CN116272828A

CN116272828A - Spiral circulation reactor and method for preparing micro-nano material by using same

Info

Publication number: CN116272828A
Application number: CN202310297531.0A
Authority: CN
Inventors: 尹应武; 王策; 陈学云; 尹政清; 程东海; 杨少梅; 胡利贤; 张海双
Original assignee: Th Unis Insight Co ltd; Xiamen University
Current assignee: Th Unis Insight Co ltd; Xiamen University
Priority date: 2023-03-24
Filing date: 2023-03-24
Publication date: 2023-06-23

Abstract

The invention relates to a spiral circulation reaction device system and a method for preparing a micro-nano material, wherein the micro-nano material is selected from one or more of a composite nano material containing calcite type nano calcium carbonate/white carbon black, a composite nano material containing spindle type nano calcium carbonate/white carbon black, a composite nano material containing aragonite type nano calcium carbonate/white carbon black, a material containing three-dimensional bamboo fungus type hydrated nano calcium silicate, a material containing two-dimensional flaky nano calcium silicate and one-dimensional calcium-based material, the method uses the spiral circulation reaction device system, and the spiral circulation reaction device system comprises a reactor main body, a fluid circulation system, a temperature control system and a data analysis control system, wherein the fluid circulation system comprises a liquid circulation pump, a spiral circulation spray head and a gas supply system. The rotary loop reactor system has the advantages of simple structure, high efficiency, energy saving, small amplification effect and wide application range, can be used for producing series products with various shapes and particle sizes in a large scale, has wide reaction condition Fan Wenhe, and is simple to operate and easy to control.

Description

Spiral circulation reactor and method for preparing micro-nano material by using same

Technical Field

The invention relates to a spin loop reactor and a method for preparing micro-nano materials by using the same.

Background

Micro-nano material refers to a material with a size between the micrometer level and the nanometer level, and is a generic term of micrometer material and nanometer material. The volume effect and the surface effect of the powder have obvious performance difference from common powder. They have very high surface area and specific volume, can provide larger contact area, are beneficial to interaction with other materials, improve the strength and toughness of the composite material, and the like. In recent years, the micro-nano material has great application potential in the aspect of improving the performance of composite materials, and is widely applied to the fields of rubber, papermaking, adhesives, plastics and the like.

Calcium carbonate is one of the most widely used inorganic chemical products with the lowest manufacturing cost, the greatest productivity and consumption, and the multifunction and biocompatibility, and therefore, is widely focused. The morphology, particle size, surface modifier and the like of the nano calcium carbonate can obviously influence the use effect of the micro-nano material. The traditional calcium carbonate synthesis reaction equipment mainly comprises three types of stirring kettles, a bubbling tower and a hypergravity reactor, and basically obtains the single-crystal micro-nano material with smaller size by forcedly mixing, reducing the concentration of reactants, rapidly reacting, inhibiting the growth of crystals and improving the nucleation rate in the crystallization process. The existing bubbling tower and stirring kettle have the defects of obvious amplification effect, poor gas-liquid mass transfer performance, uneven bubble distribution, incapability of effectively dispersing secondary nucleation caused by particle collision, product agglomeration, widened particle size distribution and the like; the existing nano material synthesis process mainly controls the particle size, and has the series of problems of single crystal form, large particle size distribution range, poor use effect, high production cost and the like.

The common stirring kettle drives a heavy stirring paddle by means of a motor and a transmission device at the top of the kettle body, and the vertical arrangement also needs to adjust the stirring rotation speed by a speed reducer, so that the vertical stirring kettle has a series of defects of huge volume, high manufacturing cost, high energy consumption, obvious amplification effect, high occupied space, poor mixing effect and the like.

The subject group previously invented high-efficiency energy-saving mixing equipment for directly carrying out radial cyclone mixing of 'material stirring materials' by using a rotary jet nozzle to replace the traditional mechanical stirring (CN 104128106A). The rotary gas distribution spray head is further innovated, gas dispersion is further enhanced through jet flow/rotational flow in the original rotational flow system, axial mixing (CN 108404700A) is enhanced by means of gas lift force, a gas-liquid contact mode (CN 111302508A) is optimized, blown raw gas is distributed in a large range along the radial direction under the help of liquid jet flow, lift force formed by bubbles can generate axial circulation, the gas-liquid contact time is greatly prolonged, the whole mixing area is in a turbulent state, secondary nucleation can be reduced, particle size is reduced, and the distribution is narrowed. It is particularly worth mentioning that the novel spiral circulation device cancels the inner guide cylinder influencing the radial mass transfer of the airlift reactor, avoids forming a dead zone, has better mixing effect, can directly contact and mix an upper liquid zone and a liquid-falling zone, can automatically adjust the proportion, and can adapt to more application scenes, but the prior work does not carry out specific process research of targeted micro-nano products. The synthesis process of the series of micro-nano new materials with different raw materials and different morphologies developed in the existing small-scale reactor and kettle-type reactor is transplanted and amplified in the novel reactor, the industrial technology suitable for large-scale and low-cost production of the micro-nano materials is developed, and the characteristics and the application effect of the product are evaluated, so that the method has economic, social and environmental benefits.

Disclosure of Invention

The invention is based on the development foundation of novel equipment and novel products in the earlier stage, and in order to overcome the defects of the quality and the production process of the micro-nano materials synthesized by the existing kettle-type and airlift reactors, the process method for synthesizing series micro-nano crystal materials and controlling the crystal form by using the spiral circulation reactor is invented through repeated experiments and optimization based on the requirements of large scale, low cost, industrialization and good product application effect.

Specifically, the invention provides a method for synthesizing micro-nano materials with different shapes and particle sizes by controlling the process in a novel rotary loop reactor, and develops a novel process capable of synthesizing calcium-based micro-nano crystal materials with various shapes and particle sizes. Specifically, the invention establishes the corresponding relation with the key parameters of the optimized process conditions of the common stirring kettle based on the research of the influence rule of the process conditions such as the concentration of the reaction materials, the gas-liquid phase flow rate, the reaction temperature, the rotational flow speed, the reaction time and the like in the rotary loop reactor on the crystal form and the grain size of the micro-nano material, and develops the calcium-based micro-nano material with different shapes such as serial particles, spindle shapes, cubes, whiskers, flakes, bamboo fungus shapes and the like and the industrialized production process under the optimized process conditions in the novel rotary loop reactor.

Specifically, the invention provides a method for preparing a micro-nano material, wherein the micro-nano material is selected from one or more of a composite nano material containing calcite type nano calcium carbonate/white carbon black, a composite nano material containing spindle type nano calcium carbonate/white carbon black, a composite nano material containing aragonite type nano calcium carbonate/white carbon black, a material containing three-dimensional bamboo fungus-shaped hydrated nano calcium silicate, a material containing two-dimensional flaky nano calcium silicate and a one-dimensional calcium-based material, and the method is characterized in that:

the method uses a rotary loop reactor system, the rotary loop reactor system comprises a reactor main body, a fluid circulation system, a temperature control system and a data analysis control system, wherein the fluid circulation system comprises a liquid circulation pump, a rotary loop spray head and a gas supply system,

the method comprises the following steps:

and (3) opening gas flow valves in a temperature control system and a gas supply system, adding water, opening a liquid circulation pump, adding cement or cement clinker or lime or carbide slag or calcium hydroxide solution, mixing to form a suspension system, introducing one or more of carbon dioxide raw gas, flue gas or air or adding soluble carbonate or sulfuric acid or sulfate through a rotary circulation nozzle, optionally adding a modifier to perform in-situ modification, stopping the reaction within a pH value range of 6-8, and preparing the nano calcium carbonate or nano calcium silicate or calcium sulfate micro-nano material containing different morphologies through silica gel formation, neutralization precipitation, double decomposition and dehydration condensation reaction.

Preferably, the spin loop reactor system employs an electromagnetic liquid flow meter;

preferably, the rotary loop reactor system comprises a main reactor, a double-channel liquid jet and gas distribution loop nozzle, a carbon dioxide raw material gas or flue gas or compressed air supply and gas circulation system, a gas flow valve and gas flow meter monitoring system, a liquid phase hybrid power system formed by a liquid circulation pump, a liquid flow meter and liquid flow valve control system, a circulating heating cooler temperature control system, a data recording and control system and a monitoring platform formed by a sensor.

Preferably, the fluid circulation system is powered by a liquid circulation pump, the reaction liquid is sent into the rotary circulation nozzle from the reactor, the gas supply system provides reaction gas by a gas holder or an air compressor, and the reaction gas is sent into the rotary circulation nozzle and collides with the liquid at an outlet; the electromagnetic liquid flowmeter and the gas flowmeter monitor the process, control the liquid valve and the gas valve to adjust the flow, and upload the data to the computer; the temperature control system maintains the temperature in the reactor stable.

Preferably, the rotary circulation spray head comprises a stator, a rotor, a sliding plastic bearing, a liquid guide pipe, a gas guide pipe and a gas annular outlet; the rotor is internally provided with a fluid cavity and a liquid nozzle, the liquid nozzle is used for pushing the rotor to rotate relative to the stator by a part of pressurized liquid from the fluid cavity, and the other part of fluid in the fluid cavity is sprayed out through other nozzles to form jet flow; the gas annular outlet is used for jetting gas from the gas flow guide pipe, and radial bubble distribution and axial circulation disturbance are formed by combining jet flow;

Preferably, the liquid circulation pump is selected from a centrifugal pump, a screw pump or a hose pump. For fluid systems with higher particle content and higher viscosity, it is more preferable to use a hose pump or screw pump.

Preferably, the temperature is controlled between 20 and 110 ℃;

preferably, the cement is Portland cement and the cement clinker is Portland cement clinker;

preferably, the modifier is selected from polymeric modifiers, preferably styrene-acrylic emulsion, sodium lignin or sodium stearate.

The production control conditions of the spin loop reactor system were determined using the following method:

(1) For the liquid-liquid mixing reaction process, the feeding amount is not more than two thirds of the volume, the circulating flow rate of the liquid in the tank per hour is selected according to 0.5-150 times of the volume of the material in the reactor, or the circulating flow rate of the liquid phase is determined according to 0.4-0.6 of the ratio of the jet distance of the liquid phase to the diameter of the reactor;

(2) For the gas-liquid mixing process, the gas distribution distance and the gas-liquid mass transfer coefficient are examined, the volume flow of the introduced gas is determined to be 1-5 times of the volume flow of the circulating liquid according to the jet distance formed by the pressure and the flow, and the power P is input through the liquid according to the mathematical model formula of the liquid volume mass transfer coefficient of the rotary circulation mixing device _L Unit gas input power P _G And the ratio of jet penetration distance to reactor diameter

Measuring and calculating;

preferably, the invention provides the following specific methods:

(1) The method for producing the in-situ modified calcite type nano calcium carbonate/white carbon black composite nano material comprises the following steps: the reaction temperature is 20-60 ℃, the concentration of calcium hydroxide is 0.5-1.5mol/L, one or more of styrene-acrylic emulsion, sodium lignin or sodium stearate is added as a modifier, the volume flow of introduced carbon dioxide or flue gas is 1-5 times of the flow of circulating liquid, the volume flow of liquid circulation is 50-100 times of the volume amount of reactor materials per hour, and the pH value of the reaction end point is 6-8; preferably, the reaction temperature is from 30 to 60 ℃, more preferably from 40 to 60 ℃; preferably, the volume flow rate of the carbon dioxide or flue gas introduced is 1 to 4 times, more preferably 2 to 4 times, the flow rate of the circulating liquid; preferably, the liquid circulation volume flow is 60 to 100 times/hour, more preferably 80 to 100 times the volume of the reactor material.

Or alternatively

(2) The method for producing spindle-shaped nano calcium carbonate/white carbon black composite nano material comprises the following steps:

the reaction temperature is 50-80 ℃, the calcium hydroxide concentration is 0.5-1.5mol/L, the flow rate of the circulating liquid is 50-120 times/hour of the volume of materials in the reactor, and the volume flow rate of the introduced carbon dioxide or flue gas is 1-5 times of the volume flow rate of the circulating liquid; the pH value of the reaction end point is 6-8; preferably, the reaction temperature is 60-80 ℃, more preferably 60-70 ℃; preferably, the volumetric flow rate of the carbon dioxide or flue gas introduced is 1 to 4 times, more preferably 1 to 3 times, the volumetric flow rate of the circulating liquid.

Or alternatively

(3) The method for producing aragonite type nano calcium carbonate/white carbon black composite nano material from cement clinker comprises the following steps:

the solid-liquid ratio of cement clinker and water is 1:2-1:5, and the flow rate of liquid circulation body is 30-100 times/hour of the volume of materials in the reactor; the volume flow of the introduced carbon dioxide or flue gas is 1-5 times of the volume flow of the circulating liquid, and the reaction time is 1-5 hours; preferably, the volumetric flow rate of the carbon dioxide or flue gas introduced is 1 to 4 times the volumetric flow rate of the circulating liquid; more preferably 1 to 3 times; preferably, the reaction time is 1.5 to 5 hours; more preferably 2-4 hours;

or alternatively

(4) The method for producing the flaky nano calcium silicate from the cement clinker comprises the following steps:

the solid-liquid ratio of cement clinker to water is 1:1-1:5, and the flow rate of liquid circulation body is 10-25 times of the volume of materials in the reactor per hour. The volume flow of the introduced air is 1-5 times of the volume flow of the circulating liquid, and the reaction time is 8-15 hours;

preferably, the liquid circulation volume flow is 12-25 times/hr of the volume of the material in the reactor; more preferably 15-20 times; preferably, the reaction time is 8-12 hours; more preferably 10-12 hours;

or alternatively

(5) The method for producing three-dimensional netlike nano calcium silicate by cement clinker has the solid-to-liquid ratio of 1:1-1:5, and the volume flow of liquid circulation is 25-90 times/hour of the volume amount of reactor materials; the volume flow of the introduced air is 1-5 times of the volume flow of the circulating liquid, and the reaction time is 8-12 hours;

Preferably, the liquid circulation volume flow is 30-80 times/hr of the volume of the reactor material; more preferably 40-70 hours;

preferably, the volume flow of the aeration air is 1-4 times, more preferably 1-3 times, preferably 2-3 times the volume flow of the circulating liquid; preferably, the reaction time is 8 to 10 hours.

The invention also provides a spiral circulation reaction device system for preparing the micro-nano material, which comprises a reactor main body, a fluid circulation system, a temperature control system and a data analysis control system, wherein the fluid circulation system comprises a liquid circulation pump, a spiral circulation spray head and an air supply system.

Preferably, the spin loop reactor system employs an electromagnetic liquid flow meter.

The novel rotary loop reactor system is shown in figure 1, and comprises a reaction container as a main reactor, a carbon dioxide raw gas or purified flue gas or compressed air or steam and other gas supply and gas circulation systems, a gas flow valve, a gas flow meter and other monitoring systems, a liquid phase hybrid power system formed by a liquid circulation pump, a liquid flow meter and liquid flow valve control system, a double-channel liquid injection and gas distribution rotary nozzle, a circulating heating cooler temperature control system, a data recording and control system, and various sensors and other monitoring platforms. The optimal control conditions of the spiral circulation reactor can be determined according to the capacity requirement, the size of the reactor and the following principles:

on the basis that optimization conditions such as reaction solvent, reaction temperature, solid-liquid ratio and the like determined by a small scale and a kettle-type reactor are not greatly adjusted, the mixing stirring rotating speed and gas flow rate are converted into the amplification production conditions such as solid and liquid material adding speed, liquid circulation flow rate and gas introducing amount of a unit reaction volume reactor in a rotary circulation reactor, and gas-liquid circulation flow rate and the like, and micro-nano products with different shapes and particle size distribution can be obtained by using different raw materials and controlling different conditions:

(1) For the liquid-liquid mixing reaction process, feeding according to the mixing time similar to that of a stirring mixing kettle, wherein the feeding amount is not more than two thirds of the volume, the circulating flow rate of liquid in a tank per hour is selected according to 0.5-150 times of the feeding amount of a reactor, and the liquid phase flow rate can be determined according to 0.4-0.6 of the ratio of the jet distance of the liquid phase to the diameter of the reactor;

earlier experiments found that the spiral circulation reactor was a mixing process of liquid rotational flow and gas circulation interaction, and gas dispersion diameter was an important evaluation index. When the gas dispersion diameter is 0.4-0.6 times of the diameter of the reactor, the mixing effect of the spiral circulation reactor is optimal, and the ratio of the liquid lifting area to the liquid dropping area is proper. The gas dispersion diameter is mainly affected by the liquid penetration distance and the gas flow rate together: the liquid penetration distance plays a decisive role, the liquid flow or pressure is increased, the jet penetration distance is increased, the gas dispersion diameter is increased, the gas flow assists in dispersion, when the gas flow is increased, the circulation degree of the mixed system is increased, the density of the liquid dropping area is increased, and the gas distribution diameter is reduced.

(2) For the gas-liquid mixing process, the gas distribution range and the gas-liquid mass transfer coefficient are required to be inspected, the gas flow is determined according to the jet distance formed by the fluid pressure and the flow, and the volume flow of the introduced gas is 1-5 times of the volume flow of the circulating liquid.

The synthesis method comprises the following steps: and (3) opening gas flow valves in a temperature control system and a gas supply system, adding water, opening a liquid circulation pump, adding cement or cement clinker or lime or carbide slag or calcium hydroxide solution, mixing to form a suspension system, introducing one or more of carbon dioxide raw gas, flue gas or air or adding soluble carbonate or sulfuric acid or sulfate through a rotary circulation nozzle, optionally adding a modifier to perform in-situ modification, stopping the reaction within a pH value range of 6-8, and preparing the nano calcium carbonate or nano calcium silicate or calcium sulfate micro-nano material containing different morphologies through silica gel, neutralization precipitation, double decomposition and dehydration condensation reaction.

The cubic nano calcium carbonate is synthesized by using the reaction vessel with the same volume, the average grain diameter of the product synthesized by the rotary circulation reactor is reduced by 27.72 percent compared with that of the product synthesized by the stirred tank reactor, the utilization rate of carbon dioxide is improved by 53.38 percent, and the performance indexes of the product reach the index requirements of the nano calcium carbonate in rubber, plastic and papermaking. By adjusting the temperature, the gas-liquid flow rate and the like, products with various shapes can be obtained. In the research of hydrated calcium silicate, various micro-nano materials can be synthesized and customized by controlling the gas-liquid flow rate and the slow growth of crystals. The patent achievements overcome the problems of single type, large particles, large particle size distribution range, high production cost and the like of the nano material products in the traditional reactor and the synthesis process.

The invention uses a novel rotary circulation reactor without an inner guide cylinder as an amplifying synthesis device, and creates in-situ synthesis of calcite type nano calcium carbonate, spindle type nano calcium carbonate, aragonite type nano calcium carbonate and white carbon black composite materials, three-dimensional bamboo fungus shape (netlike hydrated calcium silicate), two-dimensional flaky nano calcium silicate and other micro-nano calcium base materials with different shapes and particle sizes and new modified products thereof according to the corresponding relation with key parameters of a common stirring kettle, and the novel process is specifically characterized in that: the method utilizes feed gas or circulating working medium gas to form upward lift force enhanced axial mixing, forms jet flow/rotational flow enhanced radial mixing through a jet liquid column and a rotary nozzle, creates a high-efficiency rotary circulation mixing system suitable for a multiphase system, and can synthesize the calcium-based micro-nano crystal material with fixed morphology, narrow particle size distribution and excellent application performance on a large scale with low cost by adjusting and controlling key parameters such as the water-solid ratio, the circulating mixing liquid amount, the ventilation amount, the reaction temperature, the time and the like of different raw materials such as lime, carbide slag, tricalcium silicate, cement clinker, silicate cement and the like and by assisting with a modifier or a crystal form control agent if necessary.

The invention combines the novel spiral circulation reactor and the application requirement of micro-nano materials to develop the combination of the process and the equipment, and has the following advantages compared with the traditional nano material synthesis equipment and the process method:

1. The device has simple structure, high efficiency, energy saving, small amplifying effect and wide application range.

The novel rotary loop reactor has no guide cylinder, avoids dead zone, and the whole reaction zone is in turbulent flow state of several strong mixing forms of jet flow, rotational flow, up-flow and the like, thereby being beneficial to fully mixing and dispersing gas, raw materials and products and effectively reducing coalescence. According to different requirements of micro-nano material composition, morphology and particle size, the main parameters of raw materials, solid-liquid ratio, gas-liquid flow, reaction temperature time and the like are controlled in a large range, the products which are suitable for various morphologies and particle sizes can be produced in a large scale, the reaction condition is wide Fan Wenhe, the operation is simple and easy to control, and the particles are uniform.

2. Compared with the traditional stirring reaction kettle with the same size, the novel rotary loop reactor has the advantages that the gas-liquid mass transfer efficiency can be improved by more than 25%, the secondary nucleation can be effectively inhibited, the average particle size of nano calcium carbonate is reduced by 27.2% under the same volume and close process conditions, the carbon dioxide utilization rate is improved by 53.38%, and the product performance is better.

3. The novel spiral circulation reactor can synthesize spindle-shaped nano calcium carbonate, in-situ modified calcite-type nano calcium carbonate, aragonite-type nano calcium carbonate whisker and white carbon black composite material, bamboo fungus-shaped three-dimensional nano calcium silicate, two-dimensional flaky nano calcium silicate, zero-dimensional calcium-based products and other serial micro-nano products with rich morphologies under the optimized process conditions.

4. The optimal control conditions of the rotary loop reactor can be determined according to the size and the treatment capacity of the reactor and the optimal process conditions searched in the reaction kettle, on the basis that the optimal conditions such as the reaction solvent, the reaction temperature, the solid-liquid ratio and the like determined by the kettle reactor are not greatly adjusted, the stirring rotation speed and the gas flow rate which are involved in mixing are converted into the amplified production conditions such as the solid and liquid material adding speed, the liquid circulation flow rate and the gas introducing amount of the unit reaction volume reactor in the rotary loop reactor, and the gas-liquid circulation flow rate are controlled according to the following principle, so that the series of products can be obtained: for the liquid-liquid mixing reaction process, the materials are added according to the mixing time similar to that of a stirring and mixing kettle, the circulating flow rate of the liquid in the tank per hour is selected according to 0.5-150 times of the volume of the reactor, and the liquid phase flow rate can be determined according to the ratio of the liquid phase jet flow distance to the diameter of the reactor, which is 0.4-0.6.

For the gas-liquid mixing process, the gas distribution distance and the gas-liquid mass transfer coefficient are required to be inspected, and the flow rate of the introduced gas is determined to be 1-5 times of the flow rate of the circulating liquid according to the jet flow distance formed by the pressure and the flow rate. For liquid-liquid mixing processes, the gaseous working medium may exert an intensified axial mixing action. The earlier results show that the rotary loop reactor has the best mixing effect when the gas-liquid ratio is 3:2, and can be selected according to the principle; the liquid phase flow can be determined according to the ratio of the liquid jet distance to the diameter of the reactor, and finally the aperture resistance of the jet nozzle is calculated.

When the input power is constant, the nozzle size and the nature of the fluid itself will also affect the gas-liquid mass transfer effect at the spray head. The two factors can be combined through the following formula, and the penetration distance of the jet can be calculated as follows:

W _j distance d for jet penetration _j Re is the Reynolds number based on the current nozzle diameter, fr is the Froude number, g is the gravitational acceleration.

For the gas-liquid mixing process, the gas distribution distance and the gas-liquid mass transfer coefficient are required to be inspected, and the gas-liquid flow is calculated by adopting the following method according to experimental requirements: firstly, calculating the aperture of a proper jet nozzle and the flow rate of liquid according to the ratio of the penetration distance of liquid phase jet to the diameter of a container, and secondly, selecting the flow rate of gas phase according to the proper gas-liquid ratio range and combining production conditions. Thirdly, accounting the gas-liquid mass transfer coefficient according to the gas-liquid mass transfer coefficient model of the rotary loop reactor.

According to the invention, a mathematical model of the liquid volume mass transfer coefficient of the rotary circulation mixing device is established according to the mixing principle. The formula includes the liquid input power P _L Unit gas input power P _G And the ratio of jet penetration distance to reactor diameter

For example: the fitting result of the model parameters in the partial small-medium volume reactor is determined to be m=595.6, n=6.57, p=1.412 and q= -0.267 through experimental data regression analysis. Calculated liquid volume mass transfer coefficient (K _L a) Comparing with the experimental values as shown in fig. 20, it can be seen that there is good agreement between the calculated values and the experimental values, and the relative error is less than 10%.

5. Because the earlier stage research result (CN 104128106A, CN108404700A, CN 111302508A) of the research team relates to the field of fermentation engineering and wastewater treatment, the gas-liquid mass transfer effect and the mixing effect required by the production of the micro-nano material cannot be met, and because the gas-liquid mass transfer effect and the mixing effect contain higher solid content during the production of the micro-nano material, pipelines can be blocked, and new requirements are put forward for the power of the original equipment, the type of a circulating pump and the material of a sensor. In addition, the previous research results do not need to control the temperature, but the production of the micro-nano material needs to control the temperature in a certain temperature range and maintain the temperature stable. The research team carries out corresponding upgrading and transformation on the device, for example, electromagnetic liquid flowmeter, hose pump, temperature control system and other improvement means are adopted, so that the device is suitable for preparing micro-nano materials with different morphologies.

Drawings

FIG. 1 one embodiment of a spiral-flow reactor for use in the present invention

FIG. 2 is a schematic diagram of a rotary circulation gas distribution jet nozzle structure

FIG. 3 is a graph of mixing time and liquid flow rate for a 20L spiral loop reactor

FIG. 4 is a graph of mixing time and gas flow rate for a 20L spiral loop reactor

FIG. 5 is a graph of 20L stirred tank reactor mixing time versus rotational speed

FIG. 6 is a graph of carbon dioxide mass transfer efficiency and liquid flow rate for a 20L spiral loop reactor

FIG. 7 is a graph of 20L stirred tank carbon dioxide mass transfer efficiency versus rotational speed

FIG. 8 is a diagram of cubic nano calcium carbonate electron microscope synthesized by 20L rotary loop reactor

FIG. 9 is a cubic nano-calcium carbonate electron microscope image synthesized by 20L stirred tank reactor

FIG. 10 is a small scale in situ modified nano calcium carbonate electron microscope image

FIG. 11 XRD patterns of various nano calcium carbonate synthesized by 20L spiral circulation reactor

FIG. 12 is a 20L spiral loop reactor synthesized spindle-shaped nano calcium carbonate electron microscope image

FIG. 13 is a 20L stirred tank synthesized spindle-type nano calcium carbonate electron microscope image

FIG. 14 is an electron microscope image of needle-like nano calcium carbonate synthesized by 20L rotary loop reactor

FIG. 15 is an electron microscope image of needle-like nano calcium carbonate synthesized by 20L stirred tank reactor

FIG. 16 20L of raw cement clinker electron microscope

FIG. 17A-C20L spiral loop reactor synthesized platy calcium silicate electron microscopy image

FIG. 18 20L spiral circulation reactor synthesized toboggan-like calcium silicate hydrate

FIG. 19 three-dimensional network calcium silicate hydrate synthesized by spin loop reactor

FIG. 20 relative error of predicted and experimental values of liquid volume mass transfer coefficients

Detailed Description

The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it should be noted that the following embodiments are only a part of the present invention. Based on the embodiments of the present invention, those of ordinary skill in the art will recognize that product development techniques without undue burden are within the scope of the present invention.

In the description of the present invention, it should be noted that the directions or positional relationships indicated by the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc. are based on the directions or positional relationships shown in the drawings, are merely for convenience of describing the present invention and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.

EXAMPLE 1 the spin loop reactor system used in the present invention

Figure 1 provides a specific embodiment of the rotary loop reactor system of the present invention comprising a fluid circulation system, a reactor body, a temperature control system, a gas supply system, a data analysis control system. The fluid circulation system is mainly powered by a liquid circulation pump (1), reaction liquid is sent into a rotary circulation nozzle (4) from the inside of a reactor (5), reaction gas is provided by a gas holder (09) or an air compressor (11) by a gas supply system, and is sent into the rotary circulation nozzle to be collided with the liquid at an outlet. The electromagnetic liquid flowmeter (2) and the gas flowmeter (9) monitor the process, control the liquid valve (3) and the gas valve (7) to adjust the flow, and upload the data to the computer (13). The temperature control system (8) maintains the temperature in the reactor stable.

As shown in fig. 2, the rotary sprayer 9 includes a stator 11, a rotor 17, a sliding plastic bearing 12, a liquid guide pipe 13, a gas guide pipe 14, and a gas annular outlet 15; the rotor 17 is internally provided with a fluid chamber and a liquid nozzle 16, the liquid nozzle is used for pushing the rotor to rotate relative to the stator by a part of liquid with pressure from the fluid chamber, and the other part of fluid in the fluid chamber is ejected through other nozzles to form jet flow. The gas annular outlet is used for jetting gas from the gas flow guide pipe, and radial bubble distribution and axial circulation disturbance are formed by combining jet flow.

Example 2 comparative study of Process conditions and Power consumption for stirred tank and novel spiral Loop reactor to give the same mixing time

Using the apparatus shown in FIG. 1, 20L of clear water was added to a vessel having a diameter of 380mm and a height of 700 mm. The mixing time of the reactor was measured, and at normal temperature, a 3-sector nozzle (straight-through jet nozzle) 2-wide-angle nozzle (dynamic sputtering nozzle) and a rotary nozzle using a polymer material slide bearing were used, with an aspect ratio of 1.5:1.

Adding potassium chloride into the tank as an indicator, detecting the change condition of the conductivity in the reactor by using a conductivity meter, and measuring the mixing time of the reactor. Measurement of the air flow at 4m ³ At/h, the result of the measurement of the flow rate of the liquid was changed as shown in FIG. 3, which shows that the mixing effect increased with the increase of the flow rate of the liquid, but the flow rate of the liquid phase was more than 3m ³ After/h, the increase in energy consumption and the reduction in mixing time are limited.

Based on the above results, the flow rate of the liquid was further measured to be 3m ³ At/h, the measurement results of the change gas flow rate are shown in FIG. 4, and the results show that the increase of the gas flow rate is accompanied by the increase of the gas flow rate, but the excessive gas flow rate can lead to the decrease of the liquid content near the spray head and the decrease of the mass transfer effect. The results of the comparison with the stirred tank are shown in Table 1.

TABLE 1 comparison of the rotational speed or liquid flow rate required for the same mixing time

In the same reaction vessel, the rotation speed was adjusted to 50-350rpm using an anchor stirrer, and the test results of the mixing time test were repeated as shown in FIG. 4. Compared with a stirring kettle, the low-speed stirring is more energy-saving under the condition of low mixing requirement; however, when strong mixing is required, the mixing effect of a 0.75kw circulation pump pushing a rotary circulation device and the like is better, and the mixing time of the circulating liquid flow is greatly reduced. The liquid circulation was carried out at a rate of 3.5 cubic/hour for 5 minutes in a mixing reactor having a 20L charge, and the total of the liquid circulation amounts was 292 liters, which was 14.6 times the charge to the reactor, i.e., an effect of 350rpm of a stirring mixer having a power of 1.8kW was achieved.

Example 3 carbon dioxide absorption Rate comparison study of stirred tank and spiral circulation reactor for Synthesis of nano calcium carbonate

Using the apparatus shown in FIG. 1, a container having a diameter of 380mm and a height of 700mm was charged with 20L of a calcium hydroxide solution at a concentration of 0.1mol/L. The reactor height-diameter ratio is 1.5:1 by adopting a 3-sector nozzle (straight jet nozzle) and a 2-wide-angle nozzle (dynamic sputtering nozzle) and a rotary nozzle head using a high polymer material sliding bearing. And introducing carbon dioxide, and measuring the reaction time and the carbon dioxide utilization rate of the reaction system reaching balance in the gas-liquid mixing process. Under normal temperature, the fixed gas flow is 5L/min, the different liquid flows are changed, and as shown in FIG. 6, the measurement results show that the time required for the system to reach equilibrium is shortened as the liquid flow is increased, the gas-liquid mass transfer coefficient is improved, and the carbon dioxide utilization rate is improved.

In the same reaction vessel, the results of the control experiment are shown in FIG. 7, using an anchor stirrer, at a rotational speed in the range of 50-350 rpm. Compared with a stirred tank, the utilization rate of the carbon dioxide of the rotary loop reactor is obviously improved. The experimental results are shown in table 2.

TABLE 2 comparison Table of carbon dioxide single absorption and utilization results of rotary loop reactor and stirred tank

Example 4

The device shown in figure 1 is subjected to an amplification experiment to obtain effective volumes of 1500L and 20m ³ In the reactor, potassium chloride is used as a tracer, a mixing time measurement experiment is carried out, and the mixing effect and the circulation flow multiple of the spiral circulation reactor in a large system are analyzed.

With the device shown in the abstract figure, 20L of clean water is added into a container with the diameter of 380mm and the height of 700mm, and a 3-fan nozzle (straight jet nozzle) 2-wide-angle nozzle (dynamic sputtering nozzle) and a rotary nozzle using a macromolecular material sliding bearing are adoptedThe height-diameter ratio of the reactor is 1.5:1, and the fixed gas flow is 4m ³ And/h, measuring the mixing time of the rotary loop reactor under different liquid flow conditions.

With the device shown in fig. 1, 1500L of clean water is added into a container with the diameter of 1300mm and the height of 1500mm, a 3-fan nozzle (straight jet nozzle) 2-wide-angle nozzle (dynamic sputtering nozzle) and a rotary nozzle using a polymer material sliding bearing are adopted, the height-diameter ratio of the reactor is 1.25:1, and the fixed gas flow is 5m ³ And/h, measuring the mixing time of the rotary loop reactor under different liquid flow conditions.

The device shown in the abstract figure is used for adding 20m into a container with the diameter of 2.4m and the height of 7.5m ³ The clear water adopts a 3-fan nozzle (a straight jet nozzle) and a 2-wide-angle nozzle (a power sputtering nozzle) and a rotary nozzle using a high polymer material sliding bearing, and the height-diameter ratio of the reactor is 1.75:1. The fixed liquid flow is 18m ³ And/h, measuring the mixing time of the rotary loop reactor under different gas flow conditions.

The above volumes of reactors were compared with those of example 2 to obtain the ratio of the actual power per unit volume to the liquid circulation per hour to the charge required for the different volumes of reactors, under the same mixing time conditions. The equipment A is a rotary circulation reactor with the effective volume of 20L, the equipment B is a rotary circulation reactor with the effective volume of 1500L, and the equipment C is a rotary circulation reactor with the effective volume of 20m ³ Is a spiral loop reactor.

The circulation times are the ratio of the volumetric flow rate of fluid per hour to the volume of liquid in the reactor. In the large-system reactor, the energy consumption and equipment investment for regulating the liquid flow are large, so that the liquid flow of the equipment C is fixed, and the Roots blower is adopted for control and regulation.

Table 3 mixing effect and power per unit volume of different volume spiral loop reactors are compared.

As can be seen from Table 3, the comparison of the A device (20L) with the B device (1.5 m ³ ) If the fluid containing particles is not considered, the solid is highThe problems of content and the like are solved, the same mixing effect is achieved by taking a clean water pump as a power source, the large-volume rotary loop reactor has more energy-saving effect, and the reaction efficiency is higher and the secondary nucleation effect is weaker under the condition of larger unit volume power of equipment A (20L). By means of a comparative B device (1.5 m ³ ) And C device (20 m) ³ ) The power per unit volume of the spiral circulation reactor is amplified by 13 times, and the same power per unit volume is adopted, so that the same mixing effect is achieved, and the small amplification effect of the spiral circulation reactor is proved, and the application prospect is good.

The following rules apply to the relevant circulation times and operating conditions of the spiral-loop reactor obtained by example 4:

1. clear water, small amount of particles or other systems with low viscosity, and effective volume of less than 20m ³ Can be produced in an amplified manner by following the principle of maintaining the mixing power per unit fluid volume while ensuring the liquid penetration distance.

2. The reactor with higher solid content should select the pump equipment with corresponding power according to the specific gravity of the reaction liquid, and then the pump equipment is subjected to the amplification production according to the principle of keeping the mixed power of unit fluid volume and the amplification principle.

Example 5 laboratory synthesis of nano calcium carbonate compared to the effect of amplification in a spiral loop reactor

Experiment conditions of the in-situ modified nano calcium carbonate: under a certain temperature condition, adding the calcium hydroxide slurry with the mass fraction of 7% and the 1% styrene-acrylic emulsion modifier into a 500 ml reaction stirring kettle, uniformly mixing, introducing carbon dioxide to react until the pH value is=7 at the stirring rotation speed of 200rpm, filtering, washing, drying and carrying out product electron microscope characterization.

The mixture is amplified to a container with the diameter of 380mm and the effective height of 700mm and the bottom of which is conical, and 20L of clean water is added. A 3-sector nozzle (straight jet nozzle) 2-wide-angle nozzle (dynamic sputtering nozzle) and a rotary nozzle using a high polymer material sliding bearing are adopted. The device is applied to amplify and synthesize the small test. First, the optimal operation parameters of the rotary loop reactor are determined:

according to the amplification rule of the stirring reactor and the principle that the stirring power per unit fluid volume is unchanged, the rotating speed and the size of the stirring paddle are required to meet the following relation:

wherein n is the rotation speed of the stirring paddle, and d is the diameter of the stirring paddle. The rotation speed required to amplify a 70mm diameter paddle to a 350mm paddle was calculated. And determining that the liquid circulation quantity per hour corresponding to the stirring rotating speed is a multiple of the charging quantity when the same volume reactor achieves the same mixing effect according to the principle of consistent mixing time, wherein the calculation result is shown in table 4.

TABLE 4 Process conversion Table (20L) amplifying parameters in units of fluid agitation power and mixing time

From the above table, the conversion result was 137.5 times the charge amount, and the liquid circulation amount required for the amplification experiment was calculated to be 2.75m ³ And/h, the flow rate of the primary gas is 1.5 times of the volume flow rate of the liquid, namely 4.125m ³ And (h) in order to explore the influence of various factors on the morphology and the size of the nano calcium carbonate, based on the conditions, establishing an orthogonal experiment, and researching the influence of temperature, gas flow and liquid flow on the crystal size, morphology and carbon dioxide utilization rate of the nano calcium carbonate product by the solid-liquid ratio of raw materials. The experimental conditions and results are shown in table 5.

TABLE 5 orthogonal test conditions and results Table

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TABLE 6 analysis of variance table (examine the influence of factors on grain size)

The significance analysis of the effect of each factor on the grain size of the results can obtain the four factors, wherein the specific gravity order of the effect on the grain size in the rotary loop reactor is as follows: gas flow > reaction temperature > liquid flow > feedstock concentration. In trend, the higher the temperature, the larger the grain size, and the increase in gas phase flow rate is advantageous for reducing the crystal size, while the excessively small or large liquid phase flow rate is disadvantageous for reducing the crystal size.

Example 6 comparison of control effects of the crystalline form of cubic nano calcium carbonate

Weighing a certain amount of calcium hydroxide, adding water to prepare slurry with mass fraction of 7% -10%, placing into a rotary circulation reactor, and controlling gas phase flow (carbon dioxide) to 3-6m at normal temperature ³ /h, liquid flow rate 2-4m ³ And (3) adding the styrene-acrylic emulsion as a modifier, and reacting until the pH value is 7-8 to obtain the reaction end point. And carrying out suction filtration and washing on the obtained precipitate to obtain a modified calcite type nano calcium carbonate paste product, and drying to obtain a powder product. The XRD curve is shown as line B in FIG. 11, and the electron microscopy image is shown in FIG. 8.

Reconfiguring slurry 20L with mass fraction of 7% -10%, placing into stirring reactor, rotating at 200rpm under normal temperature, and gas phase flow (carbon dioxide) of 3-6m ³ And (h) repeating the experiment, carrying out suction filtration and washing on the obtained precipitate to obtain a modified calcite type nano calcium carbonate paste product, and drying to obtain a powder product, as shown in figure 9.

Table 7 comparative table of in-situ modified nano calcium carbonate properties

Compared with the stirred tank product, the particles of the product (figure 8) synthesized in the rotary loop reactor in the pilot plant test are more uniform, the average size of the particles is reduced by 27.2%, the carbon dioxide utilization rate is improved by 53.38%, the size of the product is similar to that of the product (figure 10) synthesized in the pilot plant test, and the related performance of the product meets the national product characteristics and index requirements of nano calcium carbonate in rubber, plastic, papermaking and the like.

Example 7 comparison of control effects of fusiform nano calcium carbonate Crystal forms

Weighing a certain amount of calcium hydroxide, adding water to prepare slurry with mass fraction of 7% -10%, placing into a rotary circulation reactor, controlling the temperature at 50-80deg.C, and controlling gas phase flow (carbon dioxide) to 3-6m ³ /h, liquid flow rate 2-4m ³ And/h, reacting until the pH=7-8 to obtain the final reaction point. And (3) carrying out suction filtration and washing on the reaction mixture to obtain a spindle-shaped nano calcium carbonate paste product, and drying to obtain a powder product. The xrd curve is the line A in FIG. 11, and the electron microscope is shown in FIG. 12.

Reconfiguring slurry 20L with mass fraction of 7% -10%, placing into stirring reactor, controlling temperature at 50-80deg.C, rotating at 300rpm, and gas phase flow (carbon dioxide) at 2-4m ³ And (h) repeating synthesis, filtering and washing the reaction mixed solution to obtain a calcium carbonate paste product, and drying to obtain a powder product, as shown in figure 13.

Comparing the two products, the electron microscope images shows that the spindle-shaped nano calcium carbonate is prepared by adopting a rotary loop reactor, and only partial spindle-shaped products are obtained in a stirring kettle and the size distribution is uneven. The international production of common spindle-shaped nano calcium carbonate mainly adopts high-concentration slurry, and adopts high-temperature production, and a certain crystal form control agent is needed to ensure the uniformity and small size of the product. According to the control method, through changing the operation conditions and controlling the crystal production process, spindle-shaped nano calcium carbonate with excellent performance, uniform particles and small size can be produced without additional crystal form control agents.

EXAMPLE 8 Synthesis of whisker-like nano calcium carbonate/calcium silicate hydrate composite Material

Weighing a certain amount of cement clinker, preparing 20L of slurry with solid-liquid ratio of 1:1-1:5, placing into a rotary circulation reactor, and controlling the liquid flow to be 1.5-3m under the condition of temperature of 50-80 DEG C ³ And/h, the gas flow is 2-4.5m ³ And/h, reacting for 2-8h. Filtering and washing the obtained precipitate to obtain aragonite type nano calcium carbonate paste product, and dryingAnd obtaining a powder product. The XRD curve is shown as line C in FIG. 11, and the morphology is shown in FIG. 13.

Weighing a certain amount of cement clinker, preparing 20L of slurry with solid-liquid ratio of 1:1-1:5, placing into a stirring reactor, controlling the temperature to 50-80deg.C, rotating at 150rpm, and gas phase flow (carbon dioxide) of 2-4.5m ³ And (h) repeating the experiment, carrying out suction filtration and washing on the obtained precipitate to obtain a paste product, and drying to obtain a powder product, as shown in figure 15.

The aragonite nano calcium carbonate is prepared by adopting a rotary circulation reactor, the aragonite content is 52%, the needle-shaped aragonite nano calcium carbonate is fully distributed on the surfaces of product particles, the length-diameter ratio is 10-20, and only a small amount of whisker of the product in the same-size stirring kettle is distributed on the surfaces of the product, so that the aragonite content is very low. Therefore, in the stirring reactor, the amplification experiment effect of the aragonite nano calcium carbonate is poor, and the reason for the poor gas-liquid mixing effect and uneven gas distribution is possible. The strong full-turbulence mixing effect of the rotary loop reactor is better, the amplifying effect is small, and the method has more application value in synthesizing aragonite nano calcium carbonate.

Example 9 calcium silicate hydrate morphology control

Weighing a certain amount of cement clinker, preparing 20L of slurry with solid-liquid ratio of 1:1-1:5, placing into a rotary circulation reactor, controlling the temperature to 50-80 ℃ and the liquid flow to 0.5-3m ³ And/h, the gas flow is 1-2.5m ³ And/h, reacting for 2-8h. And carrying out suction filtration and washing on the obtained precipitate to obtain a hydrated calcium silicate paste product, and drying to obtain a powder product. Product electron microscopy images 16-18 for different reaction conditions are shown.

FIG. 16 shows cement clinker raw material with a flow rate of 1.5m in the liquid phase ³ /h, gas flow 2m ³ At/h, the mixing conditions were mild and the product hydrated calcium silicate was predominantly in the form of tablets, as shown in FIGS. 17-18. As the gas-liquid flow rate increased, the flow rate in the liquid phase was 2.5m ³ /h, gas flow 3.5m ³ At above/h, the morphology of the hydrated calcium silicate product is changed from a sheet shape to a needle shape, and the hydrated calcium silicate product is connected into a hollowed-out net structure, so that the specific surface area is greatly improved, the reinforcing effect of the hydrated calcium silicate on rubber and plastic products is improved, and the surface spin loop reactor has a unique control aspect of crystal formA particular advantage. As shown in fig. 19, BET test results of the two optimized products are shown in table 8:

TABLE 8 BET monitoring results of the reaction Process of flaky and "Dictyophora Indusiata" shaped hydrated calcium silicate

Example 10 application example

The products of examples 6, 8 and 9 were chosen and pelletized by extrusion on an internal mixer with polypropylene (PP), and then injection molded into five standard bars by an injection molding machine, and a series of performance tests were performed, the average of the test results was shown in table 9, and the addition amounts were 10-30%.

TABLE 9 results of Performance test of PP-containing product (addition amount 10-30%)

According to the comparative analysis of the filling data of the PP resin, the series nano calcium carbonate products prepared by the method have better reinforcing and toughening effects. Within the addition amount of 30%, the performance of the material is kept good. The spin loop reactor has good application effect in the aspect of micro-nano material amplification production.

It should be emphasized that the embodiments described herein are illustrative rather than limiting, and therefore, the invention is not limited to the embodiments shown in the drawings, but is intended to be within the scope of the invention, either directly or indirectly, as long as equivalent structures or equivalent flow modifications are made by the teachings of the present invention and the accompanying drawings, or are employed in other related arts.

Claims

1. A method for preparing a micro-nano material, wherein the micro-nano material is selected from one or more of a composite nano material containing calcite type nano calcium carbonate/white carbon black, a composite nano material containing spindle type nano calcium carbonate/white carbon black, a composite nano material containing aragonite type nano calcium carbonate/white carbon black, a material containing three-dimensional bamboo fungus-shaped hydrated nano calcium silicate, a material containing two-dimensional flaky nano calcium silicate and a one-dimensional calcium-based material, and is characterized in that:

The method uses a rotary loop reactor system comprising a reactor body, a fluid circulation system, a temperature control system, a data analysis control system, wherein the fluid circulation system comprises a liquid circulation pump, a rotary loop spray head, a gas supply system, the method comprising the steps of:

and (3) opening gas flow valves in a temperature control system and a gas supply system, adding water, opening a liquid circulation pump, adding cement or cement clinker or lime or carbide slag or calcium hydroxide solution, mixing to form a suspension system, introducing one or more of carbon dioxide raw gas, flue gas or air or adding soluble carbonate or sulfuric acid or sulfate through a rotary circulation nozzle, optionally adding a modifier to perform in-situ modification, stopping the reaction within a pH value range of 6-8, and preparing the nano calcium carbonate or nano calcium silicate or calcium sulfate micro-nano material containing different morphologies through silica gel, neutralization precipitation, double decomposition and dehydration condensation reaction.

2. The process according to claim 1, wherein the spin loop reactor system employs an electromagnetic liquid flow meter;

preferably, the rotary loop reactor system comprises a main reactor, a double-channel liquid jet and cyclone circulation nozzle, a carbon dioxide raw material gas or flue gas or compressed air supply and gas circulation system, a gas flow valve and gas flow meter monitoring system, a liquid phase hybrid power system formed by a liquid circulation pump, a liquid flow meter and liquid flow valve control system, a circulating heating cooler temperature control system, a data recording and control system and a monitoring platform formed by a sensor;

Preferably, the fluid circulation system is powered by a liquid circulation pump, the reaction liquid is sent into the rotary circulation nozzle from the reactor, the gas supply system provides reaction gas by a gas holder or an air compressor, and the reaction gas is sent into the rotary circulation nozzle and collides with the liquid at an outlet; the electromagnetic liquid flowmeter and the gas flowmeter monitor the process, control the liquid valve and the gas valve to adjust the flow, and upload the data to the computer; the temperature control system maintains the temperature in the reactor stable;

preferably, the liquid circulation pump is selected from a centrifugal pump, a screw pump or a hose pump.

3. The method of claim 1, wherein the temperature is controlled at 20-110 ℃;

4. Process according to claim 1, wherein the production control conditions of the spin loop reactor system are determined by:

(2) For the gas-liquid mixing process, the gas distribution distance and the gas-liquid mass transfer coefficient are examined, the volume flow of the introduced gas is determined to be 1-5 times of the volume flow of the circulating liquid according to the jet flow distance formed by the pressure and the flow, and the cyclone circulation mixing device is used for mixing the gas and the liquidMathematical model formula for placing liquid volume mass transfer coefficient by inputting power P into liquid _L Unit gas input power P _G And the ratio of jet penetration distance to reactor diameter

Measuring and calculating;

5. the method according to claim 1, wherein the method is in particular:

(1) The method for producing the in-situ modified calcite type nano calcium carbonate/white carbon black composite nano material comprises the following steps: the reaction temperature is 20-60 ℃, the concentration of calcium hydroxide is 0.5-1.5mol/L, one or more of styrene-acrylic emulsion, sodium lignin or sodium stearate is added as a modifier, the volume flow of introduced carbon dioxide or flue gas is 1-5 times of the flow of circulating liquid, the volume flow of liquid circulation is 50-100 times of the volume amount of reactor materials per hour, and the pH value of the reaction end point is 6-8; preferably, the reaction temperature is from 30 to 60 ℃, more preferably from 40 to 60 ℃; preferably, the volume flow rate of the carbon dioxide or flue gas introduced is 1 to 4 times, more preferably 2 to 4 times, the flow rate of the circulating liquid; preferably, the liquid circulation volume flow is 60 to 100 times/hour, more preferably 80 to 100 times the volume of the reactor material;

Or alternatively

the reaction temperature is 50-80 ℃, the calcium hydroxide concentration is 0.5-1.5mol/L, the flow rate of the circulating liquid is 50-120 times/hour of the volume of materials in the reactor, and the volume flow rate of the introduced carbon dioxide or flue gas is 1-5 times of the volume flow rate of the circulating liquid; the pH value of the reaction end point is 6-8; preferably, the reaction temperature is 60-80 ℃, more preferably 60-70 ℃; preferably, the volumetric flow rate of the carbon dioxide or flue gas introduced is 1 to 4 times, more preferably 1 to 3 times, the volumetric flow rate of the circulating liquid;

or alternatively

Cement clinker: the solid-liquid ratio of water is 1:1-1:5, and the flow rate of liquid circulation body is 10-25 times of the volume of materials in the reactor per hour. The volume flow of the introduced air is 1-5 times of the volume flow of the circulating liquid, and the reaction time is 8-15 hours;

or alternatively

6. A spin loop reactor system for preparing the micro-nano material according to claim 1, comprising a reactor body, a fluid circulation system, a temperature control system, a data analysis control system, wherein the fluid circulation system comprises a liquid circulation pump, a spin loop spray head, a gas supply system.

7. A spiral flow reactor system according to claim 6, wherein the spiral flow reactor system employs an electromagnetic liquid flow meter;