CN1373086A - Process for preparing both sodium carbonate and silica white - Google Patents
Process for preparing both sodium carbonate and silica white Download PDFInfo
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- CN1373086A CN1373086A CN 01143247 CN01143247A CN1373086A CN 1373086 A CN1373086 A CN 1373086A CN 01143247 CN01143247 CN 01143247 CN 01143247 A CN01143247 A CN 01143247A CN 1373086 A CN1373086 A CN 1373086A
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- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
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Abstract
A process for preparing both sodium carbonate and silica white from the Na-containing compound (sodium hydroxide, Glauber salt, or sodium chloride), Si-containing material (high silicon quartz sand, diatomite, kaolinite, etc) and CO2 includes the reaction of said Si-containing material with said Na-containing compound to obtain sodium silicate, and the reaction of said sodium silicate with CO2 (or dicarbonate).
Description
The invention relates to a method for producing soda ash and white carbon black, in particular to a method related to the co-production of the soda ash and the white carbon black.
The existing soda ash and white carbon blackmanufacturing methods are independent of each other; through search, no report of the joint production of the two is found.
The soda belongs to a raw material type chemical product for large-scale production. After the project of eight five about the production of soda ash in China is finished, the project becomes one of the big countries for producing soda ash, and the annual production of soda ash exceeds 700 ten thousand tons (the yield is 744 ten thousand tons in 1998).
Among the soda ash produced globally, the ammonia-soda process is estimated to be employed by 85% (schiderli, non-waste process, page 221, university of qinghua press, 1990).
The ammonia-soda process uses sodium chloride and calcium carbonate as basic raw materials to produce soda ash through the following general reactions:
How to overcome the problems of the soda production is one of the purposes of the invention. Therefore, the invention provides a new soda ash manufacturing method, which combines the soda ash manufacturing and the white carbon black manufacturing to form a so-called soda ash-white carbon black combined manufacturing method, and the method has the advantages of reasonable utilization of raw materials and no environmental problem caused by large-amount discharge of waste.
The combined production method of soda ash and white carbon black is closely related to the existing production method of white carbon black.
Regarding the production of white carbon black, the precipitation method has been the most important method among the existing methods.
The precipitation method generally refers to a method of using sodium silicate as a raw material and an inorganic acid (usually HCl, H)2SO4、CO2) Method for precipitating dispersed silicon dioxide by reaction (encyclopedia of chemical engineering, Commission of chemical engineering, chemical industry)Encyclopedia, volume III, pages 968-972, chemical industry Press, 1993; CN 1069244A; CN 1036990C; CN 1048956C; CN 1148567A; CN 1230936A).
Precipitation produces soluble sodium salts along with silica precipitates, and sodium salts are generally not considered for recovery. Therefore, the utilization of the raw materials in the precipitation method is not ideal, and the waste materials also account for a high proportion.
How to recover the sodium salt, in particular to recover the sodium carbonate generated according to the set reaction, namely, transforming the precipitation method into a combined production method of white carbon black and soda ash, which is another object of the invention.
Obviously, if the precipitation method is limited to sodium silicate as a starting material, the economic significance of sodium salt recovery is limited, and further reasonable recovery measures need to be taken, and a little room for convolution does not exist. Therefore, breaking the limitation, Silica (SiO) will be rich2) The conversion of the waste materials (especially those rich in silica) such as rice husk ash, boiler ash, coal gangue, yellow phosphorus slag, zircon decomposition liquid, wollastonite, etc. into sodium silicate, followed by reaction with inorganic acid to prepare white carbon black, is considered to be a development of the precipitation method. The disclosures of patents CN1174168A, CN1134916A, CN1113216A, CN1115774A, CN1120016A, CN1058381A and CN1039000A belong to this category of methods. These processes, although not capable of recovering sodium salts, create advantages for further taking sodium salt recovery measures, since the preparation of white carbon black is extended to start from silica-containing raw materials.
The first method, which allows for the recovery of the sodium salt, is given by CN 1065051A. Later, CN1096524A and CN1039219C also give similar methods.
The process described in patent CN1065051A is believed to be a reaction of silica with soda ash to form sodium silicate
And reaction of carbon dioxide with sodium silicate to form white carbon black
And (4) forming.
From these two reactions, it can be seen that sodium silicate and carbon dioxide required for reaction (2) can be provided by reaction (1), and soda required for reaction (1) can be obtained from reaction (2); the above steps are repeated. With no change per cycle except that the silica was converted from crystalline quartz to amorphous powder. Therefore, the method for preparing the white carbon black by recycling the soda ash is actually a silica structure and form transformation process without other material consumption in theory except the quartz sand as the raw material, and compared with the traditional precipitation method, the method obviously has a plurality of advantages brought by reasonable utilization of the raw materials. However, since the soda ash generated in the reaction (2) is required to be used for preparing sodium silicate, the simultaneous production of the white carbon black and the soda ash as products cannot be realized.
The method disclosed in CN1096524A is basically the same as CN1065051A, except that silica-rich rice husk, rice straw, wheat straw and the like are used instead of quartz sand.
CN1039219C discloses a method for producing sodium silicate by carbothermal reduction of silica and mirabilite
And formation reaction of white carbon black
And (4) forming.
Reaction (4) in addition to the raw material sodium silicate obtained from reaction (3), the required sulfuric acid is also obtained by further converting the sulfur dioxide generated in reaction (3), and from reaction (4) in addition to the white carbon black, mirabilite is also obtained, which is recycled for reaction (3) to convert the silica into sodium silicate.
This process is substantially similar to CN1065051A and CN1096524A, and the recovered sodium salt is recycled for sodium silicate preparation, so no other product except white carbon black is produced.
In order to convert the waste sodium salt into sodium carbonate for recycling, thereby enabling the precipitation method to be a joint production method of soda ash and white carbon black, the invention provides the following technical scheme: firstly, reacting a raw material containing silica with a sodium-containing compound except soda ash to generate an intermediate compound sodium silicate; the sodium silicate then reacts directly or indirectly with carbon dioxide to produce soda ash and white carbon black.
By direct reaction, it is meant that the sodium silicate reacts with carbon dioxide
Soda ash and white carbon black are generated, and the indirect reaction refers to introducing carbon dioxide into soda ash solution and reacting the carbon dioxide and the soda ash solution as follows Is converted intoSodium bicarbonate (solution), then reacting with sodium silicate
Soda ash and white carbon black are produced.
According to the embodiment of the invention for preparing the soda ash and the white carbon black by the reaction (2), firstly, sodium silicate is diluted to 40-80 g of silicon dioxide per liter, a proper amount of sodium silicate is added into a reactor, the mixture is stirred and heated to 60-85 ℃, carbon dioxide diluted by 1-3 times of dry air or nitrogen is introduced at a constant temperature, and the introduction amount of the carbon dioxide is equal to that of the carbon dioxideNa in added sodium silicate2Based on the weight of O, in terms of Na2O∶CO2The ratio of carbon dioxide is 1: 1.2-2.0, preferably 1: 1.4-1.8, for example, 1: 1.6, the introduction speed of carbon dioxide is controlled to be 30-90 minutes, and then the reaction is finished after stirring at constant temperature for 30-90 minutes; after solid-liquid separation of the generated suspension, washing, drying and if necessary crushing solid slag to obtain white carbon black; and (3) separating out crystals from the mother liquor, calcining at 160-200 ℃ to obtain a product of soda ash, and recovering carbon dioxide generated by calcining and sending the carbon dioxide into a carbon dioxide storage cabinet for later use.
The embodiment of the process according to the invention for preparing soda ash and white carbon black from reaction (2') is carried out by first determining the amount of sodium silicate charged to the reaction and then using the Na content of the sodium silicate2On an O weight basis as Na2O∶NaHCO3Calculating the required sodium bicarbonate according to the ratio of 1: 3-5, preferably 1: 4.1, and preparing a 10% sodium bicarbonate solution (preparing and storing at the water temperature of 30-40 ℃, preparing only for the first time, and recycling the recovered sodium bicarbonate mother liquor later); adding all the sodium silicate solution and 20-40% of the sodium bicarbonate solution into the reactor, stirring, heating to 60-85 ℃, keeping constant temperature, adding the rest sodium bicarbonate solution, controlling the adding speed to be 30-90 minutes, completely adding, then keeping constant temperature, stirring for 30-90 minutes, and finishing the reaction; after solid-liquid separation of the generated suspension, washing, drying and if necessary crushing the solid slag to obtain white carbon black, evaporating the mother liquor until the volume of the mother liquor is equal to that of the added sodium bicarbonate solution, cooling to 30 ℃, keeping constant temperature, introducing carbon dioxide until the pH value of the mother liquor is less than or equal to 8.6, stopping introducing carbon dioxide, and waiting for the crystallization processAnd after the reaction is finished, the separated mother liquor can be directly used for the next preparation reaction, the crystal is calcined at 160-200 ℃ to obtain the product of soda ash, and carbon dioxide generated by calcination is recycled and sent to a carbon dioxide storage cabinet for later use.
According to another embodiment of the present invention, the soda ash and white carbon black are prepared by the reaction (2'), wherein the sodium bicarbonate solution is added into the reactor at a ratio of 20-40% of the total amount, the mixture is stirred and heated to 45-65 ℃, the temperature is kept constant, the sodium silicate and the rest sodium bicarbonate solution are added simultaneously in two parts, the adding speed is controlled to be 30-90 minutes, the mixture is heated to 60-85 ℃ after about 10 minutes, the mixture is stirred at constant temperature for 30-90 minutes, the reaction is terminated, and the obtained suspension is treated according to the method of the previous embodiment.
According to another embodiment of the present invention, the soda ash and white carbon black are prepared by the reaction (2'), wherein the sodium bicarbonate solution is added into the reactor completely, the temperature is raised to 45-65 ℃ by stirring, the temperature is kept constant, then the sodium silicate solution is added, the adding speed is controlled to be 30-90 minutes, the temperature is raised to 60-85 ℃ after about 10 minutes, the temperature is kept constant, and the stirring is carried out for 30-90 minutes, thereby ending the reaction. The resulting suspension was treated as described in relation to the previous embodiment.
The sodium-containing compound referred to in the present invention may be sodium oxide and hydrates thereof, such as sodium oxide and sodium hydroxide (caustic soda); sulfides and halides, such as sodium sulfide and sodium chloride (common salts); sodium salts of oxygen acids other than soda ash, such as sodium hydrogen sulfate, sodium sulfite, sodium sulfate (mirabilite), sodium nitrate, and the like. In the present invention, the preferable raw materials are caustic soda, mirabilite and salt, and after they are respectively mixed with silicato form sodium silicate, then they are reacted with carbon dioxide or sodium hydrogen carbonate to form the invented soda-white carbon black coproduction method.
1. Caustic method
The method is a method for realizing the co-production of soda ash and white carbon black by converting silica in a silica raw material into sodium silicate by using caustic soda and then reacting with carbon dioxide or sodium bicarbonate. The method is formed by sodium silicateWith soda ash and white carbon black
Or
And (4) forming.
The reaction (5) which is a main component of the method and constitutes a characteristic feature thereof is a process of dissolving silica in a sodium hydroxide solution in a silica-containing raw material, and belongs to one of the main methods of the known methods for preparing sodium silicate, and is called wet method or hydrothermal method (written by chemical industry publishers organization, chemical production flow diagram, upper book, pages 226 to 227, chemical industry publication, 1996; CN 1014694B; DE-OS 3313814; CN 1044634A; CN1033377C), and includes a conventional method of preparing a single product using quartz sand or quartzite with a high silica content as a raw material, and a method of separating and recovering other useful components while preparing sodium silicate using a raw material containing silica and other components, for example, a method of preparing white carbon black from an alkaline decomposition solution of zircon for preparing zirconium oxide from a silica-containing zircon ore given in CN11349 1134916A, a method of producing sodium silicate and aluminum hydroxide using fly ash given in CN1034412C, a method of preparing sodium silicate and aluminum hydroxide using fly ash, and amethod of preparing silica, CN1039000A discloses a method for co-producing sodium silicate and activated carbon by using rice hull ash, and belongs to the method.
The reaction (5) for the preparation of sodium silicate using caustic soda and a silica-containing feedstock is generally carried out in a pressure reactor. In addition to the conventional pressure reactor with stirring, other reactors such as a flow reactor (CN1014694B), a rotary reactor (CN1044634A) and a vertical tube reactor (DE-OS3313814) can be used for the preparation of sodium silicate according to reaction (5).
The known processes employ rather large concentrations ranging from 10% to 50% of caustic soda which participates in reaction (5). In the invention, the sodium silicate solution is convenient to transition to the next preparation process of soda-white carbon black, and the sodium silicate solution with the concentration of 20 percent is usually selected except for special requirements.
The molar ratio of sodium oxide to silicon dioxide, i.e. the modulus n, in sodium silicate can be adjusted by varying the ratio of silica to caustic soda charged to reaction (5). The prior art can prepare products with modulus of 1-3.5. For the soda-white carbon black co-production method, the modulus range is 1.7-2.1, and the method has special significance: this is the range required to maintain the soda ash and white carbon yield balance, i.e., to maintain the soda ash to white carbon yield ratio at about 1, and thus the modulus range of sodium silicate typically produced by the soda ash-white carbon co-production process of the present invention.
The reaction (5) of silica with caustic soda to form sodium silicate can be carried out at a temperature of 100-340 ℃ and a corresponding saturated vapor pressure, and after the reaction is completed, filtration or other separation measures are requiredif necessary, so that the final sodium silicate solution which can be clear is obtained.
After sodium silicate of the desired modulus is obtained from reaction (5), soda ash and white carbon black are prepared according to reaction (2) or (2').
Among the raw materials involved in the caustic process, sodium bicarbonate involved in the reaction (2') can be considered as another form in which carbon dioxide exists by means of soda ash, and its production does not involve additional raw materials. Therefore, the raw materials for producing soda ash and white carbon black are only caustic soda, silica and carbon dioxide. The raw material of the silica can be quartz sand, quartzite, diatomite, fly ash and the like, and the silica is not short in source and low in price. Carbon dioxide, as a major greenhouse gas for emission limitation, is available at little cost from flue gas from coal or oil fired boilers. Therefore, only caustic soda is expensive in all raw materials.
As is known, caustic soda is a product of chlor-alkali industry and is produced by using common salt as a raw material and adopting an electrolytic method. After the second war, with the development of petrochemical industry, chlor-alkali production began to take the chlorine needed for the synthesis of organic chlorides as the main objective, especially after the application of polyvinyl chloride showed significant ecological, social and economic benefits. Therefore, with the expansion of the application scale of polyvinyl chloride replacing wood and steel, the demand for chlorine is correspondingly increased, and the problem of excessive caustic soda is caused in chlor-alkali production. The excess caustic soda is solved by reacting with carbon dioxide and converting into soda ash with market demand. Therefore, in some countries where the petrochemical industry has been highly developed, such as the united states, the efficiency of chlor-alkali production is reduced by the excess of caustic soda; caustic soda, which is a by-product in the production of chlor-alkali, is sold by conversion to soda ash to increase its economic value (w.h. nebo gail et al, translation of chen shu et al, ampan school, general chemistry, fourth minute book, page 102, third minute book, page 3, people education press, 1979).
In the caustic soda method, as the raw material caustic soda, a caustic soda solution produced by electrolyzing common salt can be used as it is, and particularly, an electrolyte produced by an ion membrane method is diluted to a predetermined concentration, and is converted into sodium silicate according to the reaction (5), and further converted into soda ash and white carbon black by the action of carbon dioxide. In the above process of converting caustic soda into soda ash, the structure and form of the raw material silica are promoted to obtain white carbon black as an additional product, so that the economic value of the soda ash is further improved as compared with that of soda ash directly produced by reacting with carbon dioxide. Therefore, caustic soda, which is one of the raw materials, is considered to be acceptable in view of its economic effect, although it is relatively expensive compared to silica-containing raw materials and carbon dioxide.
The soda process can be used for co-producing soda ash and white carbon black, is beneficial to improving the economic benefit of chlor-alkali production and promoting the popularization and application of polyvinyl chloride in China.
2. Mirabilite method
The method is that after sodium silicate is converted from mirabilite, the silica is reacted with carbon dioxide or sodium bicarbonate to prepare soda ash and white carbon black, and the sodium silicate is reactedWith soda ash and white carbon black
OrAnd (4) forming.
In this method, reaction (3), which is one of the known methods for preparing sodium silicate, is called dry method (Dingyi editors, inorganic salts, pp. 90-91, chemical industry publishers 1990; CN 1039219C; CN1044931A), sodium sulfate, coke and quartz sand are mixed according to a required ratio, and then reacted in a kiln at 1300-1400 ℃ to produce a sodium silicate melt, which is discharged and then cooled, water quenched and separated to produce sodium silicate.
According to the reaction (3), sodium silicate with the modulus n of 1-3.5 can be prepared by changing the ratio of the added silica and mirabilite, and is selected when the ratio of the produced soda ash and the white carbon black is adjusted in the reaction (2) or (2').
After sodium silicate of the desired modulus is obtained from reaction (3), soda ash and white carbon black are prepared according to reaction (2) or (2').
According to the mirabilite method embodiment of the invention, the preparation process of the soda ash and the white carbon black comprises the following steps:
① sodium silicates are prepared in a known manner, i.e. according to reaction (3) and the known relevant conditions, and
preparing soda ash and white carbon black according to the reaction (2) or (2');
② recovering sulfur dioxide generated in the reaction (3), and converting into sulfuric acid (Wuhan steel)
Company editions, industrial pollution control and technical-economic analysis thereof, metallurgical industry publishers, 1991;
CN1039219C)；
③ recovering carbon dioxide formed in the reaction (3) as carbon dioxide required for the reaction (2) or (2
One of the sources used in the preparation of soda ash and white carbon black.
3. Salt method
The process for preparing soda-white carbon black with salt as raw material of sodium-containing compound includes the reaction of salt with raw material containing silica to prepare sodium silicate and the reaction of sodium silicate with carbon dioxide or sodium bicarbonate to prepare soda and white carbon black.
In the conventional methods for producing sodium silicate from common salt and silica as raw materials, the formation reaction of sodium silicate is often promoted by adding a metal oxide. In the process given in CN1043886A, oxides of vanadium and molybdenum are added; in the process given in CN1038742C, it is required that the added metal oxide be capable of converting into chloride with a lower boiling point (relative to the reaction temperature) or easy sublimation in the reaction.
According to the method of CN1038742C, when 1 part by weight of alumina is added to 4 parts by weight of common salt and 5 parts by weight of silica, the reaction is carried out at 900 to 1500 DEG C
In the sodium silicate preparation scheme of the common salt method provided by the invention, not only is no metal oxide added in the preparation process of the sodium silicate, but also the reaction process is used for separating and recovering other components from the raw material containing the silica.
The scheme provided by the invention is to prepare the sodium silicate with the required modulus by taking salt and metal minerals containing silica as raw materials and quartz sand or quartzite as a modulus regulator.
In this embodiment, the siliceous metal mineral raw material may be an iron-containing mineral such as low-grade iron ore, iron ore tailings, or the like, an aluminum-containing mineral such as kaolin, chamotte, bauxite having a low aluminum-silicon ratio, or a solid waste mineral containing metals such as fly ash, coal gangue, and the like, iron, titanium, or the like, or another silica-rich metal mineral. The minerals and salt are mixed according to the required proportion, and then are roasted at high temperature, so that the reaction can be shown as follows
The sodium silicate with the required modulus is prepared according to the reaction (8), and the proportioning calculation is preferably carried out by taking the mineral raw materials as a reference. When the amount of the mineral raw material is given, the theoretical amount of the salt to be added can be calculated from the contents of the metal oxides other than the alkali metal and the alkaline earth metal in the mineral raw material. If the SiO of the mineral raw material2The content is lower, that is, when the content of the metal oxide is higher than the required amount of the reaction, a plurality of SiO is added2To increase the SiO content of the reaction mixture2The ratio can be used to prepare sodium silicate with modulus of more than 1.7. Supplemented SiO2Amount, given as the modulus n of the sodium silicate produced, calculated according to formula (8) and reference amount of SiO in the mineral2The difference in the contents; supplemented SiO2Called modulus modifier, is added in the form of high purity quartzite or quartz sand.
According to the embodiment of the present invention for producing sodium silicate by the reaction (8), the amount of quartzite or quartz sand to be charged, the purity thereof and SiO calculated from the charged amount of the mineral raw material to be charged to the reaction are given in a certain unit2The supplementary amount is converted; the salt input amount is obtained by converting the purity of the salt and the theoretical amount and multiplying the converted purity by a coefficient k; k is called a reaction material adjustment coefficient, and the value range is 1.25-1.45. Mixing the mineral raw materials, salt, quartzite or quartz sand according to a ratio, crushing to be less than or equal to 100 meshes, putting into a reaction furnace, heating to 500-1500 ℃, reacting for 3-10 hours, and finishing the reaction. Discharging the generated melt, cooling, water quenching, dissolving and performing solid-liquid separation to obtain a sodium silicate solution; the chloride gas generated in the reaction can be cooled according to the condition and the requirement of the materials put into the reaction or according to the boiling pointAnd (3) condensing, separating and recovering, or converting into metal oxide and hydrochloric acid, or converting into oxide and chlorine.
After sodium silicate of the desired modulus is obtained from reaction (8), soda ash and white carbon black are prepared according to reaction (2) or (2').
Example 1
2000 g of 20% caustic soda solution and 625 g of quartz sand with the silica content of more than or equal to 97% and crushed to 120 meshes or less are added into a pressure reactor with stirring, the temperature is raised to 210 ℃ while stirring, the reaction is carried out for 150 minutes at the temperature and the corresponding saturated vapor pressure, the reaction is finished, and the sodium silicate solution with the silicon dioxide (weight) of 23.2% and the sodium oxide of 11.8% is obtained after filtration.
520 g of the sodium silicate solution described above are diluted with 1615 g of water (total volume about 2000 ml, concentration about 60 g/l in silica) and introduced into a stirred reactor, the temperature is raised to 70 ℃ and 99.2 g of carbon dioxide (as Na) diluted with 2 volumes of dry air are introduced at this temperature2O∶CO2Calculated as 1: 1.6), the rate of passage was maintained at 60 minutes and the entire passage was completed. Thereafter, the reaction was terminated by keeping the temperature constant and stirring for 70 minutes. Carrying out solid-liquid separation on the prepared suspension, concentrating and crystallizing mother liquor to obtain sodium carbonate containing sodium bicarbonate, calcining at 160-200 ℃ to obtain 100 g of sodium carbonate, and recovering carbon dioxide generated by calcining and sending the carbon dioxide into a carbon dioxide storage cabinet for later use; washing the solid residue twice (500 g of water for each time), and drying to obtain the product with silicon dioxide content of 95% and specific surface area of 170 m2122 g of white carbon black; the wash water is recovered to dilute the sodium silicate solution for the next reaction.
Example 2
520 g of the sodium silicate solution obtained in example 1 (120.6 g and 61.4 g of silica and sodium oxide, respectively), 2500 g of a 10% sodium bicarbonate solution (sodium bicarbonate as Na)2O∶NaHCO3Calculated as 1: 4.1), after the entire sodium silicate solution was added to the reactor, 750 g (30% of the total amount) of sodium bicarbonate solution was added, stirred and warmed to 70 ℃, and the remaining sodium bicarbonate solution was added at a rate of 29.2 g/min (about 60 minutes) at a constant temperature, and stirred for 60 minutes while maintaining the constant temperature, thereby completing the reaction. And (3) carrying out solid-liquid separation on the obtained suspension: washing and drying the solid slag to obtain the solid slag with the silicon dioxide content of 95.8 percent and the specific surface of 194 m2120 g of white carbon black; evaporating mother liquor to volume equal to the volume of sodium bicarbonate solution (about 2350 ml), cooling to 30 deg.C, introducing carbon dioxide until pH of mother liquor is less than or equal to 8.6, stopping introducing carbon dioxide, and separating after crystallizationThe sodium bicarbonate-containing solution was used directly in the next preparative reaction (first only)Preparation is needed for the second time), 101 g of soda ash is generated after the crystal is calcined at 160-200 ℃, and carbon dioxide generated by calcination is recycled and sent to a carbon dioxide storage cabinet for later use.
Example 3
The sources and amounts of the sodium silicate and sodium bicarbonate solutions were the same as in example 2. Adding one third of the total amount of the sodium bicarbonate solution into the reactor, stirring and heating to 55 ℃, keeping constant temperature, simultaneously adding the sodium silicate and the rest of the sodium bicarbonate solution at two positions, controlling the adding speed to be completely added within 60 minutes, then heating to 70 ℃ within about 10 minutes, keeping constant temperature and stirring for 60 minutes, and reacting after the adding is finished. The suspension obtained was treated in accordance with example 2 to give soda ash 98 g and white carbon black (specific surface 205 m)2G, silica content 96.1%) 118 g.
Example 4
The sources and amounts of the sodium silicate and sodium bicarbonate solutions were the same as in example 2. Adding the sodium bicarbonate solution into the reactor completely, stirring and heating to 55 ℃, keeping constant temperature, adding the sodium silicate solution, controlling the adding speed to be completely finished within 60 minutes, then heating to 75 ℃ within about 10 minutes, keeping constant temperature, stirring for 60 minutes, and finishing. The suspension obtained was treated in accordance with example 2 to give 102 g of soda ash and 120 g of white carbon black (specific surface area 220 m 2/g, silica content 94.9%).
Example 5
Adding 800 g of 20% caustic soda solution into a pressure reactor with stirring, wherein the content of silica is more than or equal to 97%, crushing the caustic soda solution into 250 g of quartzite with the granularity of less than or equal to 120 meshes, stirring, heating to 210 ℃, reacting for 150 minutes at the temperature and corresponding saturated steam pressure, and finishing the reaction. Filtration gave 1001 g of sodium silicate solution containing 22.8% and 12.0% silica and sodium oxide, respectively.
Taking 520 g of the sodium silicate solution and 2500 g of a 10% sodium bicarbonate solution, 102 g of soda ash and silica white (specific surface area 180 m) were prepared according to example 32G, silica content 96.0%) 115 g.
Example 6
Adding 800 g of 20% caustic soda solution and 270 g of diatomite with the silica content of more than or equal to 90% and the fineness of less than or equal to 120 meshes into a pressure reactor with stirring, heating to 120 ℃, keeping constant temperature, reacting for 100 minutes under the saturated vapor pressure corresponding to the temperature, finishing the reaction, and filtering to obtain 998 g of sodium silicate solution containing 23.4% of silicon dioxide and 11.4% of sodium oxide respectively.
97 g of soda ash and white carbon black (specific surface area 250 m) were prepared in example 4 using 520 g of the sodium silicate solution and 2500 g of a 10% sodium bicarbonate solution2G, silica content 95.2%) 119 g.
Example 7
Using mirabilite, coke and quartz Sand (SiO) as raw materials2Not less than 97%) of Na2SO4、C、SiO2On a basis of Na and according to2SO4∶C∶SiO2Mixing and crushing the raw materials (less than or equal to 60 meshes) according to the weight ratio of 24: 1.2: 20, putting the mixture into a reverberatory furnace, heating the mixture to 1300-1400 ℃, reacting for 1-3 hours, discharging generated melt, and cooling, water quenching, dissolving and solid-liquid separating to obtain the sodium silicate solution. The sodium silicate solution was used to prepare soda ash and white carbon black according to any one of examples 1 to 4; recovering sulfur dioxide generated in the reaction, and converting the sulfur dioxide into sulfuric acid product by a contactmethod; the carbon dioxide generated in the reaction is used as one of the carbon dioxide sources of the method and is used for preparing the soda ash and the white carbon black.
Example 8
Sodium silicate with the modulus n of 2 is prepared by taking salt and iron ore as raw materials and quartzite as a modulus regulator, and soda ash and white carbon black are further prepared.
The raw material salt contains 94% NaCl; iron ore containing 66.20% SiO2、32.30％Fe2O3(ii) a Quartzite contains 98% SiO2. In the preparation reaction of sodium silicate, the input amount of salt is required to be 1.30 times of the theoretical amount (the k value is 1.30), and when the input amount of iron ore is taken as a reference, the raw material ratio is calculated as follows:
mixing the raw materials of iron ore, salt and quartzite according to the ratio of 100: 98: 6.5, crushing the mixture to be less than or equal to 100 meshes, putting the mixture into a reaction furnace, heating to 800-1350 ℃ for reaction for 3-5 hours, and then heating to 1450-1500 ℃ for reaction for 0.5-1 hour to finish the reaction. Discharging the resultant melt, cooling, water quenching, dissolving, and performing solid-liquid separation to obtain a sodium silicate solution, and preparing soda ash and white carbon black according to any one of examples 1 to 4 with respect to the preparation method of soda ash and white carbon black; and (3) the ferric chloride gas generated in the reaction enters a cooling chamber at 700-750 ℃ to recover volatilized sodium chloride, and then enters an oxidation tower at 600-700 ℃ to react with the fed oxygen, and the generated ferric oxide and chlorine are recovered as products.
Example 9
Salt and kaolinite are used as raw materials, quartzite isused as modulus regulator, sodium silicate with modulus n of 2 is prepared, and soda ash and white carbon black are further prepared.
The raw material salt contains 94% NaCl; kaolinite contains 46.54% SiO2、39.50％Al2O3(ii) a Quartzite contains 98% SiO2. In the preparation reaction of sodium silicate, the input amount of common salt is required to be 1.30 times of the theoretical amount (the k value is 1.30), and when the input amount of kaolinite is taken as a reference, the raw material ratio is calculated as follows:
mixing kaolinite, salt and quartzite in a ratio of 100: 188: 95, crushing to be less than or equal to 100 meshes, putting into a reaction furnace, heating to 500-600 ℃ for reaction for 0.5-1 hour, heating to 800-1400 ℃ for reaction for 3-5 hours, and finally reacting at 1450-1500 ℃ for 0.5-1 hour to finish the reaction. Discharging the resultant melt, cooling, water quenching, dissolving, and performing solid-liquid separation to obtain a sodium silicate solution, and preparing soda ash and white carbon black according to any one of examples 1 to 4 with respect to the preparation method of soda ash and white carbon black; and (3) allowing the aluminum chloride gas generated in the reaction to enter a cooling chamber at 700-750 ℃ to recover volatilized sodium chloride, allowing the aluminum chloride gas to enter a hydrolysis tower at 200-300 ℃ to react with fed water vapor, recovering the generated aluminum oxide as a product, and absorbing the generated hydrogen chloride with water to convert the hydrogen chloride into hydrochloric acid for recovery.
Example 10
Salt and fly ash are used as raw materials, quartzite is used as a modulus regulator, sodium silicate with the modulus n being 2 is prepared, and soda ash and white carbon black are further prepared.
The raw material salt contains 94% NaCl; the fly ash contains 52.50 percent of SiO2、31.25％Al2O3、6.95％Fe2O3(ii) a Quartzite contains 98% SiO2. In the preparation reaction of sodium silicate, the input amount of salt is required to be 1.30 times of the theoretical amount (the k value is 1.30), and when the input amount of the fly ash is taken as a reference, the raw material ratio is calculated as follows:
mixing the fly ash, the salt and the quartzite in a ratio of 100: 170: 75, crushing to be less than or equal to 100 meshes, putting into a reaction furnace, heating to 800-1350 ℃ for reaction for 3-5 hours, heating to 1450-1500 ℃ for reaction for 0.5-1 hour, and finishing the reaction. Discharging the resultant melt, cooling, water quenching, dissolving, and performing solid-liquid separation to obtain a sodium silicate solution, and preparing soda ash and white carbon black according to any one of examples 1 to 4 with respect to the preparation method of soda ash and white carbon black; the chloride gas generated in the reaction process enters a cooling chamber at 700-750 ℃ to recover the volatilized sodium chloride and the chlorides of calcium and magnesium, then enters a cooling chamber at 250-280 ℃ to recover ferric chloride, and then enters a cooling chamber at 160-170 ℃ to recover aluminum chloride.
Example 11
Sodium silicate with the modulus n of 2 is prepared by using salt and coal gangue as raw materials and quartz sand as a modulus regulator, and soda ash and white carbon black are further prepared.
The raw material salt contains 94% NaCl; coal gangue contains 54.33% SiO2、19.59％Al2O3、7.24％Fe2O3、1.80％TiO2(ii) a Quartz sand containing 98% SiO2. In the preparation reaction of sodium silicate, the input amount of salt is required to be 1.30 times of the theoretical amount (the k value is 1.30), and when the input amount of coal gangue is taken as a reference, the raw material ratio is calculated as follows:
mixing the coal gangue, the salt and the quartzite in a ratio of 100: 122: 37, crushing to be less than or equal to 100 meshes, putting into a reaction furnace, heating to 800-1350 ℃ for reaction for 3-5 hours, heating to 1450-1500 ℃ for reaction for 0.5-1 hour, and finishing the reaction. Discharging the resultant melt, cooling, water quenching, dissolving, and performing solid-liquid separation to obtain a sodium silicate solution, and preparing soda ash and white carbon black according to any one of examples 1 to 4 with respect to the preparation method of soda ash and white carbon black; the chloride gas generated in the reaction process enters a cooling chamber at 700-750 ℃ to recover volatilized sodium chloride and chlorides of calcium and magnesium, then enters a cooling chamber at 250-280 ℃ to recover ferric chloride, and then enters a cooling chamber at 160-170 ℃ to recover aluminum chloride and enters a cooling chamber at a temperature not higher than 40 ℃ to recover titanium chloride; the recovered chloride may be further purified by fractional distillation if necessary.
Claims (10)
1. A process for preparing soda-white carbon black includes such steps as reaction of silica-contained raw material with sodium-contained compound except soda to generate sodium silicate as intermediate compound, and reaction of sodium silicate with carbon dioxide
Preparation of soda ash and white carbon black, or reaction with sodium bicarbonate as follows
Soda ash and white carbon black were prepared.
2. The process for producing soda-silica white as claimed in claim 1, wherein the following soda-silica white is prepared by reacting sodium silicate with carbon dioxide: diluting a sodium silicate solution to 40-80 g of silicon dioxide per liter, adding a proper amount of the sodium silicate solution into a reactor, stirring and heating to 60-85 ℃, keeping a constant temperature, introducing carbon dioxide diluted by 1-3 times of dry air or nitrogen, wherein the introduction amount of the carbon dioxide is Na in the added sodium silicate2Based on the weight of O, in terms of Na2O∶CO2The carbon dioxide is completely introduced at a speed of 30-90 minutes in a ratio of 1: 1.2-2.0, and then the reaction is finished after stirring at a constant temperature for 30-90 minutes; after solid-liquid separation of the generated suspension, washing, drying and if necessary crushing solid slag to obtain white carbon black; separating out crystals from the mother liquor, calcining the crystals to convert the crystals into a product of soda ash, and recovering carbon dioxide generated by calcining and sending the carbon dioxide into a carbon dioxide storage cabinet for later use.
3. The process for the co-production of soda ash and self-carbon black as claimed in claim 1, wherein said process comprisesThe soda-white carbon black is prepared by reacting sodium silicate with sodium bicarbonate, and comprises the following steps: after the amount of sodium silicate charged for reaction is determined, Na in the sodium silicate is used2On an O weight basis as Na2O∶NaHCO3Calculating the required sodium bicarbonate at a ratio of 1: 3-5, and preparing a 10% sodium bicarbonate solution (preparing and storing at a water temperature of 30-40 ℃, preparing for the first time, and recycling the recovered sodium bicarbonate mother liquor later); adding all the sodium silicate solution and 20-40% of the sodium bicarbonate solution into the reactor, stirring, heating to 60-85 ℃, keeping constant temperature, adding all the rest sodium bicarbonate solution, controlling the adding speed to be 30-90 minutes, then keeping constant temperature, stirring for 30-90 minutes, and finishing the reaction; after solid-liquid separation of the generated suspension, washing, drying and if necessary crushing solid slag to obtain white carbon black, evaporating mother liquor until the volume of the mother liquor is equal to that of the added sodium bicarbonate solution, cooling to 30 ℃, keeping constant temperature, introducing carbon dioxide until the pH value of the mother liquor is less than or equal to 8.6, stopping introducing the carbon dioxide, after the crystallization process is completed, directly using the separated mother liquor for the next preparation reaction, calcining crystals to convert the crystals into pure alkali, and recovering the carbon dioxide generated by calcination and sending the carbon dioxide into a carbon dioxide storage cabinet for later use.
4. The process for preparing soda-silica white as claimed in claim 3, wherein the sodium silicate and sodium bicarbonate are reacted with each other to form soda-silica white, the reaction is completed by adding 20-40% of the total amount of sodium bicarbonate solution into the reactor, stirring and heating to 45-65 ℃, keeping the temperature constant, adding sodium silicate and the rest of sodium bicarbonate solution at two parts simultaneously, controlling the adding speed to be 30-90 minutes, heating to 60-85 ℃ for about 10 minutes, stirring at constant temperature for 30-90 minutes.
5. The process for preparing soda-silica white as claimed in claim 3, wherein thesodium silicate solution is added to the reactor, the temperature is raised to 45-65 ℃ by stirring, the sodium silicate solution is added after maintaining the constant temperature, the adding speed is controlled to be 30-90 minutes, the temperature is raised to 60-85 ℃ after about 10 minutes, the constant temperature is maintained, and the reaction is terminated by stirring for 30-90 minutes.
6. The joint production method of soda ash and white carbon black as claimed in claim 1, wherein the sodium-containing compound is soda ash, the soda ash is prepared into a 10-50% solution, the 10-50% solution reacts with the silica-containing raw material at 100-340 ℃ and corresponding saturated vapor pressure to prepare a sodium silicate solution, and then the sodium silicate solution reacts with carbon dioxide or sodium bicarbonate to prepare soda ash and white carbon black.
7. The process for preparing soda-white carbon black as claimed in claim 1, wherein the sodium-containing compound is mirabilite, and the sodium sulfate is reacted with quartz sand and coke to obtain sodium silicate, which is then reacted with carbon dioxide or sodium bicarbonate to obtain soda and white carbon black.
8. The sodium silicate manufacturing method as set forth in claim 7, characterized in that sulfur dioxide generated in the sodium silicate production reaction is converted into sulfuric acid product by contact; the generated carbon dioxide is used as one of the carbon dioxide sources required by the method and is used for preparing soda ash and white carbon black.
9. The process for preparing soda ash and white carbon black as claimed in claim 1, wherein the sodium-containing compound is common salt, the silica-containing raw material is siliceous metal mineral, the common salt and the metal mineral are mixed in a required proportion in the presence of modulus regulator, and are calcined at high temperature to obtain sodium silicate, which is then reacted with carbon dioxide or sodium bicarbonate to prepare soda ash and white carbon black.
10. The process for preparing sodium silicate containing sodium compound as salt according to claim 9, wherein the salt, metal mineral and quartzite or quartz sand as modulus regulator are mixed according to the required proportion, crushed to 100 mesh or less, put into a reaction furnace, reacted at 500-1500 ℃ for 3-10 hours, the reaction is ended, the resultant melt is discharged, and the sodium silicate solution is prepared by cooling, water quenching, dissolution and solid-liquid separation; the chloride gas generated in the reaction process is either separated and recovered by condensation according to the boiling point, or converted into metal oxide and chlorine, or converted into oxide and hydrochloric acid for recovery.
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| CNB011432470A CN1190363C (en) | 2001-12-21 | 2001-12-21 | Process for preparing both sodium carbonate and silica white |
| PCT/CN2002/000891 WO2003070636A1 (en) | 2001-12-21 | 2002-12-16 | Method of producing a silica aerogel and a sodium carbonate |
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| CNB011432470A CN1190363C (en) | 2001-12-21 | 2001-12-21 | Process for preparing both sodium carbonate and silica white |
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| CN1190363C CN1190363C (en) | 2005-02-23 |
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Also Published As
| Publication number | Publication date |
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| WO2003070636A1 (en) | 2003-08-28 |
| CN1190363C (en) | 2005-02-23 |
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