CN103756741A - Method for preparing natural gas by using solid oxide electrolytic tank adopting renewable power - Google Patents
Method for preparing natural gas by using solid oxide electrolytic tank adopting renewable power Download PDFInfo
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- CN103756741A CN103756741A CN201310712385.XA CN201310712385A CN103756741A CN 103756741 A CN103756741 A CN 103756741A CN 201310712385 A CN201310712385 A CN 201310712385A CN 103756741 A CN103756741 A CN 103756741A
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Abstract
The invention discloses a method for preparing natural gas by using a solid oxide electrolytic tank adopting renewable power, belonging to the technical field of synthesis gas and natural gas preparation. The method comprises the steps: co-electrolyzing CO2/H2O mixed gas at high temperature through an SOEC (Solid Oxide Electrolyzer Cell) by directly utilizing renewable electrical energy on the basis of the traditional method for preparing natural gas from coal at two steps; efficiently converting the collected CO2 into CO/H2/CH4 mixed gas and pure oxygen; returning the obtained products to a natural gas preparation process so as to be methanated and used by a gasification furnace. By using the method, a novel approach for collecting CO2 in the process of preparing the natural gas by using coal is developed, the feasible application field of the SOEC is expanded, a non-grid-connected utilization way is provided for renewable energy power difficult to get on the internet, the circular utilization of the carbon resource is realized, the energy consumption for preparing the natural gas by using coal is reduced, and the problem that the non-grid-connected renewable energy power is difficult to utilize is solved.
Description
Technical field
The present invention relates to preparing synthetic gas and Sweet natural gas field, be specifically related to a kind of integrated method of preparing Sweet natural gas of electrolytic tank of solid oxide/coal preparing natural gas combining with renewable energy source electric power.
Background technology
Along with the lasting propelling of China's energy-saving and emission-reduction policy, the consumption ratio of high-quality and efficient clean energy Sweet natural gas significantly increases.Yet the energy structure of China's " oil-poor weak breath of rich coal ", causes Sweet natural gas imbalance between supply and demand to become increasingly conspicuous.Within 2012, domestic gas production reaches 1,077 hundred million m
3, apparent consumption 1,471 hundred million m of Sweet natural gas
3, insufficiency of supply-demand is 39,400,000,000 m
3, expect insufficiency of supply-demand in 2015 and may reach 75,000,000,000 m
3.Coal synthetic natural gas processed (SNG) can be utilized the low-grade coals such as coal resources, particularly brown coal of China's abundant, by clean coal technology, produces synthetic natural gas, is the effective way that China makes up Natural Gas Demand breach, the clean utilization of promotion coal high-efficiency.But still there is CO in large moulded coal preparing natural gas
2discharge the problems such as large.8 coal preparing natural gas project production capacities checking and approving through country are at present 40,000,000,000 m nearly
3/ year, if these projects are all constructed and put into operation, annual CO
2quantity discharged will reach 1.8 hundred million t, huge CO
2quantity discharged is aggravation Global Greenhouse Effect further.In May, 2013, the notice > > that the issue < < of National Development and Reform Committee traps, utilizes and seal up for safekeeping (CCUS) experiment and demonstration about promoting carbon, encourages the industries such as Coal Chemical Industry in medium-term and long-term plans, to take into full account CO
2trapping, the requirement that utilizes and seal up for safekeeping.Therefore, how effectively to utilize the CO trapping in coal preparing natural gas
2, realizing carbon resource recycle becomes an important problem.
In addition, China mainly concentrates on the ground such as Inner Mongol, Xinjiang building and plan to build ature of coal Natural Gas Projects, and these provinces, except coal resources, also have the renewable energy sources such as abundant wind energy, sun power.Renewable energy source electric power improving energy structure, reduce environmental pollution, the aspect such as promote economic development brought into play vital role, but its randomness and intermittent feature make renewable energy source electric power be difficult to grid-connected utilization, seriously hindered large-scale developing and utilizing of renewable energy source, the effect of energy-saving and emission-reduction is had a greatly reduced quality.Ended for the end of the year 2012, Wind Power In China is abandoned wind and is rationed the power supply over 20,000,000,000 kWh, is equivalent to waste 6,700,000 tons of standard coals, and direct losses surpass 10,000,000,000 yuan.How to digest a large amount of non-grid-connected renewable energy source electric power, the Efficient Conversion energy storage that realizes renewable energy source is one, renewable energy power generation field urgent problem.
Summary of the invention
The present invention is intended to design the method for the integrated preparing natural gas of a kind of electrolytic tank of solid oxide (SOEC)/coal preparing natural gas novel, that can utilize renewable energy source electric power, proposes a kind of CO trapping in coal preparing natural gas process that utilizes
2new way, expand the feasible Application Areas of SOEC, the difficult renewable energy source electric power with online provides a kind of non-grid-connected mode of utilizing.
To achieve these goals, technical scheme of the present invention is as follows:
A method of utilizing the electrolytic tank of solid oxide preparing natural gas of renewable electric power, concrete grammar comprises the steps:
(1) coal preparing natural gas: adopt conventional coal preparing natural gas system, prepare Sweet natural gas by air separation, pressurized gasification, part hydrosphere transformation, cooling, gas scrubbing and methanation step;
(2) bleed: collect respectively the CO producing in coal preparing natural gas process
2and water vapor, after mixing, obtain CO
2/ H
2o mixed gas, wherein CO
2with H
2the mol ratio of O is 1:2-4;
(3) heat exchange: utilize interchanger by CO
2/ H
2o mixed gas and coal preparing natural gas system are carried out multi-stage heat exchanger, make CO
2/ H
2the temperature of O mixed gas is elevated to the working temperature of electrolytic tank of solid oxide;
(4) power transmission and transformation: renewable electric power energy is delivered to electrolytic tank of solid oxide, utilizes rectifier to change renewable electric power energy into direct current;
(5) electrolytic tank of solid oxide electrolysis: by the CO through heat exchange
2/ H
2o mixed gas delivery, to electrolytic tank of solid oxide, under the direct current effect obtaining, is utilized electrolytic tank of solid oxide electrolysis CO in step (4)
2/ H
2o mixed gas, the working temperature of electrolyzer is 600 ℃～1000 ℃, and pressure is 0.1MPa～3.0MPa, and electrolytic tank of solid oxide generates CO, H at negative electrode
2and CH
4, at anode, generate O
2;
(6) gas storage return-air: the aerogenesis of electrolytic tank of solid oxide is passed into gas-holder, the CO/H by recycle pump, electrolysis being obtained again afterwards
2/ CH
4mixed gas and O
2be transported to the coal preparing natural gas system in step (1), repeating step (1) is further to prepare Sweet natural gas.
Above-mentioned renewable electric power energy derives from wind power generation, solar energy thermal-power-generating or photovoltaic generation.
CO in step (2)
2cO for gas scrubbing step recovery in coal preparing natural gas process
2, water vapour is the water vapor that in coal preparing natural gas process, methanation step produces.
In the electrolytic tank of solid oxide electrolytic process of step (5), according to default, adjust polarizing voltage, CO
2/ H
2o air demand and ratio, CO, H in the mixed gas that control cathode generates
2mol ratio be 1:3, CH
4molar fraction be 0～30%; The size of renewable electric power energy determines the size of polarizing voltage, polarizing voltage and CO
2/ H
2the proportional routine relation of air demand of O mixed gas.
Beneficial effect of the present invention is:
(1) the present invention mainly adopts electrolytic tank of solid oxide (SOEC) high temperature common-battery solution CO
2/ H
2o technology.SOEC has higher electrolysis speed and energy conversion efficiency, relative low temperature electrolysis be a kind of more efficiently, Conversion of energy mode cheaply.SOEC is that structure of whole solid state gaseous product is easily separated, evaporation, corrosion and the electrolyte loss problem of using liquid electrolyte to bring have been avoided, simultaneously without adopting the noble metal electrodes such as Pt, and then greatly reduce costs, can be designed to have the basic module of certain power, adjust flexibly according to demand scale simultaneously.In addition, SOEC is lower to the quality requirements of electric energy, can adapt to the fluctuation of supplying electric energy.
(2) the present invention, on conventional two-step coal process for producing natural basis, directly utilizes the renewable energy source electric power such as wind-powered electricity generation, solar energy thermal-power-generating, photovoltaic generation, by SOEC high temperature common-battery solution CO
2/ H
2o, by the CO trapping
2efficient Conversion is CO/H
2/ CH
4mixed gas and pure oxygen, products therefrom can return to coal preparing natural gas process and further use, to realize carbon resource recycle, reduce Coal Chemical Industry process energy consumption, effectively digest the renewable energy sources such as local wind energy, sun power, solve the problem that renewable energy source electric power is difficult to grid-connected utilization, can consume discontinuous, unsettled non-grid-connected renewable energy resources electricity power, reduced power wastage simultaneously.
Accompanying drawing explanation
Fig. 1 prepares the method schematic diagram of Sweet natural gas with the electrolytic tank of solid oxide that utilizes renewable electric power.
In figure: 1-air separation; 2-pressurized gasification; 3-part hydrosphere transformation; 4-cooling pool; 5-gas scrubbing; 6-methanation; 7-sulfur recovery; 8-CO
2reclaim; 9,10-valve; 11-mixing tank; 12-multi-stage heat exchanger; 13-SOEC electrolysis heap; 14-gas-holder; 15-valve; 16-gas-holder; 17-valve; 18-DC converter.
Embodiment
The invention provides a kind of method of utilizing the electrolytic tank of solid oxide preparing natural gas of renewable electric power, below in conjunction with accompanying drawing and specific examples, the present invention is described in detail, but content not thereby limiting the invention.
As shown in Figure 1, coal preparing natural gas system simplification is air separation 1, pressurized gasification 2, part hydrosphere transformation 3, cooling pool 4, gas scrubbing 5, methanation 6, sulfur recovery 7 and CO
2reclaim 8 links.Raw air, through air separation 1, obtains high purity oxygen gas by low temperature separation, and concentration can be higher than 99.5%.Coal reacts with the generating gasification of superheated vapour and oxygen to generate and is rich in H in pressurized gasification 2
2with the coal gas of CO, vapor pressure is generally at 3～4MPa, and temperature is at 1000～1300 ℃.Coal gas passes through part hydrosphere transformation 3 by H
2be adjusted into 3:1 with CO volume ratio, catalyzer is generally the cobalt-molybdenum catalyst of resistance to sulphur, and service temperature is 200～500 ℃.And then high temperature shift gas is cooled to 40 ℃ by cooling 4.Cooling synthetic gas, by gas scrubbing 5, washs with low-temp methanol, at-17～-40 ℃, utilizes methyl alcohol to H
2s and CO
2good absorptive character, are purified gas, reclaim sulphur (7) simultaneously and reclaim CO
2(8).Purified gas, under certain temperature (250～675 ℃), pressure (2.3～3.2MPa), generates synthetic natural gas SNG in methanation 6, and the byproduct steam simultaneously obtaining is recycled to pressurized gasification 1 again, is further used for gasification.
Then continue to utilize electrolytic tank of solid oxide preparing natural gas, concrete steps are as follows:
Power transmission and transformation: extensive, unstable, discontinuous non-grid-connected renewable electric power energy transfers to electrolytic tank of solid oxide, the AC rectification that rectifier 18 sends generating set is direct current, then according to system conditions, the direct current of certain voltage is applied on electrolytic tank of solid oxide SOEC heap 13.
Bleed: from the recovery CO of gas scrubbing technique 5
2in pipeline, extract a certain amount of CO
2, in the byproduct steam from methanation process 6, extract a certain amount of water vapor, the two is mixed to the reactant gases as SOEC pile 13 in proportion in mixing tank 11, extract tolerance and controlled by valve 9 and 10, keep CO
2/ H
2cO in O mixed gas
2with H
2the mol ratio of O is 1:2-4.
Heat exchange: the CO that described extraction is obtained
2/ H
2o mixed gas and coal preparing natural gas system are carried out multi-stage heat exchanger 12, to guarantee electrolysis stack operation institute heat requirement.CO in multi-stage heat exchanger 12
2/ H
2o mixed gas first with cooling pool 4 heat exchange, the energy consumption being consumed to reduce in process of cooling, then with the 3 inlet gas heat exchange of part hydrosphere transformation, make gas temperature reach 600～1000 ℃, and a little more than SOEC pile operating temperature.
Electrolytic tank of solid oxide electrolysis: SOEC pile 13 is under 600～1000 ℃ and normal pressure (0.1MPa), by CO
2/ H
2o mixed gas passes into pile cathode flow channels, by electrochemical reducting reaction and reverse water gas shift reaction, in negative electrode original position, generates synthetic gas.Synthetic gas passes into gas-holder 14 again.CO and H in synthetic gas
2ratio can be by controlling polarized potential, inlet gas group grading mode reach 1:3.In this simultaneously, at SOEC pile anode generation electrochemical oxidation reactions, the O of generation
2pass into gas-holder 16.
Gas storage return-air: when SOEC operating pressure is during higher than normal pressure (0.1MPa～3.0MPa), pile negative electrode can original position generating portion CH
4, compositional range is 0～30%.By regulating working conditions, control remaining CO and H simultaneously
2component ratio is 1:3, CH
4molar fraction can reach 30% at most.CO/H that negative electrode produces
2/ CH
4mixed gas passes into gas-holder 14 again.
Finally the mixed gas in gas-holder 14 is led to back to methanation 6 by valve 15 controls and make further synthetic natural gas, realize carbon resource recycle.Oxygen in gas-holder 16 is controlled and is passed into vapourizing furnace as vaporized chemical by valve 17, to reduce making oxygen by air separation energy consumption.
The above is the specific embodiment of the present invention, is not limited to the present invention, all any modifications of making within spirit of the present invention and principle, is equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (4)
1. a method of utilizing the electrolytic tank of solid oxide preparing natural gas of renewable electric power, is characterized in that, concrete grammar comprises the steps:
(1) coal preparing natural gas: adopt conventional coal preparing natural gas system, prepare Sweet natural gas by air separation, pressurized gasification, part hydrosphere transformation, cooling, gas scrubbing and methanation step;
(2) bleed: collect respectively the CO producing in coal preparing natural gas process
2and water vapor, after mixing, obtain CO
2/ H
2o mixed gas, wherein CO
2with H
2the mol ratio of O is 1:2-4;
(3) heat exchange: utilize interchanger by CO
2/ H
2o mixed gas and coal preparing natural gas system are carried out multi-stage heat exchanger, make CO
2/ H
2the temperature of O mixed gas is elevated to the working temperature of electrolytic tank of solid oxide;
(4) power transmission and transformation: renewable electric power energy is delivered to electrolytic tank of solid oxide, utilizes rectifier to change renewable electric power energy into direct current;
(5) electrolytic tank of solid oxide electrolysis: by the CO through heat exchange
2/ H
2o mixed gas delivery, to electrolytic tank of solid oxide, under the direct current effect obtaining, is utilized electrolytic tank of solid oxide electrolysis CO in step (4)
2/ H
2o mixed gas, the working temperature of electrolyzer is 600 ℃～1000 ℃, and pressure is 0.1MPa～3.0MPa, and electrolytic tank of solid oxide generates CO, H at negative electrode
2and CH
4, at anode, generate O
2;
(6) gas storage return-air: the CO/H that electrolysis is obtained
2/ CH
4mixed gas and O
2be transported to the coal preparing natural gas system in step (1), repeating step (1) is further to prepare Sweet natural gas.
2. method according to claim 1, is characterized in that, described renewable electric power energy derives from wind power generation, solar energy thermal-power-generating or photovoltaic generation.
3. method according to claim 1, is characterized in that, CO described in step (2)
2cO for gas scrubbing step recovery in coal preparing natural gas process
2, water vapour is the water vapor that in coal preparing natural gas process, methanation step produces.
4. method according to claim 1, is characterized in that, in the described electrolytic tank of solid oxide electrolytic process of step (5), according to default, adjusts polarizing voltage, CO
2/ H
2o air demand and ratio, CO, H in the mixed gas that control cathode generates
2mol ratio be 1:3, CH
4molar fraction be 0～30%.
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| CN107180985A (en) * | 2017-05-05 | 2017-09-19 | 中国矿业大学(北京) | Low concentration coal-bed gas assisted electrolysis CO2/H2O prepares synthetic gas method and device |
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| CN107531490A (en) * | 2015-02-06 | 2018-01-02 | 环保电力集团有限公司 | The method for producing diamond synthesis |
| CN105001965A (en) * | 2015-06-08 | 2015-10-28 | 江苏奥莱特新材料有限公司 | Releasing agent special for bare concrete and preparation method thereof |
| CN105419892A (en) * | 2016-01-13 | 2016-03-23 | 山东联星能源集团有限公司 | High-temperature co-electrolysis method for preparing clean fuels |
| CN107180985A (en) * | 2017-05-05 | 2017-09-19 | 中国矿业大学(北京) | Low concentration coal-bed gas assisted electrolysis CO2/H2O prepares synthetic gas method and device |
| CN107699915A (en) * | 2017-09-22 | 2018-02-16 | 清华大学 | A kind of temperature maintains carbon dioxide and water vapour electrolysis unit and its application process altogether certainly |
| CN107699915B (en) * | 2017-09-22 | 2019-08-16 | 清华大学 | A kind of temperature is total to electrolysis unit and its application method from maintaining carbon dioxide and water vapour |
| CN107829786A (en) * | 2017-11-29 | 2018-03-23 | 中国华能集团清洁能源技术研究院有限公司 | A kind of near-zero release coal gasification power generation system and electricity-generating method with pollutant catabolic gene |
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| CN111807366A (en) * | 2020-07-24 | 2020-10-23 | 中国科学院上海应用物理研究所 | Device and method for preparing synthesis gas with assistance of high-temperature electrochemical device |
| CN111807366B (en) * | 2020-07-24 | 2023-06-20 | 中国科学院上海应用物理研究所 | Device and method for preparing synthesis gas by assistance of high-temperature electrochemical device |
| CN113583712A (en) * | 2021-07-12 | 2021-11-02 | 浙江大学 | Multi-energy coupling complementary and sequential conversion system and method |
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