WO2014026641A1 - Apparatus and process using cao as carrier for cycled-capturing of carbon dioxide - Google Patents

Apparatus and process using cao as carrier for cycled-capturing of carbon dioxide Download PDF

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WO2014026641A1
WO2014026641A1 PCT/CN2013/081642 CN2013081642W WO2014026641A1 WO 2014026641 A1 WO2014026641 A1 WO 2014026641A1 CN 2013081642 W CN2013081642 W CN 2013081642W WO 2014026641 A1 WO2014026641 A1 WO 2014026641A1
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cao
gas
carbon dioxide
carrier
carbonization
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PCT/CN2013/081642
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French (fr)
Chinese (zh)
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白玉龙
王昀睿
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西安瑞驰节能工程有限责任公司
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Priority to CN201210292710.7A priority Critical patent/CN102773006B/en
Priority to CN201210292710.7 priority
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Publication of WO2014026641A1 publication Critical patent/WO2014026641A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/62Carbon oxides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/96Regeneration, reactivation or recycling of reactants
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/50Carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00Compounds of calcium, strontium, or barium
    • C01F11/18Carbonates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2251/00Reactants
    • B01D2251/40Alkaline earth metal or magnesium compounds
    • B01D2251/404Alkaline earth metal or magnesium compounds of calcium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/50Carbon oxides
    • B01D2257/504Carbon dioxide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2258/00Sources of waste gases
    • B01D2258/02Other waste gases
    • B01D2258/0283Flue gases
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/80Semi-solid phase processes, i.e. by using slurries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/40Capture or disposal of greenhouse gases of CO2
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/151Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

A process using CaO as a carrier for cycled-capturing of carbon dioxide, comprising: step A, exhaust gas purification processing; step B, carbonization; step C, processing of carbonized product CaCO3; step D, CO2 desorption; step E, CaO digestion; step F, lime milk refinement; step G, lime milk recycling; and step H, storage (or sequestration) of high-purity CO2. An apparatus using CaO as a carrier for cycled-capturing of carbon dioxide in a flue gas, comprising, connected via pipes and a material conveying system, a purification apparatus, a carbonization tower, a sedimentation separator, a centrifuge, a dryer, a metering apparatus, an annular calciner, a material storage warehouse, a bucket elevator, a lime digester, a coarse slurry tank, and a hydrocyclone. The process has mature conditions, simple steps, and high efficiency in CO2 capturing, while the apparatus implementing the process has a compact structure, low intensities in investment and operation, and great prospects for industrial application.

Description

一种以 CaO为载体循环捕集二氧化碳的设备及工艺 技术领域  Apparatus and process for recycling carbon dioxide by using CaO as carrier

本发明涉及二氧化碳减排领域, 具体为一种以 CaO为载体循环捕集二氧化 碳的设备及工艺。  The invention relates to the field of carbon dioxide emission reduction, and specifically relates to an apparatus and a process for recycling carbon dioxide by using CaO as a carrier.

背景技术 Background technique

二氧化碳(co2)是导致全球气候变暧的温室气体的主要成分之一, 对温室 效应的贡献率高达 55%, 由于 0)2等温室气体排放所引起的气候变化已成为全 世界关注的焦点问题。 碳捕集与封存技术 (CCS 技术) 是指将二氧化碳从相关 集中排放燃烧源中捕获并分离出来, 并采用各种方法存储以避免其排放到大气 中的一种技术, 是应对气候变化最有效的技术路径之一。 Carbon dioxide (co 2 ) is one of the main components of greenhouse gases that cause global climate change. The contribution rate to the greenhouse effect is as high as 55%. Climate change caused by greenhouse gas emissions such as 0) 2 has become the focus of attention around the world. problem. Carbon capture and storage technology (CCS technology) refers to a technology that captures and separates carbon dioxide from relevant concentrated emission sources and stores it in various ways to avoid its release into the atmosphere. It is the most effective response to climate change. One of the technical paths.

燃煤发电、 钢铁、 冶金、 水泥等行业生产过程中需要消耗大量的化石燃料, 导致大量 C02的集中排放。 0)2捕集方法主要有 3种: 燃烧前捕集, 燃烧后捕 集及富氧燃烧捕集。 其中, 燃烧后捕集是指对燃烧后排放烟气中 02进行捕集 的一类方法, 包括变压吸附、 膜分离、 物理吸收及化学吸收等, 能直接应用于 现有生产设备, 投入相对较少, 原理简单, 适用范围广, 由于化学反应的存在, 化学吸收法用于 02捕集时, 吸收能力强, 平衡分压低, 吸收过程中能维持足 够高的传质推动力, 可确保高捕集效率, 具有较高的可操作性及广阔的市场前 景。 以 MEA为代表的醇胺法利用带有羟基和胺基的碱性水溶液作为溶剂, 通过 吸收塔和再生塔组成系统对 C02进行捕集, 是目前被研究和运用较多且较为成 熟的化学吸收方法, 对 02的脱除率较高, 能适应处理 C02分压低的混合气体, 但该方法采用的吸收剂对系统具有强腐蚀性, 且再生能耗高, 容易发生氧化、 热降解、 发生不可逆反应和蒸发等造成吸收剂损失和溶液性能改变等, 极大地 限制了其应用范围。与传统醇胺法相比, 氨水吸收法具有材料成本低、吸收 C02 能力强、 再生能耗低、 吸收剂不易被其他气体成分降解、 对系统腐蚀性小等特 点, 是实现燃煤烟气中 co2有效脱除的另一种化学方法, 在国外已经进入工业 中试阶段。 但是该方法为防止吸收剂泄露, 对于系统设备的密封性要求较高, 此外对捕集到的 02解吸并再生吸收剂的过程中, 由于液相平衡分压的存在, NH3和 ¾0与 C02会一起进入到气相, 造成富集所得的 C02纯度达不到要求。 In the coal-fired power generation, steel, metallurgy, cement and other industries, a large amount of fossil fuels are consumed in the production process, resulting in a large amount of concentrated emissions of CO 2 . 0) 2 capture methods are mainly three kinds: pre-combustion capture, oxyfuel combustion and post-combustion capture trap. Among them, post-combustion capture refers to a method of capturing 0 2 in the flue gas after combustion, including pressure swing adsorption, membrane separation, physical absorption and chemical absorption, etc., which can be directly applied to existing production equipment, and input. Relatively few, the principle is simple, and the scope of application is wide. Due to the existence of chemical reaction, the chemical absorption method is used for 0 2 capture, the absorption capacity is strong, the equilibrium partial pressure is low, and the mass transfer driving force can be maintained in the absorption process. Ensure high capture efficiency, high operability and broad market prospects. The alcohol amine method represented by MEA utilizes an alkaline aqueous solution having a hydroxyl group and an amine group as a solvent, and captures C0 2 through an absorption tower and a regeneration tower constituent system, and is currently studied and used more and more mature chemicals. The absorption method has a high removal rate of 0 2 and can be adapted to treat a mixed gas with a low partial pressure of C0 2 , but the absorbent used in the method is highly corrosive to the system, and has high regeneration energy consumption, and is prone to oxidation and thermal degradation. The occurrence of irreversible reactions and evaporation, such as loss of absorbent and changes in solution properties, greatly limits the scope of application. Compared with the traditional alcohol amine method, the ammonia water absorption method has the advantages of low material cost, strong ability to absorb C0 2 , low energy consumption for regeneration, low sensitivity of the absorbent to other gas components, and low corrosivity to the system. Point, is another chemical method to achieve effective removal of co 2 in coal-fired flue gas, and has entered the industrial pilot stage abroad. However, this method is to prevent leakage of the absorbent, sealing requirements for high system equipment, the process in addition to the trapping of desorbed and regenerated absorbent 02, since the presence of a liquid phase equilibrium partial pressure, NH 3, and with ¾0 C0 2 will enter the gas phase together, resulting in the purity of C0 2 obtained by enrichment being less than required.

钙基吸收剂循环煅烧 /碳酸化反应捕集 C02采用廉价和资源丰富的石灰石、 白云石等作为 02吸收剂, 具有良好的技术经济性, 近年来受到广泛关注。 该 方法捕集 C02的过程采用双流化床反应器(吸收反应器和再生反应器), 通过连 接管实现两个反应器之间的物料交换, 在吸收反应器中, CaO与 C02发生气-固 反应吸收混合烟气中低浓度 C02,生成 CaC03 (反应式为 CaO+ C02→ CaC03), 在再生反应器中,由煤纯氧燃烧供热使 CaC03分解生成 CaO和高浓度的 C02(反 应式为 CaC03→CaO+ C02), 其中的 CaO重新回用于吸收反应器, 同时收集产 生的高浓度 C02。 由于气固反应的局限性, 采用现有循环煅烧 /碳酸化方法捕集 C02时, 当反应进行到一定程度后, CaO颗粒表面生成的致密 & 03产物层会 对 C02进一步向颗粒内部扩散产生阻碍作用, 使总体反应速率较低。 经多次循 环吸收和煅烧后, 吸附剂颗粒内部孔隙堵塞及比表面积下降, 将造成钙基吸收 剂活性降低, 此外, 由于烟气中 S02等酸性气体的存在, 在 CaO表面会形成硫 酸化产物层,严重影响碳酸化反应的进行,加速 CaO循环捕集 C02性能的衰减。 为保持较高的 C02捕集效率, 需要不断增加钙基吸收剂的投入量, 将大大增加 运行成本, 增加煅烧过程能耗, 且反应器易磨损、 沾污和腐蚀。 中国专利 ZL201010011333.6 《钙基吸收剂循环捕集二氧化碳和二氧化硫的方法》 提出采 用煅烧炉下部排出的失活 CaO制备 Ca (OH) 2溶液对烟气中 S02进行脱除, 以 消除 S02存在对钙基吸收剂循环捕集 C02带来的阻碍, 节约钙基吸收剂的投入 量。 但该方法 Ca (OH) 2溶液脱除 S02的过程中, 会同时吸收烟气中的 C02, 使吸收反应器 02进口浓度偏低, 增加捕集难度。 此外, 该专利仍沿用双流化 床配合生物质燃料纯氧燃烧的方法实现吸附剂循环再生, 大大降低了生产过程 中的废气量, 但纯氧燃烧这一技术难度较大, 投资和运行费用都较高, 另外此 方法也无法解决流化床反应器进出料密封性不强引起的外部空气进入反应器内 部, 引起 co2纯度降低的问题。 Calcium-based absorbent cycle calcination/carbonation reaction captures CO 2 using inexpensive and resource-rich limestone, dolomite, etc. as a 0 2 absorbent, which has good technical and economical properties and has received extensive attention in recent years. The method of capturing CO 2 by the method adopts a double fluidized bed reactor (absorption reactor and regeneration reactor), and material exchange between two reactors is realized through a connecting pipe, in which CaO and C0 2 occur in the absorption reactor. The gas-solid reaction absorbs the low concentration of C0 2 in the mixed flue gas to form CaC0 3 (the reaction formula is CaO+ C0 2 → CaC0 3 ). In the regeneration reactor, the combustion of coal by pure oxygen combustion causes CaCO 3 to decompose to form CaO and high. The concentration of C0 2 (reaction formula is CaC0 3 → CaO + C0 2 ), in which CaO is reused for the absorption reactor, while collecting the high concentration of CO 2 produced. Due to the limitations of the gas-solid reaction, using conventional firing cycles / trapping carbonation Method 2 C0, when the reaction was carried out to a certain extent, the surface of the particles generated CaO & dense product layer 03 be internal to the granules further C0 2 Diffusion creates an obstruction and lowers the overall reaction rate. After multiple cycles of absorption and calcination, the internal pores of the adsorbent particles are clogged and the specific surface area is decreased, which will cause the activity of the calcium-based absorbent to decrease. In addition, due to the presence of acid gas such as S0 2 in the flue gas, sulfate formation will occur on the surface of CaO. The product layer seriously affects the progress of the carbonation reaction and accelerates the attenuation of the C0 2 performance of the CaO cycle. In order to maintain a high CO 2 capture efficiency, it is necessary to continuously increase the input amount of the calcium-based absorbent, which will greatly increase the running cost, increase the energy consumption of the calcination process, and the reactor is easily worn, stained and corroded. Chinese patent ZL201010011333.6 "method of carbon dioxide capture calcium absorbent and sulfur dioxide cycle" proposed prepared using inactivated calciner discharge a lower CaO Ca (OH) 2 solution to the flue gas for the removal of S0 2, S0 2 in order to eliminate There is a hindrance to the cyclic capture of CO 2 by the calcium-based absorbent, and the amount of the calcium-based absorbent is saved. However, in the process of removing the SO 2 from the Ca (OH) 2 solution, the C0 2 in the flue gas is simultaneously absorbed, so that the inlet concentration of the absorption reactor 0 2 is low, and the difficulty of the collection is increased. In addition, the patent still uses the dual fluidized bed combined with the pure oxygen combustion of biomass fuel to realize the regeneration of the adsorbent, which greatly reduces the amount of exhaust gas in the production process, but the technology of pure oxygen combustion is difficult, investment and operating costs. Both are high, and this method can not solve the external air entering the reactor caused by the poor sealability of the fluidized bed reactor. Part, causing a problem of reduced purity of co 2 .

发明内容 Summary of the invention

针对上述现有技术中存在的不足, 本发明目的在于提供一种以 CaO为载体 循环捕集二氧化碳的工艺及设备。 该工艺条件成熟, 步骤简单, 对于 C02的捕 集效率高。 实施该工艺的设备, 其结构紧凑, 投资运行强度小, 具有良好的工 业化应用前景。 In view of the deficiencies in the prior art described above, it is an object of the present invention to provide a process and apparatus for cyclically capturing carbon dioxide using CaO as a carrier. The process conditions are mature, the steps are simple, and the capture efficiency for C0 2 is high. The equipment for implementing the process has a compact structure, low investment operation intensity, and good industrial application prospects.

为达到上述发明目的, 本发明提供的技术方案是:  In order to achieve the above object, the technical solution provided by the present invention is:

提供一种以 CaO为载体循环捕集二氧化碳的设备, 包括经管道相连的净化 装置和碳化塔, 所述碳化塔经管道依次连接有沉降分离机、 离心机、 干燥机、 计量装置、 密闭环形煅烧炉、 物料储存仓、 斗式提升机、 化灰机、 粗桨池和旋 液分离器, 所述旋液分离器再与碳化塔相连; 所述环形煅烧炉经管道还依次连 接有水冷换热器、 压缩机、 冷凝器和 02储存罐; 所述沉降分离机、 离心机和 化灰机分别通过管道与回用水池连接。 Providing an apparatus for cyclically capturing carbon dioxide by using CaO as a carrier, comprising a purification device connected to a pipeline and a carbonization tower, wherein the carbonization tower is connected by a pipeline with a sedimentation separator, a centrifuge, a dryer, a metering device, and a closed-loop type calcination a furnace, a material storage tank, a bucket elevator, a ashing machine, a coarse paddle and a hydrocyclone, wherein the hydrocyclone is connected to the carbonization tower; the annular calciner is connected to the water cooling heat exchanger through the pipeline a compressor, a condenser, and a 0 2 storage tank; the settling separator, the centrifuge, and the ashing machine are respectively connected to the return pool through a pipe.

优选地, 在所述设备中, 所述净化装置的净化气体出口通过加压机与碳化 塔底部气体入口相连; 所述碳化塔通过输送泵 a与所述沉降分离机相连; 所述 沉降分离机通过输送泵 b与所述离心机相连; 所述粗桨池通过输送泵 c与所述 旋液分离器相连; 所述旋液分离器通过输送泵 d与所述碳化塔相连;  Preferably, in the apparatus, the purge gas outlet of the purification device is connected to the bottom gas inlet of the carbonization tower through a pressurizing machine; the carbonization tower is connected to the settling separator by a transfer pump a; the settling separator Connected to the centrifuge by a transfer pump b; the coarse paddle is connected to the hydrocyclone by a transfer pump c; the hydrocyclone is connected to the carbonization tower through a transfer pump d;

所述密闭环形煅烧炉通过输送泵 e与所述水冷换热器相连;  The closed loop type calcining furnace is connected to the water-cooled heat exchanger by a pump e;

所述回用水池通过输送泵 f连接化灰机。  The reuse pool is connected to the ash machine by a transfer pump f.

优选地, 在所述设备中, 所述碳化塔腔体底部设置有气体分布器, 上部设 有气体挡板、 气体排放口和碳化剂输入口。  Preferably, in the apparatus, the bottom of the carbonization tower chamber is provided with a gas distributor, and the upper portion is provided with a gas baffle, a gas discharge port and a carbonizer inlet.

优选地, 在所述设备中, 所述环形煅烧炉为全密闭式煅烧炉, 在该炉体中 设置有辐射加热部件, 所述辐射加热部件采用电加热辐射管、 隔绝烟气的加热 辐射管或微波加热辐射管。  Preferably, in the apparatus, the annular calciner is a fully enclosed calciner, in which a radiant heating component is disposed, and the radiant heating component uses an electric heating radiant tube and a heating radiant tube for isolating the flue gas. Or microwave to heat the radiant tube.

优选地, 在所述设备中, 所述斗式提升机侧设置有卸料器, 化灰机连接在 所述卸料器底部。  Preferably, in the apparatus, the bucket elevator side is provided with a discharger, and the ashing machine is connected to the bottom of the discharger.

相应地, 本发明还提供一种以 CaO为载体循环捕集二氧化碳的工艺, 包括 下述步骤: Correspondingly, the present invention also provides a process for recycling carbon dioxide by using CaO as a carrier, including The following steps:

步骤 A, 烟气净化处理: 将烟气引入净化装置, 去除其中的 S02、 NOx、 重 金属、二恶英和飞灰等有害气体及杂质,经净化处理后的烟气中主要成分为 C02 和 N2; Step A, Flue gas purification treatment: Introduce the flue gas into the purification device to remove harmful gases and impurities such as S0 2 , NO x , heavy metals, dioxins and fly ash. The main component of the purified flue gas is C0 2 And N 2 ;

步骤 B, 碳化: 将净化处理后的烟气通过加压机加压, 再经由碳化塔底部的 入口经气体分布器进入碳化塔中,其中, C02与碳化塔内部的石灰乳溶液发生碳 化反应生成 CaC03桨料和 H20, 完成对烟气中 C02的吸收过程。 此步骤主要化 学反应式为: Step B, and carbonizing: the purified flue gas treatment by a pressing machine, and then enters the carbonation tower via an inlet through the gas distribution bottom of the carbonation tower, wherein, C0 2 carbonation of milk of lime solution inside the column carbonation reaction The CaC0 3 paddle and H 2 0 are generated to complete the absorption process of C0 2 in the flue gas. The main chemical reaction formula for this step is:

Ca(OH)2+C02+H20= CaC03j+H20+71.18KJ/mol Ca(OH) 2 +C0 2 +H 2 0= CaC0 3 j+H 2 0+71.18KJ/mol

N2经气体挡板阻隔由碳化塔顶部气体排出口排入大气中; N 2 is discharged into the atmosphere by a gas baffle barrier from the gas discharge port at the top of the carbonization tower;

步骤 C, 碳化产物 CaC03处理: 碳化反应生成的 CaC03桨料分别通过沉降 分离机分离、 离心机脱水、 干燥机干燥后形成成品轻质碳酸钙, 成品轻钙经计 量后输送至全密闭环形煅烧炉中; Step C, Carbide product CaC0 3 treatment: The CaC0 3 pulp produced by the carbonization reaction is separately separated by a sedimentation separator, dehydrated by a centrifuge, and dried by a dryer to form a finished light calcium carbonate, and the finished light calcium is metered and transported to a full-closed closed loop shape. Calcination furnace;

步骤 D, C02解吸: 成品轻钙 & 03在环形煅烧炉内在完全隔绝空气的条 件下经高温煅烧分解, 得到煅烧产物可后续利用的 CaO及高纯度的 C02气体; 此步骤主要化学反应式为: Step D, C0 2 desorption: The finished light calcium & 0 3 is decomposed by high temperature calcination in a ring-shaped calciner under complete air isolation to obtain CaO and high-purity C0 2 gas which can be subsequently used for calcination; the main chemical reaction in this step The formula is:

CaC03^^= CaO +C02†-177.97KJ/mol 步骤 E, CaO消化: 将煅烧产物 CaO运送至储存仓冷却至 60度以下, 输送 至斗式提升机, 并经卸料器离心卸载至化灰机; CaO 与化灰机内来自自水冷换 热器的热水和回用水池的清水混合消化反应后, 得到石灰乳粗桨排入粗桨池中; 此步骤主要化学反应式为: CaC0 3 ^^= CaO +C0 2 †-177.97KJ/mol Step E, CaO digestion: The calcined product CaO is transported to a storage bin and cooled to below 60 degrees, sent to a bucket elevator, and centrifugally unloaded through a discharger. The ashing machine; the CaO and the ashing machine are mixed with the hot water from the water-cooling heat exchanger and the clean water of the reused pool, and then the coarse milk slurry is discharged into the coarse paddle; the main chemical reaction formula of this step is:

CaO+H20 Ca(OH)2+65.3KJ/mol 步骤 F, 石灰乳调和精制: 粗桨池内的石灰乳输送至旋液分离器进行精制, 得到石灰乳精桨; 步骤 G, 石灰乳回收利用: 经精制后得到的石灰乳精桨输送至碳化塔, 补 充碳化塔所需的碳化剂; CaO+H 2 0 Ca(OH) 2 +65.3KJ/mol Step F, lime milk blending and refining: The lime milk in the coarse paddle is transported to a hydrocyclone for purification to obtain a lime emulsion paddle; Step G, lime milk recycling and utilization: the refined lime milk slurry obtained by the refining is sent to the carbonization tower to supplement the carbonization agent required for the carbonization tower;

步骤 H, 高纯度 02储 (封) 存: 密闭环形煅烧炉上部气态产物 C02气体 经由耐热管道输送至水冷换热器,冷却至 50°C ;冷却后高纯 02气体经压缩机、 冷凝器的作用转变为液态 C02成品, 由密闭管道输送至 02存储罐中存储。 将 其储存后可后续利用于食品加工保鲜、 饮料、 防火等领域用途, 也可通过较为 成熟的 C02封存技术将其注入当地盐水深层或海洋中封存。 Step H, high purity 0 2 storage (sealed) Storage: The upper gaseous product C0 2 gas in the closed-loop type calcining furnace is sent to the water-cooled heat exchanger via a heat-resistant pipe, cooled to 50 ° C; after cooling, the high-purity 0 2 gas passes through the compressor The function of the condenser is converted into a liquid C0 2 finished product, which is transported by a closed pipe to a storage tank of 0 2 storage. After storage, it can be used in food processing, beverage, fire prevention and other fields. It can also be injected into deep saline or marine water by more mature C0 2 storage technology.

优选地, 在所述工艺中, 步骤 A中经过净化处理后的烟气中 C02和N2的体 积浓度为分别为 10-30%、 70-90%。 Preferably, in the process, the volume concentrations of C0 2 and N 2 in the flue gas after the purification treatment in step A are 10-30% and 70-90%, respectively.

优选地, 在所述工艺中, 步骤 C 中沉降分离、 离心脱水所得的上清液进入 回用水池, 回用水池的水可根据需要回用于所述步骤 E中 CaO消化过程。  Preferably, in the process, the supernatant obtained by sedimentation separation and centrifugal dehydration in step C enters the reuse pool, and the water used in the reuse pool can be reused for the CaO digestion process in the step E as needed.

优选地, 在所述工艺中, 步骤 D中环形煅烧炉煅烧温度为 1000-1400 °C。在 此煅烧温度下, &0)3可以迅速完全地分解为 C02气体和 CaO。 煅烧 CaCO^ 设备选择对空气隔绝效果极好, 且能实现高温煅烧的环形煅烧炉, 保证收集到 的 C02纯度。 Preferably, in the process, the calcining temperature of the annular calciner in step D is 1000-1400 °C. At this calcination temperature, &0) 3 can be rapidly and completely decomposed into C0 2 gas and CaO. The calcined CaCO^ equipment is excellent in air insulation and can realize high temperature calcination of the annular calciner to ensure the purity of the collected CO 2 .

优选地, 在所述工艺中, 步骤 H中采用夹套冷水换热的方法对生成的高温 高纯度 C02进行冷却,冷却至冷却至 50°C,获得的热水回用于所述步骤 E中 CaO 消化过程。 Preferably, in the process, in step H, the generated high-temperature high-purity CO 2 is cooled by a jacket cold water heat exchange method, cooled to 50 ° C, and the obtained hot water is returned to the step E. The CaO digestion process.

本发明提供的工艺及设备具有以下有益效果: (1 ) 相对于现有方法, 本发 明采用的碳捕集材料成本低, 对系统的腐蚀性小, 节约能源; (2) Ca(OH)2乳液 对于 C02的吸收率高, 相对于固体吸收剂具有明显优势; (3 ) 在完全隔绝空气 条件下对 CaC03进行煅烧, 捕集所得的 C02纯度可达 99%以上, 有利于 C02后 续利用及处理; (4) 整个系统封闭循环, 钙吸收剂和水实现循环利用, 大大降 低运行维护费用。 The process and equipment provided by the invention have the following beneficial effects: (1) Compared with the prior method, the carbon capture material used in the invention has low cost, low corrosivity to the system, and energy conservation; (2) Ca(OH) 2 The emulsion has a high absorption rate for C0 2 and has obvious advantages over the solid absorbent; (3) Calcination of CaC0 3 under completely isolated air conditions, the purity of C0 2 obtained by the capture can reach 99% or more, which is favorable for C0 2 Subsequent use and treatment; (4) The entire system is closed, the calcium absorbent and water are recycled, which greatly reduces the operation and maintenance costs.

附图说明 DRAWINGS

图 1为本发明实施例中以 CaO为载体循环捕集二氧化碳的设备流程图。 图 2为本发明实施例的工艺流程图。 图中: 1、 净化装置; 2、 加压机; 3、 碳化塔; 3a、 气体分布器; 3b、 气体 挡板; 3c、 气体排放口; 3d、 碳化剂输入口; 4、 输送泵 a; 5、 沉降分离机; 6、 输送泵 b; 7、 离心机; 8、 干燥机; 9、 计量装置; 10、 密闭环形煅烧炉; 10a、 辐射加热部件; 11、 物料储存仓; 12、 斗式提升机; 12a、 卸料器; 13、 化灰机; 14、 粗桨池; 14a、 搅拌装置; 15、 输送泵 c; 16、 旋液分离器; 17、 输送泵山 18、 输送泵 e; 19、 水冷换热器; 20、 压缩机; 21、 冷凝器; 22、 02储存罐; 23、 回用水池; 24、 输送泵 f; 24a、 阀门。 1 is a flow chart of an apparatus for cyclically capturing carbon dioxide by using CaO as a carrier in an embodiment of the present invention. 2 is a process flow diagram of an embodiment of the present invention. In the figure: 1, purification device; 2, pressurizing machine; 3, carbonization tower; 3a, gas distributor; 3b, gas baffle; 3c, gas discharge port; 3d, carbonization agent input port; 4, delivery pump a; 5, sedimentation separator; 6, pump b; 7, centrifuge; 8, dryer; 9, metering device; 10, closed-loop type calcining furnace; 10a, radiant heating parts; 11, material storage bin; Hoist; 12a, unloader; 13, ashing machine; 14, coarse paddle; 14a, stirring device; 15, pump c; 16, hydrocyclone; 17, pump pump 18, pump e; 19, water-cooled heat exchanger; 20, compressor; 21, condenser; 22, 0 2 storage tank; 23, reuse pool; 24, transfer pump f; 24a, valve.

具体实施方式 detailed description

以下结合附图和具体实施例对本发明作进一步详细描述。 以下仅为本发明 的优选实施方式, 本发明的保护范围并不局限于此, 任何本领域的技术人员在 本发明的公开范围内, 可很容易进行的改变或变化都涵盖在本发明的保护范围 之内。 因此, 本发明的保护范围应以权利要求书的保护范围为准。  The invention is further described in detail below with reference to the drawings and specific embodiments. The following is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any changes or variations that can be easily made by those skilled in the art within the scope of the present invention are covered by the present invention. Within the scope. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

图 1所示为一种以 CaO为载体循环捕集二氧化碳的设备, 包括经管道依次 相连的用于尾气净化的净化装置 1 ; 用于 C02吸收的碳化塔 3 ; 用于碳化产物 CaC03预处理的沉降分离机 5、 离心机 7、 干燥机 8; 用于 02解吸的密闭环形 煅烧炉 10; 用于煅烧产物 CaO消化以便重新回用于碳化过程的物料储存仓 11、 斗式提升机 12、 化灰机 13 ; 用于石灰乳精制的粗桨池 14、 旋液分离器 16; 用 于 C02储存的水冷换热器 19、 压缩机 20、 冷凝器 21、 C02储存罐 22; 其中, 沉降分离机 5、 离心机 7和化灰机 13分别通过管道与回用水池 23连接。 Figure 1 shows an apparatus for cyclically capturing carbon dioxide using CaO as a carrier, comprising a purification device 1 for exhaust gas purification connected in series via a pipeline; a carbonization tower 3 for CO 2 absorption; and a carbonization product CaC0 3 pre- Treated sedimentation separator 5, centrifuge 7, dryer 8; closed closed loop calciner 10 for desorption of 0 2 ; material storage tank 11 for bucket calcination to be recycled for carbonization process, bucket elevator 12. Ash machine 13; coarse paddle 14 for lime milk refining, hydrocyclone 16; water-cooled heat exchanger 19 for C0 2 storage, compressor 20, condenser 21, C0 2 storage tank 22; Among them, the sedimentation separator 5, the centrifuge 7 and the ashing machine 13 are connected to the recycling pool 23 through pipes, respectively.

所述净化装置 1的净化气体出口经由加压机 2与碳化塔 3底部气体入口相 连; 所述碳化塔的底部设有气体分布器 3a, 上部设有气体挡板 3b、 气体排放口 3c和碳化剂输入口 3d; 所述碳化塔 3液体排出口经由输送泵 a 4与所述沉降分 离机 5入口相连; 输送泵 b 6与所述沉降分离机 5底部相连, 将富 CaC03液体 输送至所述离心机 7入口; 所述离心机 7固体排出口与所述干燥机 8入口相连, 所述干燥机 8干燥料出口与计量装置 9物料入口相连, 所述计量装置 9出口与 所述密闭环形煅烧炉 10物料入口相连;输送泵 e 18气体输入口与所述密闭环形 煅烧炉 10气体收集口相连,将高纯度 C02气体输送至所述水冷换热器 19,所述 水冷换热器 19出口与所述压缩机 20入口相连, 所述压缩机 20压缩气体出口与 所述冷凝器 21气体输入口相连, 所述冷凝器 21气体输出口与所述 C02存储罐 22相连;所述密闭环形煅烧炉 10固体产物出口与所述物料储存仓 11入口相连, 所述物料储存仓 11 出口与所述斗式提升机 12物料入口相连, 经提升后的物料 输送至所述化灰机 13 ; 所述化灰机 13桨料出口与所述粗桨池 14入口相连; 输 送泵 c 15、 输送泵 d 17的入口分别与所述粗桨池 14、 所述旋液分离器 16物料 出口相连, 所述输送泵 c 15、输送泵 d 17的出口分别与所述旋液分离器 16物料 入口、 碳化塔 3的物料入口 3d相连。 所述回用水池 23通过输送泵 f 24连接化 灰机 13。 其中, 所述粗桨池 14中设置有搅拌装置 14a。 The purge gas outlet of the purification device 1 is connected to the bottom gas inlet of the carbonization tower 3 via a pressurizing machine 2; the bottom of the carbonization tower is provided with a gas distributor 3a, the upper portion is provided with a gas baffle 3b, a gas discharge port 3c and carbonization 3D agent inlet; the carbonation tower liquid discharge port 3 a 4 and the inlet of the sedimentation separator 5 is connected via a feed pump; b 6 feed pump connected to the bottom of the sedimentation separator 5, CaC0 3 enriched liquid delivered to the The centrifuge 7 inlet; the centrifuge 7 solid discharge port is connected to the dryer 8 inlet, the dryer 8 dry material outlet is connected to the metering device 9 material inlet, the metering device 9 outlet and the closed loop The material inlets of the calciner 10 are connected; the gas inlet of the transfer pump e 18 is connected to the gas collection port of the closed closed loop calciner 10, and the high purity CO 2 gas is sent to the water-cooled heat exchanger 19, The outlet of the water-cooled heat exchanger 19 is connected to the inlet of the compressor 20, and the compressed gas outlet of the compressor 20 is connected to the gas inlet of the condenser 21, the gas outlet of the condenser 21 and the storage tank 22 of the C0 2 Connected; the closed-loop calciner 10 solid product outlet is connected to the material storage tank 11 inlet, the material storage tank 11 outlet is connected to the bucket elevator 12 material inlet, and the upgraded material is delivered to the a ashing machine 13; the ash feeder 13 blade outlet is connected to the coarse paddle 14 inlet; the delivery pump c 15, the delivery pump d 17 inlet and the coarse paddle 14, respectively, the hydrocyclone 16 material outlets are connected, and the outlets of the transfer pump c 15 and the transfer pump d 17 are respectively connected to the material inlet of the hydrocyclone 16 and the material inlet 3d of the carbonization tower 3. The recycling pool 23 is connected to the ashing machine 13 via a transfer pump f24. Wherein, the coarse paddle 14 is provided with a stirring device 14a.

在一个优选的实施例中, 所述沉降分离机 5、所述离心机 7的上清液出口与 所述回用水池 23的入口相连, 所述回用水池 23的出口通过管道与输送泵 f 24、 的入口相连, 管道上连有阀门 24a, 所述输送泵 f 24的回用水出口与所述化灰机 13清水入口相连。  In a preferred embodiment, the sedimentation separator 5, the supernatant outlet of the centrifuge 7 is connected to the inlet of the recovery pool 23, and the outlet of the recovery pool 23 is passed through the conduit and the transfer pump f. 24, the inlet is connected, the pipe is connected with a valve 24a, and the return water outlet of the transfer pump f 24 is connected to the clean water inlet of the ashing machine 13.

在另一个优选的实施例中, 所述水冷换热器 19置换的热水通过管道与所述 化灰机 13清水入口相连。  In another preferred embodiment, the hot water displaced by the water-cooled heat exchanger 19 is connected to the clean water inlet of the ashing machine 13 through a pipe.

在另一个优选的实施例中, 所述密闭环形煅烧炉 10为全密闭式煅烧炉, 在 该炉体中设置有辐射加热部件 10a, 所述辐射加热部件 10a采用电加热辐射管、 隔绝烟气的加热辐射管或微波加热辐射管。  In another preferred embodiment, the closed loop type calcining furnace 10 is a fully enclosed calcining furnace in which a radiant heating part 10a is provided, and the radiant heating part 10a is electrically heated to illuminate the tube and to isolate the flue gas. Heat the radiant tube or microwave to heat the radiant tube.

在另一个优选的实施例中, 所述斗式提升机 12侧设置有卸料器 12a, 化灰 机 13连接在所述卸料器 12a底部。  In another preferred embodiment, the bucket elevator 12 side is provided with a discharger 12a, and the ashing machine 13 is attached to the bottom of the discharger 12a.

如图 2所示, 上述设备对应的工作流程如下:  As shown in Figure 2, the workflow of the above device is as follows:

步骤 A, 烟气净化处理: 将烟气通过管道引入净化装置 1, 烟气中的 S02、 NOx、重金属、二恶英、飞灰等有害气体及杂质在净化装置 1的作用下得到去除, 经净化处理的烟气中主要成分为 C02和N2, 体积浓度为 15%、 78%。 Step A, the flue gas cleaning process: the flue gas purification device 1 is introduced through a pipe, the flue gas S0 2, NO x, heavy metals, dioxins, and other harmful gases and fly ash removed impurities obtained under the action of the purification apparatus 1 The main components of the purified flue gas are C0 2 and N 2 , and the volume concentration is 15% and 78%.

步骤 B,碳化:通过加压 2的加压作用,将净化装置 1出口的气体压力提升, 以增强碳化过程中的传质效果。 净化烟气经由碳化塔 3 底部的入口经气体分布 器 3a进入碳化塔 3中。 气体自下而上上升过程中, 其中的二氧化碳与碳化塔 3 内部的石灰乳溶液发生快速的化学反应, 二氧化碳被迅速吸收, 生成 & 03和 H20, 而 N2在上升流动过程中则不与石灰乳发生反应, 在碳化塔 3顶部聚集后 经气体挡板 3b阻隔, 最终由碳化塔顶部气体排出口 3c排入大气中。 Step B, carbonization: The pressure of the gas at the outlet of the purification device 1 is increased by the pressurization of the pressurization 2 to enhance the mass transfer effect in the carbonization process. The purified flue gas enters the carbonization tower 3 via the gas distributor 3a through the inlet at the bottom of the carbonization tower 3. The gas rises from the bottom up, the carbon dioxide and carbonization tower 3 The internal lime milk solution undergoes a rapid chemical reaction, and carbon dioxide is rapidly absorbed to form & 0 3 and H 2 0, while N 2 does not react with the lime milk during the ascending flow, and collects gas at the top of the carbonization tower 3 The baffle 3b is blocked and finally discharged into the atmosphere by the gas discharge port 3c at the top of the carbonization tower.

步骤 C, 碳化产物 CaC03处理: 碳化反应生成的 CaC03桨料含水量较高, 不宜直接进行煅烧回收 C02。输送泵 a 4将碳化生成的 CaC03桨料输送至沉降分 离机 5, 在重力的作用下, 桨料中的水和固体 CaCO^ 到初步分离; 输送泵 b 6 将沉降分离机 5底部的固体 CaC03悬浮液输送至离心机 7, 离心机 7利用高速 旋转的转鼓产生离心力将悬浮液中的固体颗粒截留在转鼓内并在力的作用下向 机外自动卸出进入干燥机 8; 干燥机 8通过热空气、烟道气或红外线等加热方式 将水分含量为 35%左右的固体 CaC03中所含的水分进一步除去, 出口物料水分 含量为 0.3%左右, 满足后续煅烧工序的要求; 沉降分离机 5及离心机 7的上清 液均分别通过管道排入回用水池 23 ;干燥后的固体 CaC03为成品的轻质碳酸钙, 其粒度和含水量均符合煅烧的要求, 成品轻钙经计量装置 9精确计量后输送至 全密闭环形煅烧炉 10物料入口。 Step C, treatment of carbonized product CaC0 3 : The CaC0 3 paddle produced by the carbonization reaction has a high water content, and it is not suitable to directly recover the C0 2 by calcination. The transfer pump a 4 transports the carbonized CaC0 3 slurry to the settling separator 5, and under the action of gravity, the water and the solid CaCO^ in the slurry are initially separated; the transfer pump b 6 will settle the solid at the bottom of the separator 5 CaC0 3 suspension is transported to the centrifuge 7, the centrifuge 7 uses a high-speed rotating drum to generate centrifugal force to trap the solid particles in the suspension in the drum and automatically discharged into the dryer 8 under the force of the machine; The dryer 8 further removes the moisture contained in the solid CaC0 3 having a moisture content of about 35% by heating by hot air, flue gas or infrared rays, and the moisture content of the outlet material is about 0.3%, which satisfies the requirements of the subsequent calcination process; The supernatants of the sedimentation separator 5 and the centrifuge 7 are respectively discharged into the reuse pool 23 through the pipeline; the dried solid CaC0 3 is the finished light calcium carbonate, and the particle size and water content thereof meet the requirements of calcination, and the finished product is light. The calcium is accurately metered by the metering device 9 and transported to the material inlet of the full-closed closed-loop calciner 10.

步骤 D, C02解吸: 在密闭环形煅烧炉 10内, 成品轻质碳酸钙在完全隔绝 空气的条件下被高温煅烧分解, 煅烧产物为 CaO及 C02。 密闭环形煅烧炉 10 内采用完全隔绝空气的辐射加热部件 10a 产生热量, 炉内煅烧区温度为 1000-1400 °C , 得到煅烧产物 CaO及 C02 ; 由于密闭环形煅烧炉 10内的特殊结 构, 炉膛空间内 C02气体浓度达 98-99.8%。 Step D, C0 2 Desorption: In the closed-loop calcining furnace 10, the finished light calcium carbonate is decomposed by high temperature calcination under conditions of complete air isolation, and the calcined products are CaO and C0 2 . The heat is generated by the radiant heating component 10a which is completely insulated from the air in the closed-loop type calcining furnace 10, and the calcination zone temperature in the furnace is 1000-1400 ° C, and the calcined products CaO and C0 2 are obtained; due to the special structure in the closed-loop calcining furnace 10, the furnace The concentration of C0 2 gas in the space is 98-99.8%.

步骤 E, CaO消化: 密闭环形煅烧炉 10出口固体物料 CaO被运送至物料储 存仓 11进行冷却, 待物料温度降至 60度以下, 输送设备将其输送至斗式提升 机 12; 斗式提升机 12将粉状 CaO物料垂直提升至一定高度, 并经卸料器 12a 的作用快速离心卸载至化灰机 13 ; 在化灰机 13内, CaO物料与机内来自水冷换 热器 19的热水及来自回用水池 23的清水混合, 进行消化反应, 生产出石灰乳 粗桨, 化灰机 13 内消化反应进行完全后, 石灰乳粗桨被排入粗桨池 14中, 粗 桨池 14内石灰乳浓度为 30%。  Step E, CaO digestion: The closed solid-state material CaO is transported to the material storage bin 11 for cooling, and the material temperature is reduced to below 60 degrees, and the conveying device transports it to the bucket elevator 12; the bucket elevator 12 The powdery CaO material is vertically raised to a certain height, and is quickly centrifugally unloaded to the ashing machine 13 by the action of the unloader 12a; in the ashing machine 13, the CaO material and the hot water from the water-cooling heat exchanger 19 in the machine And the water from the reuse pool 23 is mixed, and the digestion reaction is carried out to produce a coarse slurry of lime milk. After the digestion reaction in the ashing machine 13 is completed, the coarse slurry of the lime milk is discharged into the coarse paddle 14 and the coarse paddle 14 is The milk concentration of lime is 30%.

步骤 F, 石灰乳精制: 输送泵 c 15将粗桨池 14内的石灰乳粗桨送至精制设 备 -旋液分离器 16进行精制, 精制后的石灰乳溶液活性较高, 浓度适中, 适宜于 重新进入碳化塔 3吸附电厂尾气中的 C02。 粗桨池 14内设有搅拌装置 14a, 有 利于后续石灰乳精制及碳化反应的进行。 Step F, lime milk refining: The conveying pump c 15 sends the coarse milk coarse paddle in the coarse paddle 14 to the refining device The preparative-cyclone separator 16 is refined, and the refined lime milk solution has high activity and moderate concentration, and is suitable for re-entering the carbonization tower 3 to adsorb C0 2 in the power plant exhaust gas. The coarse paddle tank 14 is provided with a stirring device 14a, which is beneficial to the subsequent lime milk refining and carbonization reaction.

步骤 G, 石灰乳回收利用: 经精制后得到的石灰乳精桨由输送泵 d 17送至 碳化剂输入口 3d, 补充碳化塔 3内部的碳化吸收剂。  Step G, lime milk recycling: The refined lime milk slurry obtained by the refining is sent to the carbonizing agent inlet 3d by the transfer pump d 17 to supplement the carbonized absorbent inside the carbonization tower 3.

步骤 H, 高纯度 02储 (封)存: 密闭环形煅烧炉 10上部气态产物出口产 出的高纯度 C02气体纯度为 98.0-99.8%, 温度为 200°C左右, 在输送泵 e 21的 作用下经由耐热管道输送至水冷换热器 19进行冷却,冷却后气体温度降至 50°C; 冷却后高纯 C02气体经压缩机 20、 冷凝器 21 的作用转变为液态 C02成品, 由 密闭管道输送至 C02存储罐 22中, 以便后续利用。 Step H, high purity 0 2 storage (sealed) storage: The high-purity C0 2 gas produced by the upper gaseous product outlet of the closed-loop type calcining furnace 10 has a purity of 98.0-99.8%, a temperature of about 200 ° C, and a pump e 21 Under the action, it is sent to the water-cooled heat exchanger 19 through the heat-resistant pipe for cooling. After cooling, the gas temperature is lowered to 50 ° C; after cooling, the high-purity C0 2 gas is converted into the liquid C0 2 finished product by the action of the compressor 20 and the condenser 21, It is conveyed to the C0 2 storage tank 22 by a closed pipe for subsequent use.

以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明, 不 能认定本发明的具体实施方式仅限于此, 对于本发明所属技术领域的普通技术 人员来说, 在不脱离本发明构思的前提下, 还可以做出若干简单的推演或替换, 都应当视为属于本发明由所提交的权利要求书所确定的专利保护范围。  The above is a detailed description of the present invention in conjunction with the specific preferred embodiments. It is not to be understood that the specific embodiments of the present invention are limited thereto, and those skilled in the art to which the present invention pertains, without departing from the scope of the present invention. In the following, a number of simple derivations or substitutions may be made, which should be considered as belonging to the scope of patent protection as defined by the appended claims.

Claims

权 利 要 求 书 Claims
1、一种以 CaO为载体循环捕集二氧化碳的设备,包括经管道相连的净化装 置 (1) 和碳化塔 (3), 其特征在于, 所述碳化塔 (3) 经管道依次连接有沉降 分离机(5)、 离心机 (7)、 干燥机(8)、 计量装置 (9)、 密闭环形煅烧炉 (10)、 物料储存仓 (11)、 斗式提升机 (12)、 化灰机 (13)、 粗桨池 (14) 和旋液分离 器 (16), 所述旋液分离器 (16) 再与碳化塔 (3) 相连; 所述环形煅烧炉 (10) 经管道还依次连接有水冷换热器 (19)、 压縮机 (20)、 冷凝器 (21) 和 C02储 存罐 (22); 所述沉降分离机 (5)、 离心机 (7) 和化灰机 (13) 分别通过管道 与回用水池 (23) 连接。 1. A device for cyclically capturing carbon dioxide by using CaO as a carrier, comprising a purification device (1) connected to a pipeline and a carbonization tower (3), characterized in that the carbonization tower (3) is connected to a sedimentation separation by a pipeline. Machine (5), centrifuge (7), dryer (8), metering device (9), closed loop type calciner (10), material storage bin (11), bucket elevator (12), chemical machine ( 13), a coarse paddle (14) and a hydrocyclone (16), the hydrocyclone (16) is further connected to the carbonization tower (3); the annular calciner (10) is also connected via a pipeline Water-cooled heat exchanger (19), compressor (20), condenser (21) and C0 2 storage tank (22); sedimentation separator (5), centrifuge (7) and ashing machine (13) They are connected to the return pool (23) through pipes.
2、根据权利要求 1所述的以 CaO为载体循环捕集二氧化碳的设备, 其特征 在于, 所述净化装置 (1) 的净化气体出口通过加压机 (2) 与碳化塔 (3) 底部 气体入口相连; 所述碳化塔 (3) 通过输送泵 a (4) 与所述沉降分离机 (5) 相 连; 所述沉降分离机 (5) 通过输送泵 b (6) 与所述离心机 (7) 相连; 所述粗 浆池 (14) 通过输送泵 c (15) 与所述旋液分离器 (16) 相连; 所述旋液分离器 The apparatus for cyclically capturing carbon dioxide by using CaO as a carrier according to claim 1, wherein the purification gas outlet of the purification device (1) passes through the pressurizing machine (2) and the bottom gas of the carbonization tower (3) The inlet is connected; the carbonization tower (3) is connected to the settling separator (5) by a transfer pump a (4); the settling separator (5) is passed through a transfer pump b (6) and the centrifuge (7) Connected; the roughing tank (14) is connected to the hydrocyclone (16) by a transfer pump c (15); the hydrocyclone
(16) 通过输送泵 d (17) 与所述碳化塔 (3) 相连; (16) connected to the carbonization tower (3) by a pump d (17);
所述密闭环形煅烧炉 (10) 通过输送泵 e (18) 与所述水冷换热器 (19) 相 连;  The closed loop type calciner (10) is connected to the water-cooled heat exchanger (19) through a transfer pump e (18);
所述回用水池 (23) 通过输送泵 f (24) 连接化灰机 (13)。  The reuse tank (23) is connected to the ash machine (13) via a transfer pump f (24).
3、根据权利要求 1所述的以 CaO为载体循环捕集二氧化碳的设备, 其特征 在于, 所述碳化塔 (3) 腔体底部设置有气体分布器 (3a), 上部设有气体挡板 The apparatus for cyclically capturing carbon dioxide by using CaO as a carrier according to claim 1, wherein the carbonization tower (3) is provided with a gas distributor (3a) at the bottom of the chamber and a gas barrier at the upper portion.
(3b)、 气体排放口 (3c) 和碳化剂输入口 (3d)。 (3b), gas discharge port (3c) and carbonizer inlet (3d).
4、根据权利要求 1所述的以 CaO为载体循环捕集二氧化碳的设备, 其特征 在于, 所述环形煅烧炉 (10) 为全密闭式煅烧炉, 在该炉体中设置有辐射加热 部件(10a) , 所述辐射加热部件 (10a)采用电加热辐射管、 隔绝烟气的加热辐 射管或微波加热辐射管。  4. The apparatus for cyclically capturing carbon dioxide by using CaO as a carrier according to claim 1, wherein the annular calciner (10) is a fully enclosed calciner in which a radiant heating component is disposed ( 10a), the radiant heating component (10a) is an electric heating radiant tube, a heating radiant tube for isolating the flue gas or a microwave heating radiant tube.
5、根据权利要求 1所述的以 CaO为载体循环捕集二氧化碳的设备, 其特征 在于, 所述斗式提升机 (12) 侧设置有卸料器 (12a), 化灰机 (13 ) 连接在所 述卸料器 (12a) 底部。 5. The apparatus for cyclically capturing carbon dioxide by using CaO as a carrier according to claim 1, characterized in that The side of the bucket elevator (12) is provided with a discharger (12a), and the ashing machine (13) is connected to the bottom of the discharger (12a).
6、 一种以 CaO为载体循环捕集二氧化碳的工艺, 其特征在于, 该工艺包括 下述步骤:  6. A process for cyclically capturing carbon dioxide by using CaO as a carrier, characterized in that the process comprises the following steps:
步骤 A, 尾气净化处理: 将烟气引入净化装置 (1 ), 去除其中的有害气体 及杂质, 经过净化处理后的烟气中主要成分为 ( 02和 N2; Step A, exhaust gas purification treatment: introducing flue gas into the purification device (1), removing harmful gases and impurities therein, and the main components in the flue gas after purification treatment are (0 2 and N 2;
步骤 B, 碳化: 将净化处理后的烟气通过加压机(2)加压, 进入碳化塔(3 ) 中, 其中, ( 02与碳化塔 (3 ) 内部的石灰乳溶液发生碳化反应生成 CaC03浆料 和¾0, N2由碳化塔顶部气体排出口 (3c) 排入大气中; Step B, carbonization: pressurizing the flue gas after being purified by the pressurizing machine (2), and entering the carbonization tower (3), wherein (0 2 and the lime milk solution inside the carbonization tower (3) are carbonized to generate CaC0 3 slurry and 3⁄40, N 2 are discharged into the atmosphere from the top gas discharge port (3c) of the carbonization tower;
步骤 C, 碳化产物 CaC03处理: 碳化反应生成的 CaC03浆料分别通过沉降 分离机 (5 ) 分离、 离心机 (7 ) 脱水、 干燥机 (8 ) 干燥后, 形成成品轻质碳酸 钙, 成品轻钙经计量装置 (9) 计量后输送至密闭环形煅烧炉 (10) 中; Step C, Carbide product CaC0 3 treatment: The CaC0 3 slurry produced by the carbonization reaction is separated by a sedimentation separator (5), dehydrated by a centrifuge (7), and dried by a dryer (8) to form a finished light calcium carbonate, and the finished product is obtained. The light calcium is metered into the closed closed loop calciner (10) after being metered by the metering device (9);
步骤 D, C02解吸: 成品轻质碳酸钙 CaC03在密闭环形煅烧炉 (10) 内经 高温煅烧分解, 得到煅烧产物 CaO及高浓度的 C02; Step D, C0 2 desorption: the finished light calcium carbonate CaC0 3 is decomposed by high temperature calcination in a closed closed loop calciner (10) to obtain a calcined product CaO and a high concentration of C0 2;
步骤 E, CaO消化:将煅烧产物 CaO运送至储存仓(11 )冷却至 60度以下, 输送至斗式提升机 (12) , 并经卸料器 (12a) 离心卸载至化灰机 (13 ) ; CaO 与化灰机 (13 ) 内来自水冷换热器 (19) 的热水和回用水池 (23 ) 的清水混合 发生消化反应, 生成的石灰乳粗桨排入粗桨池 (14) 中;  Step E, CaO digestion: the calcined product CaO is transported to the storage silo (11) to be cooled to below 60 degrees, sent to the bucket elevator (12), and centrifugally unloaded to the ashing machine (13) via the unloader (12a). CaO is mixed with the hot water from the water-cooled heat exchanger (19) and the clean water from the reuse tank (23) in the ashing machine (13), and the resulting lime milk coarse paddle is discharged into the coarse paddle (14). ;
步骤 F, 石灰乳精制: 粗桨池 (14) 内的石灰乳输送至旋液分离器(16)进 行精制, 得到石灰乳精浆;  Step F, lime milk refining: The lime milk in the coarse paddle tank (14) is sent to a hydrocyclone (16) for refining to obtain a lime milk concentrate;
步骤 G, 石灰乳回收利用: 经精制后得到的石灰乳精浆输送至碳化塔 (3 ), 以补充碳化塔 (3 ) 内部的碳化吸收剂;  Step G, lime milk recycling and utilization: the refined milk concentrate obtained by the purification is sent to the carbonization tower (3) to supplement the carbonized absorbent inside the carbonization tower (3);
步骤 H, 高纯度 C02封存储存: 密闭环形煅烧炉 (10) 上部气态产物 C02 气体经由耐热管道输送至水冷换热器 (19) 冷却; 冷却后高纯 C02气体经压缩 机 (20)、 冷凝器 (21 ) 的作用转变为液态 C02成品, 由密闭管道输送至 C02 存储罐 (22) 中存储。 Step H, high-purity C0 2 storage: dense closed-loop calciner (10) The upper gaseous product C0 2 gas is sent to the water-cooled heat exchanger (19) via a heat-resistant pipe to cool; after cooling, the high-purity C0 2 gas is passed through the compressor (20) ), the function of the condenser (21) is converted into a liquid C0 2 finished product, which is transported by a closed pipe to C0 2 Stored in the storage tank (22).
7、根据权利要求 6所述的以 CaO为载体循环捕集二氧化碳的工艺,其特征 在于: 所述步骤 A中经过净化处理后的烟气中 ( 02和 N2的体积浓度为分别为 10-30%、 70-90%。 The process for cyclically capturing carbon dioxide by using CaO as a carrier according to claim 6, wherein: in the flue gas after the purification treatment in the step A, the volume concentrations of 0 2 and N 2 are respectively 10 -30%, 70-90%.
8、根据权利要求 6所述的以 CaO为载体循环捕集二氧化碳的工艺,其特征 在于: 所述步骤 C中沉降分离、 离心分离所得的上清液进入回用水池 (23 ) , 回用水池 (23 ) 的水根据需要回用于所述步骤 E中 CaO消化过程。  The process for cyclically capturing carbon dioxide by using CaO as a carrier according to claim 6, wherein: the supernatant obtained by sedimentation separation and centrifugation in the step C enters a reuse pool (23), and is reused in the pool. The water of (23) is returned to the CaO digestion process in step E as needed.
9、根据权利要求 6所述的以 CaO为载体循环捕集二氧化碳的工艺,其特征 在于: 所述步骤 D中密闭环形煅烧炉 (10) 煅烧温度为 1000-1400 °C。  The process for cyclically capturing carbon dioxide by using CaO as a carrier according to claim 6, wherein: the dense closed-loop calcining furnace (10) in the step D has a calcination temperature of 1000-1400 °C.
10、 根据权利要求 6所述的以 CaO为载体循环捕集二氧化碳的工艺, 其特 征在于: 所述步骤 H中采用夹套冷水换热的方法对生成的高温高纯度 C02进行 冷却, 冷却至 50°C。 10. The process for cyclically capturing carbon dioxide by using CaO as a carrier according to claim 6, wherein: in the step H, the generated high-temperature high-purity C0 2 is cooled by a jacket cold water heat exchange method, and cooled to 50 ° C.
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