CN-122006617-A - Ceramic micro-channel membrane reaction system for preparing nano calcium carbonate by utilizing calcium-containing solid waste

Abstract

The invention relates to the technical field of nano material preparation and industrial waste recycling, in particular to a ceramic micro-channel membrane reaction system for preparing nano calcium carbonate by utilizing calcium-containing solid waste, which comprises a calcium-containing ore solution preparation unit, a CO 2 gas preparation unit, a primary modified membrane reactor and a secondary modified membrane reactor, wherein the primary modified membrane reactor and the secondary modified membrane reactor are arranged in series, a primary gas-liquid separation tank is arranged between the primary modified membrane reactor and the secondary modified membrane reactor, the calcium-containing ore solution preparation unit is communicated with an in-membrane channel of the primary modified membrane reactor, the CO 2 gas preparation unit is communicated with the outer sides of membranes of the primary modified membrane reactor and the secondary modified membrane reactor, and hydrophobic and corrosion-resistant modified functional layers are formed on surfaces of membrane components of the primary modified membrane reactor and the secondary modified membrane reactor. The invention improves the fixation rate of CO 2 and the conversion rate of calcium element in carbide slag by improving the reaction rate and the mass transfer efficiency, and ensures the high uniformity of the product.

Inventors

• ZHOU JUN
• ZHOU LINA
• LIAO JINGWEN
• Jing Shaotao
• YU CHANGJUN
• FAN CHUIGANG

Assignees

• 南京工业大学
• 卡本洛克科技(北京)有限公司
• 原初科技（北京）有限公司

Dates

Publication Date

20260512

Application Date

20260206

Claims (10)

1. 1. The ceramic micro-channel membrane reaction system for preparing nano calcium carbonate by utilizing calcium-containing solid waste is characterized by comprising a calcium-containing ore solution preparation unit, a CO 2 preparation unit, a primary modified membrane reactor and a secondary modified membrane reactor, wherein the primary modified membrane reactor and the secondary modified membrane reactor are arranged in series, a primary gas-liquid separation tank is arranged between the primary modified membrane reactor and the secondary modified membrane reactor, the calcium-containing ore solution preparation unit is communicated with an intra-membrane channel of the primary modified membrane reactor, and the CO 2 preparation unit is communicated with the outer sides of membranes of the primary modified membrane reactor and the secondary modified membrane reactor; wherein, the membrane component matrix of the primary modified membrane reactor and the secondary modified membrane reactor is porous ceramic material, and the membrane surfaces are all formed with hydrophobic and corrosion-resistant modified functional layers.
2. 2. The ceramic micro-channel membrane reaction system for preparing nano calcium carbonate by utilizing calcium-containing solid waste according to claim 1, wherein the surfaces of the membrane component shells of the primary modified membrane reactor and the secondary modified membrane reactor are provided with an annular air distribution cavity communicated with the CO 2 air distribution unit through quick-connection type sealing interfaces; Preferably, a plurality of through holes of 0.2-0.5 mm are alternately formed in the annular air distribution cavity.
3. 3. The ceramic microchannel membrane reaction system for preparing nano calcium carbonate by utilizing calcium-containing solid waste according to claim 1, further comprising a product collecting unit, wherein the product collecting unit is communicated with the secondary modified membrane reactor, and a secondary gas-liquid separation tank is arranged between the product collecting unit and the secondary modified membrane reactor.
4. 4. The ceramic microchannel membrane reaction system for preparing nano calcium carbonate by utilizing calcium-containing solid waste according to claim 1, wherein a primary additive adding mechanism is arranged on the calcium-containing ore solution preparing unit; The auxiliary agent in the primary auxiliary agent adding mechanism comprises any two or three of polyphosphate compounds, organic polymer compounds and surfactants.
5. 5. The ceramic microchannel membrane reaction system for preparing nano calcium carbonate by utilizing calcium-containing solid waste according to claim 1, wherein a secondary auxiliary agent adding mechanism is arranged on the primary gas-liquid separation tank; The auxiliary agent in the secondary auxiliary agent adding mechanism comprises a surfactant.
6. 6. The ceramic microchannel membrane reaction system for preparing nano calcium carbonate from calcium-containing solid waste according to claim 4 or 5, wherein the polyphosphate compound comprises any one or more of sodium pyrophosphate, ammonium polyphosphate, sodium hexametaphosphate, ammonium magnesium phosphate, and particles of polyphosphoric acid bacteria extract PolyP; the organic polymer compound comprises any one or more of polyglutamic acid, polyvinyl chloride acid, polyacrylic acid, polyethylene oxide, starch and chitosan; The surfactant comprises any one or more of anionic sodium stearate, sodium dodecyl sulfate, alpha-sodium alkenyl sulfonate, rhamnolipid and sophorolipid, cationic octadecyl trimethyl ammonium chloride, benzalkonium chloride, nonionic sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester.
7. 7. The ceramic micro-channel membrane reaction system for preparing nano calcium carbonate by utilizing calcium-containing solid waste according to claim 3, wherein a pH on-line monitor and a pH monitoring electromagnetic control valve are sequentially arranged on a pipeline between the primary gas-liquid separation tank and the secondary modified membrane reactor and a pipeline between the secondary gas-liquid separation tank and the product collecting unit.
8. 8. The ceramic microchannel membrane reaction system for preparing nano calcium carbonate by utilizing calcium-containing solid waste according to claim 1, wherein an electric control flow pump is arranged on a pipeline between the calcium-containing ore solution preparation unit and the primary modified membrane reactor.
9. 9. The ceramic microchannel membrane reaction system for preparing nano calcium carbonate by utilizing calcium-containing solid waste according to claim 1, wherein the electric control flowmeter is arranged on the pipeline between the CO 2 gas distribution unit and the first-stage modified membrane reactor and the second-stage modified membrane reactor.
10. 10. The ceramic microchannel membrane reaction system for preparing nano calcium carbonate from calcium-containing solid waste according to claim 3, wherein the primary gas-liquid separation tank and the secondary gas-liquid separation tank are both reversely communicated with the CO 2 gas distribution unit.

Description

Ceramic micro-channel membrane reaction system for preparing nano calcium carbonate by utilizing calcium-containing solid waste Technical Field The invention relates to the technical field of nano material preparation and industrial waste resource utilization, in particular to a ceramic micro-channel membrane reaction system for preparing nano calcium carbonate by utilizing calcium-containing solid waste. Background The global warming problem is becoming more serious, carbon dioxide is taken as a main greenhouse gas, and emission reduction and resource utilization of the carbon dioxide become key problems for realizing sustainable development. In the carbon capturing, utilizing and sealing (CCUS) technology, CO 2 is converted into a stable carbonate product through a mineralization way, and the method has the dual benefits of carbon fixation and high value-added material production, and has wide prospects. Meanwhile, a large amount of carbide slag generated in industrial processes such as acetylene and the like has the main component of calcium hydroxide, the content of calcium resources is high, and the traditional disposal mode faces environmental protection and recycling pressure. Therefore, calcium-containing solid waste such as carbide slag is used as a calcium source to cooperatively capture CO 2 in industrial waste gas to prepare high-value nano calcium carbonate, a technical route of treating waste with waste and changing waste into valuable is formed, and the method has remarkable environmental and economic values. At present, the process for preparing nano calcium carbonate by utilizing calcium-containing solid waste is mainly divided into a direct carbonization method and an indirect carbonization method. The direct carbonization method has simple process, but has the problems of low calcium dissolution rate, serious impurity interference, wide product particle size distribution and the like. In order to improve the purity and controllability of the product, indirect carbonization methods are widely studied, for example, an ammonium salt (such as ammonium chloride) solution is adopted to leach calcium components in solid waste to form soluble calcium salts, and then CO 2 is introduced to carry out carbonization precipitation. Although the method improves the reaction selectivity, a complex reaction system of high-concentration ammonia nitrogen and chloride ions is introduced, so that equipment corrosion is serious, the reaction environment is harsh, the subsequent wastewater treatment difficulty is high, and continuous and efficient production is difficult to realize by multi-step intermittent operation. To enhance the reaction process, the prior art has attempted to introduce advanced reaction and separation units. In terms of the reactor, the micro-channel reactor (such as CN112619572B, CN 217042515U) can realize controllable preparation and continuous synthesis of nano particles by virtue of extremely high specific surface area and mass transfer efficiency, and part of design can integrate the surface modification function. However, the micro-channel structure is easy to be blocked due to solid particles or crystallized products, especially has poor stability in a high-solid-content or easily-scaling system, and although the prior anti-blocking structure design (such as CN 222369062U) is focused on mechanical filtration and blocking removal, the problems of corrosion and chemical scaling of the channel material by high-alkalinity and high-ionic strength medium can not be fundamentally solved, and the complexity of the system is increased. In terms of mass transfer and separation enhancement, ceramic membranes are used in separation processes of demanding systems due to their excellent chemical stability, thermal stability and mechanical strength. For example, porous ceramic membranes can be used for high temperature gas-solid filtration (CN 102010187B), and can be extended to membrane distillation applications by surface hydrophobic modification (CN 102423641B). However, in mineralization reaction environment where high pH and high ammonia and chlorine coexist, the traditional ceramic membrane still faces serious challenges that inorganic salts (such as calcium carbonate and silicate) are easy to deposit on the surface and in pore channels of the membrane to cause rapid attenuation of permeation flux, conventional physical flushing or chemical flushing has limited effect in a strongly corrosive medium and possibly damages the membrane structure, in addition, a single membrane separation unit is difficult to be efficiently coupled with a carbonization reaction process, gas (such as CO 2) is mostly introduced in a bubbling mode, the contact area of gas and liquid is small, the mass transfer efficiency is low, local oversaturation is easy to cause product agglomeration, and the nano vaterite calcium carbonate with uniform particle size and controllable crystal form is not favorable to be obtained