CN113371721A - Green and cyclic production method of silica gel - Google Patents
Green and cyclic production method of silica gel Download PDFInfo
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- CN113371721A CN113371721A CN202110825942.3A CN202110825942A CN113371721A CN 113371721 A CN113371721 A CN 113371721A CN 202110825942 A CN202110825942 A CN 202110825942A CN 113371721 A CN113371721 A CN 113371721A
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- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
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Abstract
The invention provides a green circulating production method of silica gel, which comprises the following steps: (1) producing sodium silicate by using quartz sand, sulfur-containing solid waste sodium salt and high-sulfur petroleum coke powder in a certain proportion, and producing sulfur dioxide-containing flue gas at the temperature of 250-300 ℃; (2) the flue gas containing sulfur dioxide in the step (1) enters a sulfur incinerator, sulfur and supplementary air are added to continue burning to enable the concentration of the sulfur dioxide in the flue gas to reach a certain concentration, then the flue gas enters an acid cleaning purification section for purification, is dried and dehydrated by concentrated sulfuric acid, enters a converter for catalysis and conversion into sulfur trioxide, and is finally absorbed by the concentrated sulfuric acid to obtain industrial-grade sulfuric acid; (3) and (3) producing silica gel by using the sodium silicate produced in the step (1) and the sulfuric acid produced in the step (2), desalting sodium sulfate brine produced in the silica gel production process, and using the produced sodium sulfate for producing the sodium silicate. According to the green cycle production method of the silica gel, provided by the invention, a green cycle is formed in the production process of the silica gel, and three wastes are not discharged.
Description
Technical Field
The invention relates to the field of silica gel production, and particularly relates to a green cyclic production method of silica gel.
Background
The main raw materials of the silica gel production process are sodium silicate and sulfuric acid, silicic acid gel is generated by a sol-gel method, and then washing and drying are carried out to obtain the finished product silica gel. The product of the whole production process comprises finished silica gel, sodium sulfate water and hot moisture.
Sodium silicate, is the most widely developed product in the inorganic silicon industry, is the basic raw material of other inorganic silicon products, has extremely wide application, and is almost spread in various departments of national economy. The production of this product has been gradually abandoned in developed countries, and instead imported from our developing countries or processed into downstream products in our developing countries for export, resulting in a continuous increase in the production scale in our countries in recent years. In recent two years, with the adjustment of domestic energy policies, the implementation of a policy of replacing coal with natural gas leads to the rapid rise of the production cost of sodium silicate, and some sodium silicate production enterprises originally located in Shandong, Hebei, North Jiangsu and Henan are closed in succession, and then enter areas with abundant coke oven gas resources in Shanxi, inner Mongolia and the like to rebuild plants so as to reduce the production cost.
The preparation method of the sulfuric acid comprises a sulfur method and an ore smelting method, theoretically, only sulfur-containing substances can be used for preparing the sulfuric acid, such as high-sulfur coal, sodium sulfate, high-sulfur petroleum coke and the like, and are influenced by the concentration of sulfur-containing gas generated by decomposing different sulfur-containing substances, and the existing methods for treating the sulfur-containing gas are all that alkaline liquid is directly added and sprayed to neutralize the sulfur-containing gas into sulfate and sulfite solution and then discharge the sulfate and sulfite solution, so that resource waste is caused.
Sodium sulfate salt water and hot moisture produced in the production process of silica gel are very precious renewable resources, and how to reasonably, fully and effectively utilize the resources is a key problem to be solved urgently in green production of silica gel.
Disclosure of Invention
The invention aims to provide a green circulating production method of silica gel aiming at the defects of the prior art. Based on the problems, the invention provides a green cycle production method of silica gel, and the production process of the silica gel forms green cycle without three-waste discharge.
The technical scheme of the invention is realized as follows:
a green cycle production method of silica gel comprises the following steps:
(1) reacting raw materials of quartz sand, sulfur-containing solid waste sodium salt and high-sulfur petroleum coke powder according to a certain proportion at a specific reaction temperature to generate sodium silicate, and producing sulfur dioxide-rich flue gas with the temperature of 250-300 ℃; the high-sulfur petroleum coke powder refers to petroleum coke powder with the sulfur content of more than 4 percent by mass;
(2) the flue gas rich in sulfur dioxide in the step (1) enters a sulfur incinerator, sulfur is added to improve the flue gas rich in sulfur dioxide and an appropriate amount of air is supplemented for continuous combustion, so that the sulfur dioxide in the flue gas leaving the sulfur incinerator reaches a certain concentration, then the flue gas enters an acid cleaning purification section for purification, concentrated sulfuric acid is dried and dehydrated, then the flue gas enters a converter and is converted into sulfur trioxide under the catalysis of a catalyst, and finally the sulfur trioxide is absorbed by the concentrated sulfuric acid to obtain industrial-grade sulfuric acid;
(3) and (3) producing silica gel by using the sodium silicate produced in the step (1) and the sulfuric acid produced in the step (2). The sodium sulfate aqueous solution of output carries out the desalination processing through water processing system in the silica gel production process, and the water backward flow after the desalination is used for the silica gel washing, and the sodium sulfate of output can be used for the soda production of steeping, and the hot humid gas of silica gel stoving output carries out the temperature through heat recovery utilization system and promotes, and the reuse is dried in the silica gel, forms green circulation.
In the green cycle production method of silica gel, the sulfur-containing solid waste sodium salt in the step (1) is one or more of sodium salts such as sodium sulfate, sodium thiosulfate, sodium thiocyanate and sodium sulfite.
According to the green cycle production method of silica gel, in the step (1), the mass ratio of the quartz sand, the sulfur-containing solid waste sodium salt and the high-sulfur petroleum coke powder is 7: 4.3: 2-8: 4.8: 3.
according to the green cycle production method of silica gel, continuous reaction is adopted in the step (1), and the retention time of raw materials in the furnace is 22-26 hours.
According to the green cycle production method of silica gel, the specific reaction temperature in the step (1) is 1350-1450 ℃.
According to the green circulating production method of silica gel, sulfur is added in the step (2) to improve the concentration of sulfur dioxide in sulfur-containing flue gas to 5.5-8%.
According to the green circulating production method of silica gel, the specific step of the sulfuric acid pickling purification section purification in the step (2) is to remove a small amount of sodium sulfate and other dust in the flue gas and reduce the temperature to 35-40 ℃.
In the green cycle production method of silica gel, the catalyst in the step (2) is a vanadium catalyst.
According to the green circulating production method of silica gel, the temperature of the final concentrated sulfuric acid continuous absorption in the step (2) is 55-65 ℃.
In the green cycle production method of silica gel, the concentration of the industrial-grade sulfuric acid in the step (2) is 93 plus or minus 0.5% or 98 plus or minus 0.5%.
The invention has the following advantages and beneficial effects:
(1) the sodium sulfate brine produced in the production process of the silica gel is desalted through the water treatment system, the desalted water flows back and is used for washing the silica gel, the produced salt is used for producing sodium silicate, the hot moisture produced by drying the silica gel is subjected to temperature rise through the heat recycling system and is reused for drying the silica gel, and the silica gel forms green circulation in the production process and has no three-waste discharge.
(2) The invention utilizes quartz sand and sulfur-containing solid waste sodium salt as raw materials, and high-sulfur petroleum coke powder as a heat source to finally obtain sodium silicate, and sulfur-containing flue gas for producing sodium silicate is used for producing sulfuric acid.
(3) The sodium salt containing sulfur is used for replacing carbonate to prepare sodium silicate, so that the emission of carbon dioxide is reduced, and the carbon neutralization target can be realized early.
Drawings
FIG. 1 is a flow chart of the process steps of a green cycle production method of silica gel according to the present invention;
FIG. 2 is a flow chart of a green cycle production method of silica gel provided by the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the contents in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
A green cycle production method of silica gel comprises the following steps:
(1) the method comprises the following steps of producing sodium silicate by using quartz sand, sulfur-containing solid waste sodium salt and high-sulfur petroleum coke powder (sulfur content is more than 4%) as raw materials in a certain proportion at a specific reaction temperature for a certain reaction time, and producing sulfur dioxide-rich flue gas at the temperature of 250-300 ℃;
(2) the flue gas rich in sulfur dioxide in the step (1) enters a sulfur incinerator, sulfur and supplementary air are added to continuously burn to improve the concentration of the sulfur dioxide in the flue gas rich in sulfur dioxide to reach a certain concentration, then the flue gas enters an acid cleaning purification section for purification, concentrated sulfuric acid is dried and dehydrated, then the flue gas enters a converter and is converted into sulfur trioxide under the catalysis of a catalyst, and finally the sulfur trioxide is absorbed by the concentrated sulfuric acid to obtain industrial-grade sulfuric acid;
(3) silica gel is produced with the sodium silicate of step (1) production and the sulphuric acid of step (2) production, and the sodium sulfate salt water of output carries out desalination through water treatment system in the silica gel production process, and the water backward flow after the desalination is used for water treatment system's silica gel washing, and the salt of output can be used for the sodium silicate production, and the hot humid gas of silica gel stoving output carries out the temperature through heat recovery utilization system and promotes, and the reuse is dried for silica gel, forms green circulation.
The principle of the invention is as follows: the sulfur in the industrial high-sulfur solid waste is used as a sulfuric acid source of the raw material for producing the silica gel, the process of spraying and absorbing the sulfur dioxide-rich flue gas into sulfate by using the alkaline liquor is optimized to the process of purifying and absorbing the sulfur-rich flue gas to prepare sulfuric acid after the sulfur concentration of the flue gas is improved, the sulfur is recycled in the industrial chain of producing the silica gel, and the emission of the solid waste is reduced.
Preferably, the sulfur-containing solid waste sodium salt in the step (1) is one or more of sodium salts such as sodium sulfate, sodium thiosulfate, sodium thiocyanate and sodium sulfite. More preferably, the mass ratio of the quartz sand, the sulfur-containing solid waste sodium salt and the high-sulfur petroleum coke powder in the step (1) is 7: 4.3: 2-8: 4.8: 3. more preferably, the ratio of the quartz sand, the sulfur-containing solid waste sodium salt and the high-sulfur petroleum coke powder in the step (1) is 8:4.8: 3.
preferably, the step (1) is a continuous reaction, and the residence time of the raw materials in the furnace is 22-26 hours. Under the technical scheme, sufficient time is provided for full reaction among the raw materials, so that the content of insoluble substances in the sodium silicate at the later stage is reduced, and the quality and yield of the sodium silicate are improved.
Preferably, the specific reaction temperature in the step (1) is 1350-1450 ℃. Under the technical scheme, sulfur-containing solid waste salt and quartz sand fully react at the temperature, the quartz sand is a hard, wear-resistant and chemically stable silicate mineral, the internal index performance of the generated sodium silicate depends on the accurate control of the furnace temperature and time, and the incomplete reaction can be caused when the temperature is lower than 1350 ℃ and the reaction time is lower than 22 hours; the temperature is higher than 1450 ℃, the reaction time is longer than 26 hours, coking in the furnace can be caused, and the normal use of the equipment is influenced.
Preferably, the sulfur is added in the step (2) to improve the concentration of sulfur dioxide in the sulfur-containing flue gas to 5.5-8%. Under the technical scheme, the method is the optimal concentration range for self-heating production of sulfuric acid by a sulfur dioxide contact method, and the concentration is high in acid preparation conversion rate and good in absorption effect.
Preferably, the specific step of the sulfuric acid cleaning and purifying section in the step (2) is to remove a small amount of sodium sulfate and other dust in the flue gas and reduce the temperature to 35-40 ℃.
Preferably, the catalyst in the step (2) is a vanadium catalyst. Under this technical scheme, vitriol catalyst is the catalyst that is widely used in sulphuric acid production facility, mainly converts sulfur dioxide into sulfur trioxide, and this catalyst catalytic efficiency is high, and long service life, conversion rate are guaranteed.
Preferably, the temperature of the final continuous absorption by concentrated sulfuric acid in the step (2) is 55-65 ℃. The temperature of 55-65 ℃ is the optimum temperature for continuous absorption of concentrated sulfuric acid, and the concentrated sulfuric acid contains a large amount of unionized sulfuric acid molecules, has dehydration property and is often used as a drying agent. Concentrated sulfuric acid can combine with water to produce hydrate with different composition and release heat. The hydrate of sulfuric acid has H2SO4·H2O、H2SO4·2H2O、H2SO4·4H2O, etc., when the temperature is lower than 55 ℃, the hydrates are separated out in a crystal form, and when the temperature is higher than 65 ℃, the heat waste is caused, and the bumping risk is easily generated.
Preferably, the concentration of the industrial-grade sulfuric acid in the step (2) is 93 plus or minus 0.5% or 98 plus or minus 0.5%.
Example 1
(1) The method comprises the following steps of mixing raw materials of quartz sand, sulfur-containing solid waste sodium salt and high-sulfur petroleum coke powder according to a mass ratio of 7: 4.3: 2, uniformly mixing and adding the mixture into a regenerative reverberatory furnace, controlling the feeding speed to stay in the furnace for 24 hours, keeping the furnace temperature at 1380 ℃, overflowing generated sodium silicate molten salt from a discharge hole, and cooling by water quenching to obtain sodium silicate with the modulus of 3.2 and the mass fraction of water-insoluble substances of 1.64%; the outlet temperature of the reverberatory furnace tail gas is 248 ℃. And producing the flue gas which contains 2.17 percent of sulfur dioxide by volume and is rich in sulfur dioxide at the temperature of 250-300 ℃.
(2) The flue gas rich in sulfur dioxide in the step (1) enters a sulfur incinerator, the flue gas is sprayed into the sulfur incinerator through a liquid sulfur spray gun at the speed of adding 45 kilograms of molten sulfur into every thousand cubic meters of flue gas and is continuously combusted at the temperature of 1000 ℃, the flue gas at the outlet of the sulfur incinerator is cooled to 248 ℃ after heat is recovered by a waste heat boiler, the concentration of sulfur dioxide in the flue gas reaches 5.6% by volume, then the flue gas enters an acid cleaning section to be cleaned to remove dust in the flue gas and is cooled to about 35 ℃, the flue gas is dried and dehydrated by concentrated sulfuric acid, then the flue gas enters a converter and is converted into sulfur trioxide by a vanadium catalyst, and finally the concentrated sulfuric acid with the mass fraction of 98% is absorbed in an absorption tower at the temperature of 60 ℃ to obtain industrial-grade sulfuric acid, the concentration of the industrial-grade sulfuric acid is 92.5%, and the qualified product meets the specification of GB/T534-.
(3) With the sodium silicate of step (1) production and the sulphuric acid production coarse pore silica gel of step (2), the sodium sulfate salt water of output carries out the desalination through water treatment system in the silica gel production process, and the water reflux after the desalination is used for water treatment system's silica gel washing, and the salt of output is used for the sodium silicate production, and the hot humid gas of silica gel stoving output carries out the temperature through heat recovery utilization system and promotes, and the reuse is dried in the silica gel, forms green circulation. The material ratios and reaction conditions of this example are shown in Table 1. The process flow chart of the green cycle production method of silica gel provided by the invention is shown in figure 1. The flow block diagram of the green cycle production method of silica gel provided by the invention is shown in figure 2.
Example 2
(1) Uniformly mixing raw materials including quartz sand, sulfur-containing solid waste sodium salt and high-sulfur petroleum coke powder according to a mass ratio of 8:4.8:3, adding the mixture into a heat accumulating type reverberatory furnace, controlling the feeding speed to stay in the furnace for 26 hours, keeping the furnace temperature at 1420 ℃, overflowing generated sodium silicate molten salt from a discharge hole, and cooling the sodium silicate molten salt through water quenching to obtain sodium silicate with a modulus of 3.3 and a mass fraction of water-insoluble substances of 1.25%; and producing the flue gas which contains 3.54 percent of sulfur dioxide by volume and is rich in sulfur dioxide at the temperature of 250-300 ℃.
(2) The flue gas rich in sulfur dioxide in the step (1) enters a sulfur incinerator, sulfur is added in the embodiment 1 to improve the concentration of sulfur dioxide in the flue gas rich in sulfur dioxide to 6.5% by volume fraction, then the flue gas enters an acid cleaning and purifying section to remove a small amount of sodium sulfate and other dust in the flue gas and is cooled to about 38 ℃, then the flue gas is dried and dehydrated by concentrated sulfuric acid, then the flue gas enters a converter and is converted into sulfur trioxide by adopting a vanadium catalyst, and finally the flue gas is continuously absorbed by the concentrated sulfuric acid with the mass fraction of 98% at 55 ℃ to obtain industrial-grade sulfuric acid, wherein the concentration of the industrial-grade sulfuric acid is 93.5%, and the industrial-grade sulfuric acid meets the qualified products;
(3) with the sodium silicate of step (1) production and the sulphuric acid production coarse pore silica gel of step (2), the sodium sulfate salt water of output carries out the desalination through water treatment system in the silica gel production process, and the water reflux after the desalination is used for water treatment system's silica gel washing, and the salt of output is used for the sodium silicate production, and the hot humid gas of silica gel stoving output carries out the temperature through heat recovery utilization system and promotes, and the reuse is dried in the silica gel, forms green circulation. The material ratios and reaction conditions of this example are shown in Table 1.
Example 3
(1) Uniformly adding raw materials of quartz sand, sulfur-containing solid waste sodium salt and high-sulfur petroleum coke powder into a heat accumulating type reverberatory furnace according to the mass ratio of 7:4.5:3, controlling the feeding speed to stay in the furnace for 23 hours, reacting at 1380 ℃ for 23 hours to produce the modulus of 3.1, wherein the mass fraction of water-insoluble substances is 1.74% of sodium silicate, and producing sulfur-containing flue gas containing 4.11% of sulfur dioxide by volume and at the temperature of 250-300 ℃;
(2) the sulfur-containing flue gas in the step (1) enters a sulfur incinerator, sulfur is added in the embodiment 1 to improve the concentration of sulfur dioxide in the sulfur-containing flue gas to 6.0% by volume fraction, then the flue gas enters an acid cleaning and purifying working section to remove a small amount of sodium sulfate and other dust in the flue gas and is cooled to about 35 ℃, then the flue gas is dried and dehydrated by concentrated sulfuric acid, then the flue gas enters a converter to be converted into sulfur trioxide by a vanadium catalyst, and finally the flue gas is absorbed by the concentrated sulfuric acid with the mass fraction of 98% at 65 ℃ for continuous absorption to obtain industrial-grade sulfuric acid, wherein the concentration of the industrial-grade sulfuric acid is 93.0%, and the qualified product meets the specification of GB/T534-;
(3) with the sodium silicate of step (1) production and the sulphuric acid production coarse pore silica gel of step (2), the sodium sulfate salt water of output carries out the desalination through water treatment system in the silica gel production process, and the water reflux after the desalination is used for water treatment system's silica gel washing, and the salt of output is used for the sodium silicate production, and the hot humid gas of silica gel stoving output carries out the temperature through heat recovery utilization system and promotes, and the reuse is dried in the silica gel, forms green circulation. The material ratios, reaction conditions and test results of this example are shown in table 1.
Comparative example 1:
(1) raw materials of quartz sand and sodium carbonate salt are mixed according to a mass ratio of 7: 3.1, uniformly mixing and adding the mixture into a regenerative reverberatory furnace, controlling the feeding speed to stay in the furnace for 24 hours, keeping the furnace temperature at 1380 ℃ (taking coking gas as a heat source), overflowing generated sodium silicate molten salt from a discharge hole, quenching with water and cooling to obtain sodium silicate with the modulus of 3.2 and the mass fraction of water-insoluble substances of 1.35%; the outlet temperature of the tail gas of the reverberatory furnace is 248 ℃. And (3) producing the carbon dioxide flue gas with the temperature of 250-300 ℃.
(2) The molten sulfur is sprayed into a sulfur burning furnace to be continuously burned at the temperature of 1000 ℃, after the heat of the gas at the outlet of the sulfur burning furnace is recovered by a waste heat boiler, the temperature of the flue gas is reduced to 248 ℃, the concentration of sulfur dioxide in the flue gas reaches 5.6 percent by volume, then the flue gas is reduced to about 35 ℃, dried and dehydrated by concentrated sulfuric acid, then the flue gas enters a converter to be converted into sulfur trioxide by adopting a vanadium catalyst, and finally 98 percent concentrated sulfuric acid is absorbed in an absorption tower at the temperature of 60 ℃ to obtain industrial-grade sulfuric acid, the concentration of the industrial-grade sulfuric acid is 92.5 percent, and the industrial-grade sulfuric acid meets the qualified products specified in GB/T534-2014.
(3) With the sodium silicate of step (1) production and the sulphuric acid production coarse pore silica gel of step (2), the sodium sulfate salt water of output carries out the desalination through water treatment system in the silica gel production process, and the water reflux after the desalination is used for water treatment system's silica gel washing, and the salt of output is used for the sodium silicate production, and the hot humid gas of silica gel stoving output carries out the temperature through heat recovery utilization system and promotes, and the reuse is dried in the silica gel, forms green circulation. The material ratio, the reaction conditions and the detection results of the comparative example are shown in table 1.
Comparative example 2:
(1) raw materials of quartz sand and sodium hydroxide are mixed according to a mass ratio of 7: 9.3, uniformly mixing and adding the mixture into a reaction kettle, controlling the feeding speed to stay in the reaction kettle for 26 hours, keeping the temperature of the kettle at 180 ℃, and overflowing generated sodium silicate liquid from a discharge hole to obtain sodium silicate with the modulus of 1.0 and the mass fraction of water-insoluble substances of 1.46 percent.
(2) The molten sulfur is sprayed into a sulfur burning furnace to be continuously burned at the temperature of 1000 ℃, after the heat of the flue gas at the outlet of the sulfur burning furnace is recovered by a waste heat boiler, the temperature of the flue gas is reduced to 248 ℃, the concentration of sulfur dioxide in the flue gas reaches 6.5 percent by volume, then the flue gas is reduced to about 35 ℃, dried and dehydrated by concentrated sulfuric acid, then the flue gas enters a converter to be converted into sulfur trioxide by adopting a vanadium catalyst, and finally 98 percent concentrated sulfuric acid is absorbed in an absorption tower at the temperature of 55 ℃ to obtain industrial-grade sulfuric acid, the concentration of the industrial-grade sulfuric acid is 92.8 percent, and the industrial-grade sulfuric acid meets the qualified products specified in GB/T534-2014.
(3) With the sodium silicate of step (1) production and the sulphuric acid production coarse pore silica gel of step (2), the sodium sulfate salt water of output carries out the desalination through water treatment system in the silica gel production process, and the water reflux after the desalination is used for water treatment system's silica gel washing, and the salt of output is used for the sodium silicate production, and the hot humid gas of silica gel stoving output carries out the temperature through heat recovery utilization system and promotes, and the reuse is dried in the silica gel, forms green circulation. The material ratio, the reaction conditions and the detection results of the comparative example are shown in table 1.
Comparative example 3:
(1) uniformly mixing raw materials quartz sand and sodium carbonate according to a mass ratio of 7:3.3, adding the mixture into a regenerative reverberatory furnace, controlling the feeding speed to stay for 23 hours in the furnace, reacting at a temperature of 1380 ℃ for 23 hours to obtain a production modulus of 3.1, producing sodium silicate with a mass fraction of water-insoluble substances of 1.59%, and producing carbon dioxide-containing flue gas with a temperature of 250-300 ℃;
(2) selecting gas with the concentration of sulfur dioxide in the metallurgical industry reaching 6.0% in volume fraction, entering an acid cleaning section for cleaning to remove a small amount of sodium sulfate and other dust in flue gas, cooling to about 40 ℃, then drying and dehydrating by concentrated sulfuric acid, then entering a converter for converting into sulfur trioxide by adopting a vanadium catalyst, and finally continuously absorbing at 65 ℃ by using the concentrated sulfuric acid to obtain industrial-grade sulfuric acid, wherein the concentration of the industrial-grade sulfuric acid is 92.6%, and the industrial-grade sulfuric acid meets the qualified product specified in GB/T534-;
(3) with the sodium silicate of step (1) production and the sulphuric acid production coarse pore silica gel of step (2), the sodium sulfate salt water of output carries out the desalination through water treatment system in the silica gel production process, and the water reflux after the desalination is used for water treatment system's silica gel washing, and the salt of output is used for the sodium silicate production, and the hot humid gas of silica gel stoving output carries out the temperature through heat recovery utilization system and promotes, and the reuse is dried in the silica gel, forms green circulation. The material ratio, the reaction conditions and the detection results of the comparative example are shown in table 1.
TABLE 1 raw materials, reaction conditions and product test results of the present invention
As can be seen from Table 1, the purity of the sulfuric acid prepared by the high-sulfur solid waste flue gas absorption acid preparation method is consistent with that of the sulfuric acid produced by the pure sulfur method and the metallurgical flue gas absorption method in the comparative example, and meets the standard of industrial sulfuric acid; the modulus of the sodium silicate prepared by quartz sand and high-sulfur solid waste salt is consistent with that produced by a soda ash method, the silica gel productivity can be ensured, and the process adds high-sulfur petroleum coke powder, so that the water insoluble substance is slightly higher than that produced by the soda ash method, and the insoluble substance can be further processed to be used as a heat insulation material; the raw materials generated by the process are used for synthesizing the silica gel product, the appearance and the inner hole structure of the obtained silica gel can meet the requirements of coarse-hole silica gel, the pore volume and the specific surface are higher than those of products produced by other processes, the yield of sodium silicate produced by a wet method is higher than that of sodium silicate produced by a wet method, and the appearance of the silica gel produced by metallurgical flue gas acid is white. The process realizes the green production circulation of the silica gel, and reduces the carbon dioxide emission of the upstream and downstream industries of the silica gel.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A green cycle production method of silica gel is characterized by comprising the following steps:
(1) reacting raw materials of quartz sand, sulfur-containing solid waste sodium salt and high-sulfur petroleum coke powder according to a certain proportion at a specific reaction temperature to generate sodium silicate, and producing sulfur dioxide-rich flue gas with the temperature of 250-300 ℃;
(2) the flue gas rich in sulfur dioxide in the step (1) enters a sulfur incinerator, sulfur is added to improve the flue gas rich in sulfur dioxide and an appropriate amount of air is supplemented for continuous combustion, so that the sulfur dioxide in the flue gas leaving the sulfur incinerator reaches a certain concentration, then the flue gas enters an acid cleaning purification section for purification, concentrated sulfuric acid is dried and dehydrated, then the flue gas enters a converter and is converted into sulfur trioxide under the catalysis of a catalyst, and finally the sulfur trioxide is absorbed by the concentrated sulfuric acid to obtain industrial-grade sulfuric acid;
(3) and (3) producing silica gel by using the sodium silicate produced in the step (1) and the sulfuric acid produced in the step (2).
2. The green cycle production method of silica gel as claimed in claim 1, wherein the sulfur-containing solid waste sodium salt in step (1) is one or more of sodium salts such as sodium sulfate, sodium thiosulfate, sodium thiocyanate, sodium sulfite and the like.
3. The green cycle production method of silica gel as claimed in claim 1, wherein the mass ratio of the quartz sand, the sulfur-containing solid waste sodium salt and the high-sulfur petroleum coke powder in the step (1) is 7: 4.3: 2-8: 4.8: 3.
4. the green cycle production method of silica gel according to claim 1, wherein the step (1) is a continuous reaction, and the residence time of the raw materials in the furnace is 22-26 hours.
5. The green cycle production method of silica gel as claimed in claim 1, wherein the specific reaction temperature in step (1) is 1350-1450 ℃.
6. The green cycle production method of silica gel as claimed in claim 1, wherein the sulfur is added in the step (2) to increase the concentration of sulfur dioxide in the sulfur-containing flue gas to 5.5-8%.
7. The green cycle production method of silica gel as claimed in claim 1, wherein the specific step of cleaning in the acid cleaning and purification section of sulfuric acid in step (2) is to remove a small amount of sodium sulfate and other dust in the flue gas and cool the temperature to 35-40 ℃.
8. The green cycle production method of silica gel as claimed in claim 1, wherein the catalyst in step (2) is vanadium catalyst.
9. The green recycling production method of silica gel as claimed in claim 1, wherein the temperature of the final concentrated sulfuric acid absorption in step (2) is 55-65 ℃.
10. The method for green cycle production of silica gel according to claim 1, wherein the concentration of industrial-grade sulfuric acid in step (2) is 93 ± 0.5% or 98 ± 0.5%.
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