matched with the permeation flux of the membrane material, so that the aim of simultaneously obtaining chemicals with high added values and high-purity hydrogen is finally achieved.
The device comprises a membrane reactor 1 and a proton conducting membrane 2, wherein the proton conducting membrane 2 is arranged in the membrane reactor 1, one side of the side wall of the membrane reactor 1 is provided with a feed gas inlet device 3 and a purge gas inlet device 4, the other side of the side wall of the membrane reactor 1 is provided with a chemical collecting device 5 corresponding to the feed gas inlet device 3 and a high-purity hydrogen collecting device 6 corresponding to the purge gas inlet device 4.
The proton conduction membrane 2 is arranged in the membrane reactor 1 to form a proton conduction membrane feeding side I area and a blowing side II area; wherein, the two sides of the proton conduction membrane feeding side I area of the membrane reactor 1 are respectively provided with a feed gas lead-in device 3 and a collecting device 5 for collecting chemicals, and the two sides of the purging side II area are respectively provided with a purge gas lead-in device 4 and a collecting device 6 for collecting high-purity hydrogen.
The invention has the advantages that:
the device and the method can simultaneously prepare high-purity hydrogen and chemicals, and can regulate and control the ratio of hydrogen to carbon monoxide, the selectivity and the yield of ethylene and the yield of hydrogen in the Fischer-Tropsch synthesis gas by regulating the flow rate and the temperature of the feed gas and the purge gas. Meanwhile, the hydrogen in-situ removed by the proton conducting membrane in the preparation process is permeated to the purging side based on the transmission of hydrogen protons in oxide lattices of the membrane material, the selectivity of the proton conducting membrane to the hydrogen is 100%, other gases cannot permeate through the proton conducting membrane reactor (such as methane, ethane, propane, propylene, ethylene and carbon monoxide), and therefore the obtained hydrogen is high-purity hydrogen without impurities and subsequent water-gas shift reaction treatment is not needed.
The high-purity hydrogen prepared by the method of the invention does not contain CO impurities which poison catalyst Pt, and can be directly used in fuel cells. Meanwhile, H in Fischer-Tropsch synthesis gas prepared by the method2The volume ratio of the/CO is 2, and the catalyst can be directly used for Fischer-Tropsch synthesis or methanol synthesis without being adjusted.
The device of the method is simple, the preparation procedures and the cost of the Fischer-Tropsch synthesis gas and the high-purity hydrogen are greatly reduced, the membrane reactor realizes high process reinforcement, and the process energy consumption is obviously reduced. Meanwhile, the method has strong practicability, and is beneficial to the wide application of the proton-conducting membrane reactor in hydrogen-involved reactions such as methane aromatization, propane dehydrogenation and the like.
Drawings
FIG. 1 is a schematic view of an apparatus according to the present invention; wherein: 1. a membrane reactor; 2. a proton conducting membrane; 3. a raw material gas introduction device; 4. a purge gas introduction means; 5. a Fischer-Tropsch synthesis gas or ethylene collection device; 6. high-purity hydrogen's collection device.
FIG. 2 is a schematic diagram of a process for the simultaneous production of high purity hydrogen and Fischer-Tropsch synthesis gas according to the present invention;
FIG. 3 is a schematic diagram of a process for the simultaneous production of high purity hydrogen and ethylene provided by the present invention;
FIG. 4 is a graph showing the results of an experiment for the simultaneous production of high purity hydrogen and Fischer-Tropsch synthesis gas according to example 2 of the present invention;
Fig. 5 shows the results of the ethane dehydrogenation to ethylene in different operation modes provided in example 3 of the present invention.
Detailed Description
The following examples are presented to further illustrate embodiments of the present invention, and it should be understood that the embodiments described herein are for purposes of illustration and explanation only and are not intended to limit the invention.
The method and the device can directly reform the synthesis gas (H) of the methane steam2And CO in the ratio of 3) or in-situ removing part of hydrogen in ethane dehydrogenation, condensing and drying to obtain high-purity hydrogen (directly used for fuel cells), and simultaneously obtaining ethylene or H2Fischer-Tropsch synthesis gas (H) consisting of CO 22/CO), can be used directly for the preparation of polyethylene or for fischer-tropsch synthesis reactions. In situ removal of hydrogen breaks the thermodynamic equilibrium limit, increasing the ethylene yield or syngas yield. The two processes are coupled together through a hydrogen proton conductor membrane, achieving a high degree of process intensification and reducing process energy consumption.
In the implementation process of the method, at the feeding side, methane and steam are subjected to reforming reaction at high temperature to generate synthesis gas, wherein part of hydrogen in the synthesis gas permeates to the purging side through the proton conducting membrane, hydrogen protons are desorbed on the purging side to obtain hydrogen, carbon monoxide cannot permeate through the proton conducting membrane and is limited at the feeding side, and Fischer-Tropsch synthesis gas (H) is obtained at the feeding side 22) and finally, two naturally separated high-purity hydrogen and Fischer-Tropsch synthesis gases obtained at the feeding side and the blowing side simultaneously have higher industrial application value.
Example 1
An apparatus for simultaneously obtaining high-purity hydrogen and chemicals, as shown in fig. 1, comprises: the device includes membrane reactor 1 and proton conduction membrane 2, in membrane reactor 1 was located to proton conduction membrane 2, 1 lateral wall one side of membrane reactor was equipped with the leading-in device 3 of feed gas and the leading-in device 4 of sweeping gas, the opposite side be equipped with the corresponding collection chemical's of leading-in device 3 of feed gas collection device 5, and with the corresponding collection high-purity hydrogen's of leading-in device 4 of sweeping gas collection device 6.
The proton conduction membrane 2 is arranged in the membrane reactor 1 to form a proton conduction membrane feeding side I area and a blowing side II area; wherein, the two sides of the proton conduction membrane feeding side I area of the membrane reactor 1 are respectively provided with a feed gas lead-in device 3 and a collecting device 5 for collecting chemicals, and the two sides of the purging side II area are respectively provided with a purge gas lead-in device 4 and a collecting device 6 for collecting high-purity hydrogen.
Example 2
The method for simultaneously preparing high-purity hydrogen and Fischer-Tropsch synthesis gas comprises the following steps:
by using the device of the embodiment, the raw material gas introducing device introduces raw material gas methane and water vapor into the first area of the feeding side of the proton conducting membrane in the membrane reactor, the inert gas helium is introduced into the second area of the purging side in the membrane reactor by the raw material gas introducing device for purging, the raw material gas undergoes a high-temperature reforming reaction at a high temperature to generate synthesis gas with the volume ratio of hydrogen to carbon monoxide of 3, the hydrogen partial pressure gradient exists on the two sides of the proton conducting membrane by the gas formed in the reaction, part of the hydrogen permeates to the purging side under the action of the hydrogen partial pressure gradient and is led out by the collecting device 6, high-purity hydrogen is obtained after condensation and drying, meanwhile, the carbon monoxide cannot be limited on the feeding side through the permeation of the proton conducting membrane, and the residual hydrogen and carbon monoxide on the feeding side form the Fischer-Tropsch synthesis gas (H) by the hydrogen and the carbon monoxide 22/CO), is led out by the collecting device 5, and the principle of the reaction process is shown in fig. 2 and 4.
The proton conducting membrane is a two-phase ceramic membrane BaCe prepared by adopting an improved sol-gel method0.85Fe0.15O3-δ-BaCe0.15Fe0.85O3-δ(BCF8515-BCF1585) powder, a subsequent sintering compact BCF8515-BCF1585 double-phase ceramic membrane is adopted as a proton conduction membrane (Wanghaihui, Chenshun, Wanglanji, Chenyan, a double-phase ceramic material of homologous double perovskites and a preparation method and application thereof, patent publication No. CN 105198424B), the powder is polished to 0.6mm thickness, and Ni/Al is filled2O3The proton conducting membrane of the catalyst adopts a silver ring at 96Sealing in a membrane reactor at 0 ℃.
The film may further comprise La5.5WO11.25-δAnd BaCe0.65Zr0.20Y0.15O3-δ–Ce0.85Gd0.15O2-δAnd other proton conducting membranes are used for replacement, and the membrane materials are proton conducting membranes for simultaneously conducting protons and electrons, so that hydrogen generated by raw material gas reaction can be removed in situ by transmitting hydrogen protons, and corresponding characteristics can be achieved.
The sealing performance of the membrane reactor is firstly verified before the catalytic reaction, in the implementation, as the 100 percent sealing can not be realized between the silver ring and the alumina tube, as long as the hydrogen leakage amount of the membrane reactor detected by the gas chromatography is not more than 1 percent, the sealing performance of the membrane reactor is considered to be good, and the subsequent reaction test can be carried out. During the reaction, impurities (including CO and CH) in the high-purity hydrogen collected at the purging side are detected by gas chromatography 4，C2H6、C2H4) The concentration of (a) does not exceed 10ppm level, which indicates that the membrane reactor has good sealing performance, and it is noted that the impurities collected from the hydrogen gas are not transported through the dense proton-conducting membrane but are caused by incomplete sealing of the membrane reactor.
Further, after the temperature of the reactor was slowly lowered from the sealing temperature of 960 ℃ to 900 ℃, a mixed gas of methane and steam was introduced into the feed side, and the amount of methane introduced was 0.86 mL/min depending on the permeation capability of the proton conductive membrane-1The ventilation amount of water vapor was 1.16 mL/min-1Introducing 20-100 mL/min on the purge side-1The high-purity helium gas is used for synchronously preparing high-purity hydrogen and Fischer-Tropsch synthesis gas, namely, the feed gas is subjected to high-temperature reforming reaction at high temperature to generate synthesis gas with the volume ratio of 3 of hydrogen to carbon monoxide, the formed gas utilizes the hydrogen partial pressure gradient action at two sides of a proton conduction membrane in the reaction, so that part of the formed hydrogen permeates under the hydrogen partial pressure gradient action to reach a purging side and is guided out by a collecting device 6, the high-purity hydrogen is obtained after condensation and drying, meanwhile, the carbon monoxide cannot permeate through the proton conduction membrane and is limited at a feeding side, and the rest hydrogen at the feeding side is not permeated through the proton conduction membrane and is limited at the feeding side Fischer-Tropsch synthesis gas (H) consisting of hydrogen and carbon monoxide22/CO), is derived by the collecting device 5.
The feed gas and helium gas introduction flow rate is obtained by calibrating a soap bubble flowmeter. The yield of hydrogen produced, as well as the conversion of alkanes and the selectivity and yield of chemicals can be calculated from the corresponding measurements after calibration.
The measurements were performed by Gas Chromatography (GC) in which hydrogen gas was generated on the purge side and the content of each component in the feed side derived gas, and the gas to be measured was subjected to condensation drying to remove water vapor before being subjected to gas chromatography.
Respectively measuring the flow rate F of methane led in from the feeding side by a soap bubble flowmeterCH4,inWater vapor flow rate FH2OPurge side helium flow rate FHeAnd flow rate F of gas flowing out from two sides after coolingCH4,out、FCO,out、FH2And FpermeateAnd calculating the ratio of synthesis gas generated at two sides, the yield of generated hydrogen, the conversion rate of methane and the selectivity of carbon monoxide by the following formulas:
in the above disclosure:
s is the effective membrane area, cm, of the proton-conducting membrane2；
JH2For purging to measure the yield of hydrogen, mL min-1·cm-2；
FpermeateFlow rate on the permeate side, mL. min-1；
CH2Concentration of hydrogen at permeate side,%;
X(CH4) And s (co) is the conversion of methane and the selectivity of carbon monoxide,%, respectively;
FCH4,out、FCO,out、FH2The flow rates of methane, carbon monoxide and hydrogen in the collected gas, mL.min, are respectively detected by a GC feeding side guide-out device-1；
FCH4,inFlow rate of methane introduced to the feed side, mL. min-1；
Ratio(H2the/CO) is the ratio of hydrogen and carbon monoxide collected on the feed side.
As can be seen from said FIG. 4, it was found by GC examination that when the purge gas flow rate was increased from 20 to 100 mL-min in the reactor under the production conditions of the above examples-1While, the yield of purge side hydrogen increased from 0.54 to 0.97mL min-1·cm-2. At the same time, the volume ratio of hydrogen to carbon monoxide on the feed side gradually decreased, when the flow rate of the purge gas was 60mL min-1During the process, the volume ratio of hydrogen to carbon monoxide in the synthesis gas obtained from the feeding side is about 2, and meanwhile, the conversion rate of methane and the selectivity of carbon monoxide also reach 90% respectively, which shows that the hydrogen partial pressure on two sides of the membrane reactor is increased by increasing the flow velocity of the inert gas on the purging side, so that more hydrogen is removed to the permeation side, and the purpose of simultaneously preparing high-purity hydrogen and Fischer-Tropsch synthesis gas on two sides of the membrane reactor is further realized. Meanwhile, a stability test of 100h shows that all the performances of the membrane reactor are stable, and the sealing property of the membrane reactor is still good.
Meanwhile, it is to be noted that in the present embodiment, since 100% complete sealing between the silver ring and the alumina tube cannot be achieved, it is fully understandable that the concentration of CO impurities in the collected high purity hydrogen gas is of the order of 2 to 3ppm by gas chromatography, and it is demonstrated from the principle and experimental point of view that high purity hydrogen gas can be produced and directly used for fuel cells by the present method.
In conclusion, the device and the method of the invention can be used for simultaneously preparing two naturally separated high-purity hydrogen and Fischer-Tropsch synthesis gas in the proton conduction membrane reactor, and have wide application prospects.
Example 3
The method for simultaneously preparing high-purity hydrogen and ethylene comprises the following steps:
by using the apparatus described in the above embodiment, the raw material gas introducing apparatus introduces raw material gas ethane into the first region on the feeding side of the proton conducting membrane in the membrane reactor, the purge gas introducing apparatus introduces helium into the second region on the purging side of the membrane reactor, the raw material gas undergoes catalytic dehydrogenation reaction at high temperature to generate hydrogen and ethylene, hydrogen formed in the reaction causes a hydrogen partial pressure gradient to exist on both sides of the proton conducting membrane, so that part of the hydrogen permeates to the purging side under the action of the hydrogen partial pressure gradient and is guided out by the collecting apparatus 6, high purity hydrogen is obtained after condensation and drying, meanwhile, ethane and ethylene cannot be transported in the proton conducting membrane and are limited on the feeding side, and the remaining ethylene on the feeding side is guided out by the collecting apparatus 5, and the principle of the reaction process is shown in fig. 3 and 5.
The proton conduction membrane material is BCF8515-BCF1585, the thickness of the membrane is 0.6mm, the proton conduction membrane is sealed in the membrane reactor at 960 ℃ by adopting a self-made silver ring, and before the catalytic reaction, the sealing performance of the membrane reactor is firstly verified; while the proton conductive membrane may also be made of La5.5WO11.25-δ–La0.87Sr0.13CrO3-δWhen the membrane material is replaced, the membrane can transmit hydrogen protons to remove hydrogen in situ, and corresponding characteristics can be achieved.
The method comprises the following specific steps:
1) sealing the feed side proton-conducting membrane in the membrane reactor;
2) introducing raw material gas of ethylene into a feeding side I of the proton conducting membrane through a gas introducing device 3, and simultaneously introducing purge gas into a purging side II of the proton conducting membrane through a gas introducing device 4; the raw material gas of the ethylene is ethane; the purge gas is high-purity helium (the purity is 99.99%);
3) at the feed side I of the membrane reactor, to be sureWhen the sealing property is considered to be good, the temperature of the feeding side I of the reactor is slowly reduced from 960 ℃ to 775 ℃, and then 0.5 mL/min is introduced into the feeding side I-1The purge side of the ethane is first purged without inert gas, at which point there is no hydrogen partial pressure gradient across the membrane, and hydrogen cannot permeate through the proton conducting membrane, at which point the hydrogen produced by dehydrogenation of ethane is not removed. Under the same reaction conditions, 40mL min was introduced on the purge side subsequently -1The helium is purged, and the proton conducting membrane removes hydrogen generated by ethane dehydrogenation in situ, so that the selectivity and the yield of the ethylene can be improved.
The introduction amount of the feed gas and the helium is obtained by calibrating a soap bubble flowmeter. The hydrogen production on both sides, the ethane conversion and the ethylene selectivity and yield can be calculated from the corresponding measurements after calibration, as described in example 2.
As can be seen from said FIG. 5, in the reactor under the production conditions of the above examples, when the purge gas was not introduced into the purge side, no hydrogen was removed, and the selectivity and yield of ethylene were 58% and 41%, respectively, when the purge side was introduced at 40 mL. min-1The helium purge of (1) while the ethane conversion remained essentially unchanged, the ethylene selectivity and yield reached 66% and 45%, respectively, and the ethylene selectivity and yield increased by about 14% and 10%, respectively, with the hydrogen removal over that without the hydrogen removal, indicating that the in-situ hydrogen removal can suppress the occurrence of side reactions during the dehydrogenation of ethane, thereby increasing the ethylene selectivity and yield while obtaining high purity hydrogen on the purge side. The example illustrates that by using a membrane reactor to remove hydrogen generated by ethane dehydrogenation in situ, ethylene and hydrogen obtained by ethane dehydrogenation can be successfully separated in situ, the purpose of simultaneously preparing high-purity hydrogen and ethylene is achieved, separation processes are reduced, process enhancement is achieved, and the method has a wide application prospect and can be applied to hydrogen-involved reactions such as methane aromatization and propane dehydrogenation.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (3)
1. A method for obtaining high-purity hydrogen and chemicals simultaneously by reaction in a proton-conducting membrane reactor is characterized in that: carrying out high-temperature reforming reaction in the membrane reactor, transmitting hydrogen protons in a proton conducting membrane of the membrane reactor by utilizing the hydrogen partial pressure gradient effect, removing hydrogen generated by the reaction in situ, and further simultaneously obtaining naturally separated chemicals and high-purity hydrogen in the membrane reactor;
introducing raw material gas in the high-temperature reforming reaction into a feeding side I area in a membrane reactor, reacting the raw material gas at 900 ℃, introducing purge gas into a purging side II area of the membrane reactor during the reaction, so that hydrogen formed in the high-temperature reaction process of the raw material gas in the feeding side I area is transmitted to the purging side in the form of hydrogen protons in oxide lattices of a proton conduction membrane by utilizing the hydrogen partial pressure gradient effect, hydrogen is desorbed and formed on the surface of the membrane in the purging side II area, high-purity hydrogen is obtained in the purging side II area, and chemicals formed in the reaction process are obtained in the feeding side I area; a proton conduction membrane is arranged in the membrane reactor, and the reactor is divided into a feeding side I area and a blowing side II area;
The proton conducting membrane is a mixed conductor ceramic membrane, wherein the mixed conductor ceramic membrane is a material for simultaneously conducting protons and electrons, and the material for simultaneously conducting protons and electrons is a single-phase proton conducting membrane material, a metal-ceramic two-phase proton conducting membrane material or a ceramic-ceramic two-phase proton conducting membrane material;
the raw material gas is a mixed gas of methane and steam;
the chemical is H2Fischer-tropsch synthesis gas/CO = 2.
2. The process for simultaneously obtaining high purity hydrogen and chemicals by reaction in a proton conducting membrane reactor according to claim 1, wherein: the single-phase proton conducting membrane material is BaCeO3、SrCeO3Or La5.5WO11.25-δSingle-phase proton conducting membrane material(ii) a The metal-ceramic two-phase proton conduction membrane material is Ni-BaCeO3Or Ni-SrCeO3A base metal-ceramic biphasic proton conducting membrane material; the ceramic-ceramic two-phase proton conducting membrane material is BaCe0.65Zr0.20Y0.15O3-δ–Ce0.85Gd0.15O2-δ、La5.5WO11.25-δ–La0.87Sr0.13CrO3-δOr BaCe0.85Fe0.15O3-δ-BaCe0.15Fe0.85O3-δA ceramic-ceramic two-phase proton conducting membrane material.
3. The process for simultaneously obtaining high purity hydrogen and chemicals by reaction in a proton conducting membrane reactor according to claim 1, wherein: the structural form of the membrane is a sheet membrane, a tubular membrane or a hollow fiber membrane.
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