CN114620753A - Low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat - Google Patents
Low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat Download PDFInfo
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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Abstract
The invention discloses a low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat, which comprises the following steps of: A. calcining limestone, and separating solid from gas to obtain calcium oxide and heat Q1The kiln gas of (2); B. the calcium oxide obtained in the step A is used as a raw material to be subjected to dry digestion to obtain digestion reaction heat Q2And calcium hydroxide powder; C. c, adding normal-temperature water into the calcium hydroxide powder obtained in the step B to prepare calcium hydroxide slurry, and carrying out quenching and tempering impurity removal to obtain raw calcium hydroxide slurry with the concentration and temperature meeting the carbonization requirement; D. c, reacting the calcium hydroxide raw slurry obtained in the step C with the kiln gas obtained in the step A to obtain carbonization reaction heat Q3Light calcium carbonate cooked slurry and carbonization tail gas; E. d, dehydrating the light calcium carbonate slurry generated in the step D to form light calcium carbonateWet calcium carbonate powder, using Q1、Q2、Q3And drying the light calcium carbonate wet powder, and crushing and grading to finally obtain a light calcium carbonate product. The invention can save energy, reduce consumption and reduce tail gas.
Description
Technical Field
The invention relates to the field of inorganic chemistry, in particular to a low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat.
Background
The light calcium carbonate is called light calcium (containing nano calcium carbonate, called nano calcium for short), is one of the most widely used inorganic non-metal products at present, and is widely used in the industries of rubber, papermaking, plastics, paint, printing ink, printing, cables, food, medicine, daily necessities, feed, lubricating oil and the like due to the advantages of no toxicity, no harm, environmental friendliness, high cost performance and the like. The main production process of light calcium carbonate is a carbonization method, and is mainly based on Ca (OH)2With CO2The acid-base neutralization reaction between the two to generate CaCO in liquid phase3Precipitation (carbonization for short in the industry) generally comprises the procedures of calcination, digestion, slurry impurity removal, carbonization, surface treatment, solid-liquid separation, drying, crushing, classification and the like, and is a typical high-energy-consumption and high-emission process.
In the prior art, a large amount of heat energy is consumed for calcining limestone into calcium oxide; a large amount of heat energy is generated when calcium oxide reacts with water to generate calcium hydroxide; the calcium hydroxide reacts with carbon dioxide gas to generate calcium carbonate, and heat energy is also released. The utilization rate of the heat energy is extremely low, the heat energy is often naturally discharged into the atmosphere and is occasionally utilized, and the heat energy is only used for heating and producing auxiliary water for life. On the other hand, if the digestion reaction of calcium oxide adopts wet digestion, the normal temperature of the digestion solution needs to be heated to about 45 ℃, and an energy-consuming heating process is also needed; before the calcium hydroxide slurry reacts with carbon dioxide gas, the calcium hydroxide slurry can be produced by forced cooling, and an energy-consuming and temperature-reducing process is needed; drying and dewatering of the light calcium slurry after solid-liquid separation also requires energy-consuming heating. As mentioned above, the traditional light calcium production process has long process flow, large conveying capacity of intermediate liquid phase, repeated heating and cooling phenomena, and simultaneously, a large amount of chemical reaction heat cannot be effectively extracted and utilized, so that waste is caused, energy consumption is low, and carbon dioxide tail gas emission is serious.
Chinese patent document CN102958843A discloses "slaked lime particles, light calcium carbonate, paper and coated paper using the same, and a method for producing light calcium carbonate" in 2013, 3/6, wherein: slaked lime particles having a cumulative volume of particles having a particle diameter of 1.0 μm or less in a volume particle size distribution of 20% or less and a cumulative volume of particles having a particle diameter of 100 μm or less of 95% or more. In the step of obtaining the slaked lime particles, it is preferable to add slaked water to quicklime in a molar ratio of 2.5 or less to quicklime and mix the slaked water and the quicklime. Slurrying the slaked lime particles, and carbonating the slaked lime slurry at 20 to 70 ℃ by blowing a gas containing carbon dioxide to convert the slaked lime slurry into light calcium carbonate. The obtained precipitated calcium carbonate can be used as a filler for paper or a pigment for coated paper. The method solves the problem of large liquid phase conveying capacity of the traditional process based on wet digestion to a certain extent, simplifies the process flow of the light calcium carbonate production, but does not relate to the recovery and utilization of chemical reaction heat and process waste heat, reduces the carbon emission and the like.
Chinese patent document CN109666187A discloses "a method for preparing light calcium carbonate based on slaked lime" in 2019, 1 month and 17 days, which comprises: firstly, slaked lime powder is selected to prepare calcium hydroxide slurry; then introducing the calcium hydroxide slurry into a first reaction cavity through a first water inlet, closing a second discharge hole, and introducing high-pressure carbon dioxide gas through a first gas inlet; a first stirrer is arranged in the first reaction cavity; then detecting the pH value of the calcium hydroxide slurry, and if the pH value meets a preset pH value, obtaining a calcium carbonate suspension; then heating the calcium carbonate suspension to 45-95 ℃, and adding a coating agent; and finally, filtering, washing, drying and crushing the calcium carbonate suspension to obtain the light calcium carbonate. According to the invention, high-pressure carbon dioxide is introduced and the first stirrer is arranged in the first reaction cavity, so that the conversion of calcium hydroxide slurry into calcium carbonate suspension is accelerated, and the production efficiency of calcium carbonate is improved; by adding the coating agent, the quality of the calcium carbonate is improved. The method can be regarded as an extension of the patent CN102958843A, changes the carbonization condition, increases the surface treatment process, and also does not pay attention to the problems of reducing energy consumption and carbon emission.
Chinese patent document CN109879304A discloses "a nano/submicron calcium carbonate high-efficiency carbonization process" in 2019, 6 months and 14 days, which comprises the steps of: calcining a limestone raw material to generate quicklime, adding water to digest the lime to generate lime milk, and preparing the lime milk into calcium hydroxide raw slurry with solid content of 20-50%; reducing the granularity of calcium hydroxide in the suspension to below 2 microns by a mechanical mode, then putting the obtained superfine raw slurry into a carbonization tower, introducing kiln gas to carry out carbonization reaction until the pH value of reaction slurry is 6.5-7, and stopping carbonization to obtain nano/submicron calcium carbonate slurry; carrying out wet surface treatment on the slurry by using a surface modifier, and carrying out filter pressing dehydration, drying and crushing to obtain nano/submicron calcium carbonate; the invention reduces the solid particles in the raw slurry from 5-10 microns to below 2 microns, greatly shortens the carbonization time of the raw slurry, reduces the product agglomeration and improves the production efficiency. The method only focuses on the carbonization link in the production of light calcium carbonate, aims to improve the carbonization reaction speed and efficiency by refining calcium hydroxide particles, and has very limited effect of shortening the carbonization time on energy conservation, consumption reduction and emission reduction in the whole process of the production of the light calcium carbonate.
In conclusion, the existing production process of light calcium cannot adapt to the aims of energy conservation, consumption reduction and emission reduction in modern industrial production, and particularly does not meet the national development strategy of 'carbon peak reaching and carbon neutralization', so that the energy-saving improvement on the production process of light calcium is accelerated, and the development of a new process which is more environment-friendly, energy-saving and low-carbon is urgent.
Disclosure of Invention
Based on the problems, the invention provides a low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat, the light calcium carbonate is produced by adopting a process combining a dry process and a wet process, the liquid phase volume and the conveying energy consumption of the procedures before carbonization are greatly reduced, simultaneously, the heat energy generated in each production link is effectively extracted and utilized, the energy-saving and consumption-reducing effects are obvious, kiln gas generated by calcining limestone is fully utilized, and the problem of carbon dioxide tail gas emission is greatly solved.
In order to realize the purpose of the invention, the invention adopts the following technical scheme: a low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat comprises the following steps:
A. calcining limestone, and separating solid from gas to obtain calcium oxide and heat Q1The kiln gas of (2);
B. the calcium oxide obtained in the step A is used as a raw material to be subjected to dry digestion to obtain digestion reaction heat Q2And calcium hydroxide powder;
C. adding normal-temperature water into the calcium hydroxide powder obtained in the step B to prepare calcium hydroxide slurry, and carrying out quenching and tempering impurity removal to obtain calcium hydroxide raw slurry with the concentration and temperature meeting the carbonization requirements;
D. c, reacting the calcium hydroxide raw slurry obtained in the step C with the kiln gas obtained in the step A to obtain carbonization reaction heat Q3Light calcium carbonate cooked slurry and carbonization tail gas;
E. d, dehydrating the light calcium carbonate slurry generated in the step D to form light calcium carbonate wet powder, and using Q1、Q2、Q3And drying the light calcium carbonate wet powder, and crushing and grading to finally obtain a light calcium carbonate product.
Preferably, the kiln gas obtained in the step A is high-temperature kiln gas, the high-temperature kiln gas is firstly used as a heat source to carry out primary drying heat exchange on the light calcium carbonate wet powder obtained in the step E to obtain intermediate-temperature kiln gas, the intermediate-temperature kiln gas is subjected to primary and secondary heat exchange in sequence to heat digestion steam and process return water in sequence, the heat exchange and the temperature reduction are carried out to obtain low-temperature kiln gas, and the low-temperature kiln gas is used for the carbonization reaction of the calcium hydroxide raw slurry in the step D.
Preferably, in step B, the heat of digestion reaction Q generated by the dry digestion of calcium oxide2And E, taking steam as a carrier, heating the steam by using medium-temperature kiln gas to form superheated steam, and then taking the superheated steam as a heat source to carry out secondary drying on the light calcium carbonate wet powder obtained in the step E.
Preferably, in step D, the calcium hydroxide raw slurry and low-temperature kiln gas are subjected to carbonization reaction to generate carbonization reaction heat Q3And D, performing three-stage drying on the light calcium carbonate wet powder obtained in the step E as a heat source.
Preferably, in the step E, a multi-heat source synergistic distributed multi-stage drying mode is adopted for the light calcium carbonate wet powder: high-temperature kiln gas is used as heat source Q1And working medium, performing primary drying in an airflow dryer to remove light componentsThe water content of the wet calcium carbonate powder is reduced to 35 percent; using heat of digestion reaction Q2And primary drying waste heat to generate high-temperature steam which is used as a heat source and a working medium to carry out secondary drying in a steam rotary dryer, so that the water content of the light calcium carbonate wet powder is further reduced to 25%; by using heat of carbonization reaction Q3And secondary drying waste heat, heating circulating air through a high-efficiency heat converter to generate high-temperature air, performing tertiary drying in a belt-type flow-through dryer as a heat source and a working medium, finally reducing the water content of the light calcium carbonate wet powder to be below 0.5%, and crushing and grading to finally obtain a light calcium carbonate product.
Preferably, in the step A, the temperature of the kiln gas is 240-300 ℃; and D, drying the light calcium carbonate wet powder by using an airflow dryer, wherein the average temperature of an air inlet end of the airflow dryer is 260 +/-5 ℃, and the average temperature of an air outlet end of the airflow dryer is 160 +/-5 ℃.
Preferably, in the step B, dry digestion is carried out in a closed adiabatic reactor, the solid-liquid mass ratio of calcium oxide to water is 1: 1.0-1.2, the calcium oxide is immediately digested when the temperature is not lower than 80 ℃ after being taken out of the kiln, the digestion water is preheated by medium-temperature kiln gas at the temperature of not lower than 60 ℃, the dynamic digestion is adopted in the digestion process, and the static digestion is changed after the liquid phase disappears.
Preferably, the temperature of the calcium hydroxide raw slurry obtained in the step C is not higher than 35 ℃, and the concentration is not higher than 15%.
Preferably, in the step D, the carbonization reaction adopts a two-stage series-connection bubbling carbonization process, and the carbonization reactor is provided with a water circulation jacket to extract the carbonization reaction heat Q3The carbonization initial temperature is not higher than 35 ℃, and the end point temperature is not higher than 75 ℃.
Preferably, the CO in the kiln gas produced in step A2Concentration of 32% -37%, CO2D, performing two-stage series bubbling carbonization reaction as a carbon source, and after the carbon source is absorbed by calcium hydroxide, carbonizing residual CO in tail gas2The concentration is 5 to 7 percent; after the heat energy carried in the kiln gas is recovered, the heat energy is introduced into the light calcium carbonate cooked slurry at a low flow rate to further absorb CO2Final evacuation of CO from the exhaust gas2The concentration is less than 3%.
The low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat, which is designed by the technical scheme, is introduced in detail by the following main steps:
(1) feeding limestone with uniform particle size into a lime kiln to be calcined, and introducing high-temperature kiln gas generated in the calcining process into an airflow dryer after two-stage dust removal to obtain clean heat Q1The high-temperature kiln gas is used for primary drying of the light calcium carbonate to obtain medium-temperature kiln gas; the medium-temperature kiln gas is subjected to primary and secondary heat exchange to obtain low-temperature kiln gas serving as CO2The source is used for the subsequent carbonation reaction (carbonization for short) of calcium oxide;
(2) adopting a dry digestion process to prepare calcium hydroxide powder by taking the lime fired in the step (1) as a raw material, and extracting the reaction heat Q of the hydration reaction of calcium oxide and water in the process in the form of water vapor2Heating the water vapor through primary heat exchange to obtain superheated steam at the temperature of about 130 ℃, and performing secondary drying on the light calcium carbonate through a steam drum dryer as a heat source; the superheated steam brings out the material moisture and reduces the temperature to saturated steam at about 120 ℃;
(3) after curing and heat exchange are carried out in the step (2), shunting calcium hydroxide powder at the temperature of lower than 80 ℃, directly processing 50% of the calcium hydroxide powder into a calcium hydroxide product, adding normal-temperature water into the other 50% of the calcium hydroxide powder to prepare calcium hydroxide slurry, and carrying out tempering and impurity removal to obtain calcium hydroxide raw slurry with the concentration and the temperature meeting the carbonization requirements; it should be reminded that if the flow splitting is not carried out in the step, the existing heat and the heat generated by the subsequent chemical reaction are less than the heat required by the wet digestion and the subsequent process of all the calcium hydroxide powder. From the perspective of comprehensively utilizing heat energy and reducing tail gas emission, the calcium hydroxide powder is recommended to be shunted in the step; however, the shunting means never influences the implementation effect of energy conservation and emission reduction; according to the long-term actual measurement of the inventor, 50% or more of calcium hydroxide is shunted, and the drying requirement of the light calcium carbonate product generated by converting the residual calcium hydroxide can be met by the process waste heat and the chemical reaction heat without external heat supply. The technicians in the field can make proper proportion adjustment according to the process characteristics and the product requirements of the factory;
(4) pumping the calcium hydroxide raw slurry into a carbonization tower, addingAdding required crystal form control agent and dispersant, etc., and carrying out two-stage carbonization reaction with low-temperature kiln gas at the temperature of lower than 60 ℃ in a liquid phase to generate light calcium carbonate (slurry) with certain crystal form and granularity; simultaneously, extracting carbonization reaction heat Q in the form of hot water at about 60 ℃ and carbonization tail gas at 70 ℃ by a water circulation jacket of a carbonization tower3Heating the hot water to about 80 ℃ through an absorption heat pump, heating the hot water and the 120 ℃ saturated steam obtained in the step (2) through a high-efficiency heat converter to obtain high-temperature air, and performing three-stage drying on the light calcium carbonate in a belt type through-flow dryer as a heat source and a working medium;
(5) and (3) settling and thickening the light calcium slurry, carrying out surface treatment after the solid content reaches more than 25%, adding an emulsifier to realize good dispersion of oleic acid in a water phase at a lower temperature, and finishing surface treatment on calcium carbonate particles by 15% oleic acid water emulsion under the action of high shear to obtain the light calcium finished product slurry. (note: if ordinary light calcium is used, surface treatment is not needed);
(6) carrying out solid-liquid separation on the light calcium product slurry by using a plate and frame filter press to obtain a filter cake with the solid content of more than 63%, and sending the filtrate back to a digestion system for recycling after the filtrate is treated by a water treatment system;
(7) adopting a multi-heat source cooperative distributed multi-stage drying mode, and adopting the above-mentioned Q1、Q2、Q3And (3) drying the filter cake obtained in the step (6) as a main heat source, and then crushing, grading and packaging to obtain a light calcium carbonate product.
Compared with the traditional process, the method is mainly improved as follows:
firstly, the high-temperature kiln gas generated during limestone calcination is fully recovered and utilized, heat is extracted through an airflow dryer, primary heat exchange and secondary heat exchange respectively according to the temperature characteristics of the kiln gas, the heat is used for primary drying of light calcium carbonate and heating of digestive steam and process return water, and the temperature of the kiln gas is reduced from about 260 ℃ to 60 ℃ to obtain low-temperature kiln gas. At the same time, the rich CO is utilized2The high-temperature kiln gas directly dries the light calcium carbonate, can effectively neutralize free basic groups generated by the light calcium at high temperature, inhibits the alkali return of the product, and reduces the pH value of the product.
And secondly, the dry method is adopted to digest the calcium oxide to obtain the calcium hydroxide powder, compared with the process of digesting the calcium hydroxide slurry by the wet method, the digestion reaction efficiency is greatly improved, and the volume and the weight of the intermediate product are remarkably reduced (about 80% of water can be reduced according to the actual measurement of the inventor), so that a transfer storage tank and supporting facilities for storing a large amount of slurry are reduced, the energy consumption of material transportation is reduced, and the process is simplified.
Thirdly, the high-temperature steam is fully extracted and the great amount of digestion reaction heat Q generated in the dry digestion is utilized2And waste heat of tail gas of the air flow dryer, superheated steam is used as a working medium to carry out secondary drying on the light calcium through the steam rotary dryer, and saturated steam is formed after the superheated steam carries moisture, so that heat energy can be further extracted. Compared with saturated steam, the superheated steam drying method has the outstanding advantages of small heat transfer resistance, high moisture migration speed, high drying efficiency and high heat energy utilization rate (up to about 90 percent).
Fourthly, calcium hydroxide powder generated by the dry digestion reaction is added with normal temperature water to be prepared into calcium hydroxide slurry with lower temperature, the initial temperature condition of carbonization can be met without adopting forced cooling, and the energy consumption is reduced.
Fifthly, low-temperature kiln gas is obtained after heat extraction and is used as a carbon source for carbonizing the calcium hydroxide raw slurry, and the carbonization reaction heat Q is fully extracted and utilized through circulating heat exchange and heating by a heat pump3The circulating air is heated by the heat energy converter to form circulating hot air which is used as a working medium to carry out three-stage drying on the light calcium product in the belt type through-flow dryer.
Sixthly, a two-stage series carbonization process is adopted, and the calcium hydroxide slurry is taken as a continuous phase to fully absorb CO in the low-temperature kiln gas2After the heat exchange of the carbonized tail gas, the carbonized tail gas is led into the light calcium carbonate boiled slurry at a low flow rate to further absorb CO2Compared with the traditional carbonization process, the method can remove CO in the kiln gas2Increases the absorption rate from about 76% to over 90%, and reduces the total carbon emission.
Seventhly, performing surface treatment on the calcium carbonate slurry obtained by carbonization at a lower temperature, then thickening the slurry, and dehydrating when the content of calcium carbonate in the slurry is increased to more than 25 percent, so as to shorten the dehydration time; and a filter press is adopted to carry out filter pressing dehydration on the thick slurry, the water content of a filter cake is controlled to be lower than 40%, and the drying energy consumption is reduced.
Eighthly, a multi-heat source cooperative distributed multi-stage drying mode is adopted. High-temperature kiln gas is used as heat source Q1And working medium, carry on the first grade to dry in the pneumatic drier; using heat of digestion reaction Q2And primary drying waste heat to generate high-temperature steam which is used as a heat source and a working medium to carry out secondary drying in a steam rotary dryer; by using heat of carbonization reaction Q3And secondary drying waste heat (where an external heat source Q can be supplemented as required)Outer cover) The circulating air is heated by the high-efficiency heat converter to generate high-temperature air which is used as a heat source and working medium to carry out three-stage drying in the belt-type flow-through dryer. It can be seen that the calcination heat energy (high-temperature kiln gas) and the digestion heat energy (water vapor) are extracted and utilized by the previous stage respectively, then flow to the next stage, and finally are recycled at the high-efficiency heat converter, a small amount of heat loss of a system pipeline is removed, and the system heat energy is almost continuously recycled and utilized, so that the comprehensive heat energy utilization rate of the process can reach more than 90%, the requirement of the light calcium drying process on external heat energy is greatly reduced, and the effects of energy conservation and emission reduction are obvious.
The method is used for the industrial production of the light calcium carbonate, has the outstanding advantages of simple process, small liquid phase conveying capacity of intermediate products, high utilization rate of chemical reaction heat and waste heat, less discharge of three-waste pollutants, low carbon and environmental protection, and has the advantages of remarkably reduced production cost, fully released profitability and more market competitiveness on the premise of basically consistent main technical indexes compared with the light calcium carbonate product obtained by the prior art. What is more, under the great trend of carbon peak reaching and carbon neutralization, the traditional high-energy-consumption and high-pollution light calcium carbonate production mode is difficult to continue, and the process method which is provided by the method and accords with the green chemistry and low-carbon economic principle undoubtedly has great and profound significance for breaking the development difficulty of the light calcium carbonate industry.
The following data are calculated for the light calcium carbonate manufacturing enterprises with a production capacity of one hundred thousand tons per year as an example:
firstly, three major liquid phase temperature control energy consumptions can be saved through system comprehensive heat energy recovery and utilization:
digestion and heating: heating from room temperature of about 23 deg.C to about 45 deg.C, and heating with heat of about
36×10000×1000Kg×4.2Kj/Kg.℃×(45-23)＝3.33×1010Kj
Cooling and carbonizing: cooling from 50 deg.C to 35 deg.C for carbonization, and reducing temperature for neutralization
57×10000×1000Kg×4.2Kj/Kg.℃×(50-35)＝3.59×1010Kj
And (3) heating surface treatment: the average temperature is increased from 55 ℃ to 65 ℃, and the heat is required to be about
60×10000×1000Kg×4.2Kj/Kg.℃×(65-55)＝2.52×1010Kj
The total of the three heat is about 9.44 multiplied by 1010Kj, according to standard coal 2.93X 107And by calculating Kj/ton, about 3221.8 tons/year of standard coal can be saved. The average coal consumption (6500 Kcal/Kg) of the current active light calcium product in the industry is about 135 Kg/ton, and the saved coal is used for drying light calcium and can dry about 2.57 ten thousand tons of active light calcium products.
And secondly, combining or reducing intermediate processes, reducing the conveying capacity of the intermediate liquid phase, and saving power consumption:
table 1: comparison of liquid-phase transport amounts of the inventive Process and the conventional Process
As shown in table 1, the amount of liquid phase required to be transported by the conventional process is about 262 ten thousand cubic per year accounting for the annual capacity of the company of ten thousand tons of light calcium carbonate; the total amount of the process is about 153 cubic meters, the liquid phase conveying capacity of 109 cubic meters is reduced, the amplitude is reduced by 41.6 percent, the electricity consumption can be saved by about 60 kilowatt-hour (calculated by a mortar pump at the rate of 55KW per cubic meter per hour) by only one cubic meter, the electricity consumption per ton of the product is about 6 kilowatt-hours on average, the electricity consumption per ton of the product in the calcium carbonate industry is 180 degrees as a base number, and only one cubic meter saves about 3.3 percent of electricity.
Thirdly, the light calcium is dried by utilizing the waste heat and the reaction heat of the production system, and no external energy consumption is needed under the condition of the invention.
The present invention features that the heat of digestion and carbonization reaction is used to dry light calcium carbonate. Similarly, the light calcium capacity accounting of one hundred thousand tons/year theoretically requires about 7.4 ten thousand tons of intermediate raw material calcium hydroxide, but the invention is based on the characteristics of the calcium carbonate industry (calcium hydroxide and light calcium are produced simultaneously) and the characteristics of the plant carry out 50 percent diversion on the intermediate product calcium hydroxide, namely 14.8 ten thousand tons of calcium hydroxide are required. In other words, 11.3 million tons of calcium oxide are available for extracting the heat of digestion reaction, and the dry pressure digestion converts 7.64 million tons of water into 120 ℃ steam, which provides about the following heat of drying:
7.64×10000×1000Kg×2201Kj/Kg＝16.81×1010kj, corresponding to 5737 tons of standard coal.
The heat quantity which can be extracted by the high-temperature kiln gas of the vertical kiln is as follows:
8500m3/h×270Kj/m3/3600＝1912.5Kw
the total heat quantity is 1912.5Kw × 360 × 24 × 3600Kj/h ═ 5.95 × 1010Kj
Corresponding to 2030 tons of standard coal.
The heat extractable for the carbonation reaction is:
7.4×10000×1000×118×1000Kj/74＝11.8×1010kj, equivalent to 4027 tons of standard coal.
The total of the above three part heat (16.81+5.95+ 11.8). times.1010Kj＝34.5610Kj is equivalent to 11650 tons of standard coal, according to the heat energy utilization scheme, the heat energy recovery and utilization rate can reach 91%, the actually available heat energy is equivalent to 11650 multiplied by 0.91 to 10601 tons of standard coal, and the product of the dry light calcium carbonate is 10601 multiplied by 1.07 multiplied by 1000/113 to 100381 tons, so that the heat requirement of drying 10 ten thousand tons of light calcium is completely met, namely the self-sufficiency of the heat required by drying is realized, and no external heat supply is needed.
Considering the scheme to shunt 50% calcium hydroxide, if accounting according to non-shunting, the total available heat energy is about (16.81/2+5.95+11.8) × 1010Kj＝26.15×1010Kj, in the aboveUnder the technical condition, the available heat energy is about 8032 tons of standard coal, and the dry light calcium 8032 multiplied by 1.07 multiplied by 1000/113 is 76055 tons, namely 76% of the dry heat energy of 10 ten thousand tons of light calcium is solved by internal circulation, only 24% of external heat supply is needed, and the energy-saving effect of the process method is still very obvious.
Fourthly, pollutant emission is reduced:
through the two-stage carbonization absorption of the carbon dioxide kiln gas in the carbonization process and the reabsorption of the residual carbon dioxide in the carbonized tail gas by using the calcium carbonate slurry, the absorption rate of the carbon dioxide in the kiln gas is improved from 76 percent to over 90 percent, 10 ten thousand tons of light calcium carbonate are produced, and the emission of the carbon dioxide gas can be reduced by about 0.9 ten thousand tons.
By combining the processes, 10 ten thousand tons of light calcium are produced, the power consumption of ineffective liquid phase transmission power can be reduced by about 60 ten thousand kilowatts, and 600 tons of carbon dioxide are reduced; the drying saves coal consumption by about 10601 tons compared with standard coal, and reduces emission of 26428 tons of carbon dioxide; the kiln gas absorption reduces about 9000 tons of carbon dioxide emission, reduces 36028 tons of carbon dioxide emission in total, reduces 9825.8 tons of carbon emission, reduces about 98.258Kg of carbon emission of light calcium ton products, has a carbon emission level of 160 Kg/ton compared with that of the current common light calcium industry, realizes over 61% carbon emission reduction, and has remarkable social and ecological benefits.
Drawings
FIG. 1 is a flow chart of a conventional process for producing light calcium carbonate;
FIG. 2 is a flow chart of the process for producing the light calcium carbonate of the present invention;
FIG. 3 is a heat energy comprehensive utilization route diagram of the production system of light calcium carbonate according to the present invention;
Detailed Description
The invention is further described with reference to the following detailed description and accompanying drawings.
Comparative example
(1) Sending limestone with uniform granularity into a lime kiln to burn lime, and purifying high-temperature kiln gas generated in the calcination process through two-stage dust removal and water spraying; reducing the temperature to below 80 deg.C, and pressurizing to 0.08Mpa with air compressor to obtain CO2The source is used for the subsequent carbonation reaction (carbonization for short) of calcium oxide;
(2) taking the lime fired in the step (1) as a raw material, adding process water which is 5 times of the mass of the lime and is preheated to more than 45 ℃ for wet digestion to prepare calcium hydroxide slurry, and directly emptying water vapor;
(3) carrying out three-stage refining and impurity removal on the calcium hydroxide slurry in the step (2) to obtain calcium hydroxide raw slurry with the temperature of about 50 ℃ and the solid content of about 14.5%;
(4) cooling the calcium hydroxide slurry to below 35 deg.C by refrigerator, pumping into carbonization tower, adding required crystal form control agent and dispersant, reacting with CO at 80 deg.C2The kiln gas with the content of about 34 percent is carbonized in a bubbling carbonization tower to generate light calcium carbonate (slurry) with certain crystal form and granularity; CO in kiln gas2Absorption and utilization rate of (2) is about 76%, carbonization tail gas temperature is about 70 ℃, and CO is2Content about 8.1%, directly emptied;
(5) the solid content of the light calcium carbonate slurry is about 18 percent, the light calcium carbonate slurry is cured for 12 hours, the temperature is reduced from about 70 ℃ to 50 ℃, the light calcium carbonate slurry is heated to more than 57 ℃ by drying waste heat for surface treatment, saponification liquid of about 3.0 percent oleic acid (relative to the dry weight of calcium carbonate) is added, and the mixture is continuously stirred for 50min to complete the surface treatment of calcium carbonate particles, so that the light calcium carbonate finished product slurry is obtained.
(ordinary light calcium does not need surface treatment);
(6) the light calcium finished slurry is squeezed and dehydrated by a plate and frame filter press to obtain a filter cake with solid content of more than 60%, and the filtrate is directly sent back to a digestion system for recycling after being treated by a water treatment system;
(7) and (2) drying the filter cake in a disc dryer by using high-temperature heat conduction oil generated by a heat conduction oil furnace as a working medium at a temperature range of 240-150 ℃ to obtain a light calcium semi-finished product with the water content of less than 0.5%, crushing, grading and packaging to obtain a light calcium carbonate product with the sampling number of SF-PCC-1. The production process flow chart of this comparative example is shown in FIG. 1.
Examples
(1) Feeding limestone with uniform particle size into a lime kiln to be calcined, and introducing high-temperature kiln gas generated in the calcining process into an airflow dryer after two-stage dust removal to obtain clean heat Q1High temperature kiln gas ofThe medium-temperature kiln gas (about 265 ℃ on average) is used for primary drying of the light calcium carbonate to obtain medium-temperature kiln gas (about 161 ℃ on average); the medium-temperature kiln gas is subjected to primary and secondary heat exchange to obtain low-temperature kiln gas (average about 67 ℃) which is used as CO2The source is used for the subsequent carbonation reaction (carbonization for short) of calcium oxide;
(2) adopting a dry digestion process to take the lime (average about 85 ℃) fired in the step (1) as a raw material, adding 60 ℃ digestion water with equal mass, preparing calcium hydroxide powder in an adiabatic reactor, extracting reaction heat Q2 of the hydration reaction of calcium oxide and water in the process in a steam form, heating the steam through primary heat exchange to obtain 130 ℃ superheated steam, and performing secondary drying on the light calcium carbonate through a steam drum dryer as a heat source; the superheated steam brings out the material moisture and reduces the temperature to 120 ℃ saturated steam;
(3) after curing and heat exchange are carried out in the step (2), shunting calcium hydroxide powder at the temperature of lower than 80 ℃, directly processing 50% of the calcium hydroxide powder into a calcium hydroxide product, adding normal-temperature water into the other 50% of the calcium hydroxide powder to prepare calcium hydroxide slurry, and carrying out quenching and tempering to remove impurities to obtain calcium hydroxide raw slurry with the concentration of 14.3% and the temperature of 33.7 ℃, which meets the carbonization requirement;
(4) pumping the calcium hydroxide raw slurry into a carbonization tower, adding a required crystal form control agent, a dispersing agent and the like, and performing two-stage carbonization reaction with low-temperature kiln gas at the temperature of lower than 60 ℃ in a liquid phase to generate light calcium carbonate (slurry) with certain crystal form and granularity; simultaneously, extracting carbonization reaction heat Q in the form of hot water at about 60 ℃ and carbonization tail gas at 70 ℃ by a water circulation jacket of a carbonization tower3Heating hot water to about 80 ℃ through an absorption heat pump, heating the hot water and the 120 ℃ saturated steam obtained in the step (2) through a high-efficiency heat converter to obtain high-temperature air, and performing three-stage drying on the light calcium carbonate in a belt type through-flow dryer as a heat source and a working medium;
(5) and performing sedimentation thickening on the light calcium slurry, performing surface treatment after the solid content reaches more than 25%, adding an emulsifier to realize good dispersion of oleic acid in a water phase at a lower temperature, and continuously dispersing the oleic acid water emulsion with the concentration of 13% and the addition of 3.0% for 40min under the action of high shear to finish the surface treatment on calcium carbonate particles to obtain the light calcium finished product slurry. (note: if ordinary light calcium is used, surface treatment is not needed);
(6) carrying out solid-liquid separation on the light calcium product slurry by using a plate and frame filter press to obtain a filter cake with the solid content of more than 63%, and sending the filtrate back to a digestion system for recycling after the filtrate is treated by a water treatment system;
(7) adopting a multi-heat source synergistic distributed multi-stage drying mode, and adopting the above-mentioned Q1、Q2And Q3And (3) drying the filter cake obtained in the step (6) as a heat source, crushing, grading and packaging to obtain a light calcium carbonate product, wherein the sampling number is GF-PCC-2. The production process flow chart of the embodiment refers to fig. 2, and the production system heat energy comprehensive utilization route chart refers to fig. 3.
The index comparison condition of the light calcium carbonate products obtained in the comparative example and the economic and environmental protection comparison condition of the two process operations are respectively shown in tables 2 and 3:
table 2: index comparison table of light calcium product obtained in embodiment of the invention and product obtained in traditional process
As can be seen from Table 2, the light calcium carbonate GF-PCC-2 prepared by the process of the invention is obviously superior to SF-PCC-1 in four indexes of whiteness, pH, oil absorption value and thixotropic index under the condition that the total technical indexes are equivalent to those of light calcium carbonate SF-PCC-1 obtained by the traditional process. The drying medium is directly contacted with the materials, and the heat exchange is direct and sufficient; the drying temperature is low, the three-stage drying temperature gradient is reasonable, and the thermal aging of the organic active substances on the surface of the product is inhibited.
Table 3: economic and environmental protection index comparison table of embodiment and comparative example of the invention
The comparison of economic and environmental indexes in table 3 shows that the process method has technical advantages over the conventional process from another dimension, that is, on the premise of the same output, the new process can realize less energy consumption, lower pollutant emission and lower production cost, which undoubtedly has great practical significance for removing the 'two high' cap from the conventional high-energy consumption and high-emission industry of light calcium carbonate to realize transformation upgrading and upgrading synergism.
Claims (10)
1. A low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat is characterized by comprising the following steps:
A. calcining limestone, and separating solid from gas to obtain calcium oxide and heat Q1The kiln gas of (2);
B. the calcium oxide obtained in the step A is used as a raw material to be subjected to dry digestion to obtain digestion reaction heat Q2And calcium hydroxide powder;
C. adding normal-temperature water into the calcium hydroxide powder obtained in the step B to prepare calcium hydroxide slurry, and carrying out quenching and tempering impurity removal to obtain calcium hydroxide raw slurry with the concentration and temperature meeting the carbonization requirements;
D. c, reacting the calcium hydroxide raw slurry obtained in the step C with the kiln gas obtained in the step A to obtain carbonization reaction heat Q3Light calcium carbonate cooked slurry and carbonization tail gas;
E. d, dehydrating the light calcium carbonate slurry generated in the step D to form light calcium carbonate wet powder, and using Q1、Q2、Q3And drying the light calcium carbonate wet powder, and crushing and grading to finally obtain a light calcium carbonate product.
2. The low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat according to claim 1, characterized in that the kiln gas obtained in the step A is high-temperature kiln gas, the high-temperature kiln gas is firstly used as a heat source to carry out primary drying heat exchange on the light calcium carbonate wet powder obtained in the step E to obtain intermediate-temperature kiln gas, the intermediate-temperature kiln gas is subjected to primary and secondary heat exchange in sequence to heat digestion steam and process return water in sequence, the heat exchange is carried out to reduce the temperature to obtain low-temperature kiln gas, and the low-temperature kiln gas is used for carbonization reaction of calcium hydroxide raw slurry in the step D.
3. The low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat as claimed in claim 2, wherein in the step B, the digestion reaction heat Q generated by the dry digestion of calcium oxide2And E, taking steam as a carrier, heating the steam by using medium-temperature kiln gas to form superheated steam, and then taking the superheated steam as a heat source to carry out secondary drying on the light calcium carbonate wet powder obtained in the step E.
4. The low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat as claimed in claim 3, wherein in the step D, the calcium hydroxide raw slurry and low-temperature kiln gas are subjected to carbonization reaction to generate carbonization reaction heat Q3And D, performing three-stage drying on the light calcium carbonate wet powder obtained in the step E as a heat source.
5. The low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat as claimed in claim 4, wherein in the step E, a distributed multi-stage drying mode with multiple heat sources in coordination is adopted for the light calcium carbonate wet powder: high-temperature kiln gas is used as heat source Q1And working medium, carrying out primary drying in an airflow dryer, and reducing the water content of the light calcium carbonate wet powder to 35%; using heat of digestion reaction Q2And primary drying waste heat to generate high-temperature steam which is used as a heat source and a working medium to carry out secondary drying in a steam rotary dryer, so that the water content of the light calcium carbonate wet powder is further reduced to 25%; by using heat of carbonization reaction Q3And secondary drying waste heat, heating circulating air through a high-efficiency heat converter to generate high-temperature air, performing tertiary drying in a belt-type flow-through dryer as a heat source and working media to reduce the water content of the light calcium carbonate wet powder to below 0.5%, and crushing and grading to finally obtain a light calcium carbonate product.
6. The low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat as claimed in claim 1, wherein in the step A, the temperature of kiln gas is 240-300 ℃; and D, drying the light calcium carbonate wet powder by using an airflow dryer, wherein the average temperature of an air inlet end of the airflow dryer is 260 +/-5 ℃, and the average temperature of an air outlet end of the airflow dryer is 160 +/-5 ℃.
7. The low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat according to claim 2 is characterized in that in the step B, dry digestion is carried out in a closed adiabatic reactor, the solid-liquid mass ratio of calcium oxide to water is 1: 1.0-1.2, the calcium oxide is immediately digested when the temperature is not lower than 80 ℃ after being discharged from a kiln, the digestion water is preheated by medium-temperature kiln gas at the temperature of not lower than 60 ℃, dynamic digestion is adopted in the digestion process, and the dynamic digestion is converted into static digestion after the liquid phase disappears.
8. The low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat as claimed in claim 1, wherein the temperature of the calcium hydroxide raw slurry obtained in the step C is not higher than 35 ℃ and the concentration is not higher than 15%.
9. The low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat as claimed in claim 1, wherein in the step D, the carbonization reaction adopts a two-stage series-connected bubbling carbonization process, and the carbonization reactor is provided with a water circulation jacket to extract the carbonization reaction heat Q3The initial carbonization temperature is not higher than 35 ℃, and the final carbonization temperature is not higher than 75 ℃.
10. The low-carbon process method for producing light calcium carbonate by comprehensively utilizing chemical reaction heat as claimed in claim 9, wherein CO in the kiln gas generated in the step A2Concentration of 32% -37%, CO2D, performing two-stage series bubbling carbonization reaction as a carbon source, and after the carbon source is absorbed by calcium hydroxide, carbonizing residual CO in tail gas2The concentration is 5 to 7 percent; after the heat energy carried in the kiln gas is recovered, the heat energy is introduced into the light calcium carbonate cooked slurry at a low flow rate to further absorb CO2Final evacuation of CO from the exhaust gas2The concentration is less than 3%.
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