Method for preparing sodium silicate by utilizing organic silicon three wastes in green recycling manner
Technical Field
The invention relates to a method for preparing sodium silicate by recycling organic silicon three wastes, belonging to the technical field of organic silicon.
Background
In the production process of the production chain of the organic silicon monomer enterprise from methyl chloride synthesis to middle and lower reaches products, a large amount of three wastes, namely waste liquid, waste solid and waste gas, can be generated. The main components of the three wastes contain silicon element or exist in the modes of silicon methyl bond, silicon chlorine bond, silicon oxygen silicon bond and the like. Most of the three wastes of the organic silicon are classified into dangerous wastes, and the treatment cost of the dangerous wastes is very high, so that the dangerous wastes do not generate benefit, but cause the waste of raw materials and occupy the production cost, and the treatment cost of the dangerous wastes is an important component of the production cost of a monomer enterprise.
The current process for preparing sodium silicate is various: high-temperature calcination of fly ash and sodium carbonate, wet reaction of quartz and caustic soda, wet reaction of rice hull ash and caustic soda and the like. From the analysis of the process characteristics of these methods, their disadvantages are as follows:
in patent CN201911396101.4, fly ash and sodium carbonate are roasted at high temperature, and then are subjected to water dissolving, decoloring and flocculant purification to prepare sodium silicate. The disadvantages of the process are: high-temperature roasting is needed, and the energy consumption is high; the need for activated carbon decolorization, how the used activated carbon is treated, which obviously increases the treatment cost; flocculants are needed, and how to recover the flocculants in the later period, the incomplete recovery inevitably causes pollution to the environment; from these points, the process disadvantage of recovering silicon element from fly ash is very obvious.
Patent CN105271276A adopts a wet process of quartz sand and caustic soda to prepare sodium silicate. And (3) dropwise adding ammonia water after the quartz reacts with the caustic soda, and then heating and reacting the silica gel and the rest caustic soda solution to prepare the sodium silicate. This process has two problems: quartz sand contains a large amount of impurity elements such as heavy metals and has color problems, how to eliminate heavy metal ions and decolor is not explicitly described in the patent, and the application of sodium silicate to other fields is limited by not decoloring and not removing impurities; by adopting the ammonia water reaction, the characteristic that the ammonia water is easy to dissolve in water inevitably causes the peculiar smell of the sodium silicate solution, so the problem of excessive ammonia water is solved, and the patent is not explicitly described.
Patent CN101456555A provides a method for recovering silicon element from rice hull ash, which is a wet method for recovering silicon dioxide. The patent first further pulverizes rice hull ash, then soaks and heats with 2mol/L (about 8%) NaOH solution to prepare sodium silicate. The patent also has the problem that the sodium silicate solution is colored and needs to be decolored after the rice hull ash is soaked. Furthermore, a new process for producing high modulus water glass and activated carbon from rice hull ash has been disclosed before the patent, and a method for recovering silica from rice hull ash is disclosed: heating and pressure up to 6 kg are required to recover silica with high leaching yield (about 90%). The operation with pressure will certainly increase the difficulty of the process production. Therefore, although the method for recovering silicon dioxide from rice hull ash is a method for recovering silicon element, the problems of operation under pressure, need of decolorization and the like cannot be solved, the method can not be used for three wastes of large-scale industrialized organic silicon monomer recovery enterprises, and the application prospect is limited.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the method for preparing the sodium silicate by recycling the organic silicon three wastes in an environment-friendly manner is scientific and reasonable in design, fully utilizes the silicon-containing three wastes, waste alkali liquor and waste acid liquor, is environment-friendly, achieves the aim of generating high-value products by 'mutual restriction of wastes', and has high industrial application value.
The method for preparing sodium silicate by utilizing the green recycled organic silicon three wastes comprises the following steps:
(1) burning the three wastes containing silicon for 1-5s at the temperature of 900-1300 ℃ to obtain solid-phase siliceous slag;
(2) mixing siliceous slag and waste alkali liquor, heating and stirring at 80-100 ℃ for 1-8h, introducing into a centrifuge, and then carrying out primary centrifugal separation on a solid-liquid phase;
(3) the liquid phase enters a stirring kettle, waste acid liquid is added into the stirring kettle, stirring is carried out for 0.5-3h, sodium silicate is converted into solid-phase silicic acid, the liquid phase is discharged (metal ions and the like are remained in the liquid phase and do not need to be decolored), and the solid-phase silicic acid is remained in the stirring kettle;
(4) adding waste alkali liquor into a stirring kettle containing solid-phase silicic acid, dissolving silicic acid again, adding toluene, heating at the temperature of 110-.
In the silicon-containing three wastes, the waste gas is waste gas generated upstream and downstream of an organic silicon monomer production enterprise and vent tail gas such as monomer synthesis vent tail gas, rectification vent tail gas, tank area vent tail gas, cracking disproportionation vent tail gas, methyl chloride synthesis, cracking pressurized tail gas, water cracking ring and downstream deep processing tail gas; the waste solids are hydrolysate of a tail gas washing system of the monomer synthesis device, pulp residue hydrolysate and semisolid viscous material of a chloromethane synthesis device; the waste liquid is slurry residue generated by synthesizing organic silicon monomer, organic silicon cracking kettle substrate, azeotrope of organic silicon monomer, organic silicon disproportionation kettle substrate, methyl silicic acid generated by a comprehensive utilization device, water washing tower oily matter and caustic sludge.
In the three wastes containing silicon, the main components are monomer or monomer mixture (both gas phase and liquid phase) containing silicon methyl and silicon-chlorine bond, and organosilicon hydrolysate (both liquid phase and solid phase) containing silicon-oxygen-silicon bond. The main component of ash slag generated by burning the components at high temperature is SiO2The siliceous slag is SiO2The incineration residue with the mass content of more than 98.5 percent has high recycling value.
The waste alkali liquor and the waste acid liquor are both generated in the production operation of the organic silicon chloromethane synthesizer.
The alkali content in the waste alkali liquor is 5-8 wt%; the HCl content in the waste acid solution is 20-27 wt%.
The reversible transformation of the silicic acid and the sodium silicate involved in the steps (3) and (4) can be repeated for 1-5 times, namely, waste acid is added to convert the sodium silicate into the silicic acid, then waste alkali liquor is added to convert the silicic acid into the sodium silicate, and finally the silicic acid is converted into the silicic acid. Repeated aim at constantly will wrap in the silicic acid heavy metal ion that is mingled with etc. and lead to solution colored impurity to dissolve in the liquid phase, ensure that silicic acid is pure, be favorable to finally obtaining colorless sodium silicate solution, save sodium silicate solution decoloration step.
In the step (4), preferably, the refluxing time with water is 0.5-5h, stirring, standing and layering are carried out, and the lower-layer sodium silicate solution has excellent fluidity and can be smoothly discharged out of the reaction kettle. The step of water reflux is used for finely adjusting the water content of the sodium silicate solution, and then the content of silicon dioxide, namely the modulus, is adjusted, so that the problem that the fluidity of the sodium silicate solution is poor due to the fact that the modulus is too high is avoided, and the product cannot be smoothly discharged out of the reaction kettle, so that production accidents are caused.
In the reversible transformation of different forms of sodium silicate and silicic acid, the chemical reaction equation involved is as follows:
the invention fully considers the composition characteristics of the three wastes of the organic silicon monomer production enterprises, traces the source, recycles the silicon element in the organic silicon three wastes in a mode of easy conversion and recovery (namely silicon dioxide), reduces the waste of the silicon element and reduces the treatment cost of the three wastes. Specifically, the three wastes mainly comprise silicon-containing monomers, monomer mixtures, hydrolysates and the like which exist in three states of gas, liquid and solid. These wastes contain a large amount of silicon elements, and the treatment cost is too high as hazardous wastes, which causes extremely high production cost for monomer generation enterprises. The invention changes the three wastes after being burnt into ash containing more than 98.5 percent of silicon dioxide component, and has high recovery value. Meanwhile, waste alkali liquor and waste acid liquor generated in the synthesis process of the organic silicon monomer chloromethane are fully utilized, reversible conversion characteristics of sodium silicate and silicic acid are utilized, silicon elements are recovered in a sodium silicate mode, the process is a green process for converting three wastes into high-quality products, the waste generated in organic silicon monomer enterprises is mutually utilized to complete preparation of the sodium silicate, and a green and environment-friendly method is provided for recycling the waste of the organic silicon monomer enterprises.
The invention aims to recover silicon element by taking silicon-containing three wastes of organic silicon monomer enterprises as raw materials and waste acid and alkali of the organic silicon monomer enterprises as auxiliaries. The modulus of the prepared sodium silicate can be specifically adjusted according to the requirements of the later application field of the sodium silicate.
Compared with the prior art, the invention achieves the following beneficial effects:
(1) the method takes the concept of environmental protection, fully utilizes the three-waste characteristic of an organic silicon monomer enterprise, namely the main component contains silicon element, and takes the waste alkali liquor and the waste acid liquor of the chloromethane synthesis device of the organic silicon monomer enterprise as the auxiliary agent for recovering the silicon element, thereby realizing the chemical reaction of the silicon-containing three wastes and the waste alkali liquor and the waste acid liquor, achieving the purpose of generating high-value products by 'mutual restriction of wastes', and having high industrial application value;
(2) the solution obtained by soaking and reacting the ash slag containing the silicon three wastes after incineration with the waste alkali liquor is brown, but the invention skillfully utilizes the reversible transformation (shown as a chemical reaction equation) of different forms of the sodium silicate and the silicic acid to fully separate the colored substances from the silicic acid, can realize the decolorization treatment of the sodium silicate solution without adopting a conventional decolorizing agent, abandons the decolorization operation and reduces the decolorization cost;
(3) according to the invention, toluene is used as a water-carrying agent, part of water is carried away from the sodium silicate solution, the formation of sodium silicate is promoted, the modulus of the sodium silicate is finely adjusted, the hidden danger that the flowability of the sodium silicate is poor and the sodium silicate cannot be discharged from production equipment due to overhigh modulus is eliminated, and the toluene can be easily separated from the sodium silicate solution through layering, so that the full recycling is realized.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The silicon-containing three wastes are burned for 1s at 950 +/-30 ℃ to obtain solid-phase siliceous slag. Mixing siliceous slag and 5 percent of waste alkali liquor, stirring for 8 hours at 80 ℃, introducing into a centrifugal machine, and carrying out primary centrifugal separation on a solid-liquid phase; the liquid phase enters a stirring kettle, 20% waste acid liquid is added into the stirring kettle and stirred for 3 hours, sodium silicate is converted into solid-phase silicic acid, the liquid phase is discharged, and the solid-phase silicic acid is left in the stirring kettle; and adding 5% of waste alkali liquor into the stirring kettle containing the solid-phase silicic acid again, dissolving the silicic acid again, adding toluene, heating at 110 ℃, refluxing and carrying water for 0.5h, layering the sodium silicate solution and the toluene, wherein the lower layer is a yellowish sodium silicate solution with good fluidity (modulus of 3.2-3.9), and the upper layer of toluene is recycled.
Example 2
The silicon-containing three wastes are incinerated for 3s at the temperature of 1000 +/-50 ℃ to obtain solid-phase siliceous ash. Mixing siliceous slag and 5% waste alkali liquor, heating at 90 deg.C, stirring, introducing into a centrifuge, and performing first centrifugal separation to obtain solid-liquid phase; the liquid phase enters a stirring kettle, 24% waste acid liquid is added into the stirring kettle and stirred for 2 hours, sodium silicate is converted into solid-phase silicic acid, the liquid phase is discharged, and the solid-phase silicic acid is left in the stirring kettle; adding 5% waste alkali solution into the stirring kettle containing solid-phase silicic acid again to dissolve silicic acid; then repeating the reaction for 1 time by using 24 percent waste acid and 5 percent waste alkali liquor to convert the sodium silicate into silicic acid and then into sodium silicate; and then adding toluene into the sodium silicate solution, heating and refluxing at 110 ℃ for 5h, layering the sodium silicate solution and the toluene, wherein the lower layer is colorless and transparent sodium silicate solution with excellent fluidity (modulus of 1.2-2.2), and the upper layer of toluene is recycled.
Example 3
After the three wastes containing silicon are incinerated for 4s at the temperature of 1100 +/-20 ℃, solid-phase siliceous slag is obtained. Mixing siliceous slag and 6% waste alkali liquor, heating at 100 deg.C, stirring, introducing into a centrifuge, and performing first centrifugal separation to obtain solid-liquid phase; the liquid phase enters a stirring kettle, 27% waste acid liquid is added into the stirring kettle and stirred for 1 hour, sodium silicate is converted into solid-phase silicic acid, the liquid phase is discharged, and the solid-phase silicic acid is left in the stirring kettle; adding 6% of waste alkali liquor into the stirring kettle containing the solid-phase silicic acid again to dissolve the silicic acid, and then repeating the steps for 2 times by using 27% of waste acid and 6% of waste alkali liquor to convert the sodium silicate into the silicic acid and then into the sodium silicate; and then adding methylbenzene into the sodium silicate solution, heating and refluxing at 130 ℃ for 3h, layering the sodium silicate solution and the methylbenzene, wherein the lower layer is a colorless and transparent sodium silicate solution with good fluidity (modulus of 2.2-2.8), and the methylbenzene on the upper layer is recycled.
Example 4
The silicon-containing three wastes are incinerated for 5s at 1250 +/-50 ℃ to obtain solid-phase siliceous slag. Mixing siliceous slag and 8% waste alkali liquor, heating at 100 deg.C, stirring, introducing into a centrifuge, and performing first centrifugal separation to obtain solid-liquid phase; the liquid phase enters a stirring kettle, 27% waste acid liquid is added into the stirring kettle and stirred for 0.5h, sodium silicate is converted into solid-phase silicic acid, the liquid phase is discharged, and the solid-phase silicic acid is left in the stirring kettle; adding 7% of waste alkali liquor into the stirring kettle containing the solid-phase silicic acid again to dissolve the silicic acid, and then repeating the steps for 3 times by using 27% of waste acid and 7% of waste alkali liquor to convert the sodium silicate into the silicic acid and then into the sodium silicate; and then adding toluene into the sodium silicate solution, heating and refluxing at 130 ℃ for 2h, layering the sodium silicate solution and the toluene, wherein the lower layer is a colorless and transparent sodium silicate solution with good fluidity (modulus of 2.8-3.2), and the upper layer of toluene is recycled.
Comparative example 1
The silicon-containing three wastes are incinerated for 3s at the temperature of 1000 +/-50 ℃ to obtain solid-phase siliceous ash. Mixing siliceous slag and 5 percent of waste alkali liquor, stirring for 8 hours at 80 ℃, introducing into a centrifugal machine, and carrying out primary centrifugal separation on a solid-liquid phase; and (3) enabling the liquid phase to enter a stirring kettle, adding methylbenzene, heating at 110 ℃, refluxing for 0.5h with water, layering the sodium silicate solution and the methylbenzene, wherein the lower layer is the sodium silicate solution which is general in fluidity (modulus is 3.1-3.8) and dark brown, and the methylbenzene on the upper layer is recycled.
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.