CN114380296A - Method and device for producing precipitated white carbon black and formate - Google Patents

Method and device for producing precipitated white carbon black and formate Download PDF

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CN114380296A
CN114380296A CN202111636433.2A CN202111636433A CN114380296A CN 114380296 A CN114380296 A CN 114380296A CN 202111636433 A CN202111636433 A CN 202111636433A CN 114380296 A CN114380296 A CN 114380296A
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formate
carbon black
reaction
reaction kettle
white carbon
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CN114380296B (en
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王君如
周航
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Sichuan Mabian Longtai Phosphorus And Electricity Co ltd
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Sichuan Mabian Longtai Phosphorus And Electricity Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/40—Carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part

Abstract

The invention provides a method and a device for producing precipitated white carbon black and formate, and aims to solve the problems of high raw material cost, low byproduct recovery benefit, environmental protection hidden danger in wastewater discharge and the like in the existing precipitated white carbon black production. The method comprises the following steps: CO purification treatment: obtaining CO purified gas; carbonylation synthesis: carrying out carbonylation reaction on CO purified gas and silicate solution to obtain a solid-liquid mixture of precipitated white carbon black and formate; and (3) product separation preparation: and carrying out solid-liquid separation on the obtained solid-liquid mixture of the precipitated white carbon black and the formate, washing and drying the solid phase to obtain a precipitated white carbon black product, and concentrating the liquid phase to obtain a formate product. According to the method, two products of precipitated white carbon black and formate are generated by reacting CO with a silicate solution, so that the value of the product is increased, carbon fixation and emission reduction are realized by utilizing CO, the use of sulfuric acid is omitted, the emission of wastewater is reduced, and the effects of consumption reduction, value increase, energy conservation and emission reduction are achieved.

Description

Method and device for producing precipitated white carbon black and formate
Technical Field
The present invention belongs to precipitated Silica (SiO)2·nH2O), in particular to a method and a device for producing precipitated white carbon black and formate.
Background
Precipitated Silica (SiO)2·nH2O) is a white powder in appearance, insoluble in water and acid, soluble in strong base and hydrofluoric acid, and has excellent characteristics of porosity, large internal surface area, high dispersibility, light weight, good chemical stability, high temperature resistance, non-flammability, no toxicity, no odor, good electrical insulation, and the like. It is used as reinforcing filler in rubber industry, mainly for shoes, tyres and other light-colored rubber products. Can be used as a carrier or a flowing agent in the industries of pesticide, feed and the like, can be used as a rubbing agent in toothpaste, and can be used as a dispersing agent, an anti-settling agent or a delustering agent in the coating industry.
At present, the white carbon black is prepared by a precipitation reaction method of silicate (usually sodium silicate, commonly called 'sodium silicate') and inorganic acid (mainly sulfuric acid and a few hydrochloric acid) in production, and the reaction formula is as follows:
Na2O·mSiO2+H2SO4+nH2O→Na2SO4+mSiO2·nH2O↓+H2O
the precipitated white carbon black produced by the method has the problem of high cost, and 1.3t of sodium silicate with the modulus of 3.3-3.4 and 0.5t of sulfuric acid with the concentration of 98 percent are consumed for producing 1 ton of precipitated white carbon black; meanwhile, about 30-35m of byproduct can be produced when 1 ton of precipitated white carbon black is produced3The wastewater containing sodium sulfate (or sodium chloride) has low value and high recovery cost, and the wastewater containing sodium sulfate (or sodium chloride) is mostly discharged by simple treatment in production, so the wastewater containing sodium sulfate (or sodium chloride) has hidden danger of environmental protection.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method and a device for producing precipitated white carbon black and formate, and solves the technical problems of high raw material cost, low byproduct recovery benefit, environmental protection hidden trouble in wastewater discharge and the like in the existing precipitated white carbon black production process.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for producing precipitated silica and formate comprises the following steps:
step S1, CO purification treatment: obtaining CO purified gas;
step S2, carbonylation synthesis: carrying out carbonylation reaction on the CO purified gas and a silicate solution to obtain a solid-liquid mixture of precipitated white carbon black and formate;
step S3, separating and preparing products: and carrying out solid-liquid separation on the obtained solid-liquid mixture of the precipitated white carbon black and the formate, washing and drying the solid phase to obtain a precipitated white carbon black product, and concentrating the liquid phase to obtain a formate product.
The reaction mechanism of the present invention is as follows:
(1) oxo synthesis of formic acid
H2O+CO→HCOOHΔH＝-24.547kJ/mol
(2) Reaction of formic acid with sodium silicate
2HCOOH+Na2O·mSiO2+xH2O→2NaHCOO+mSiO2·nH2O ↓ (white carbon black)
Among them, sodium formate is an organic carboxylate, which is white crystal or powder and widely used in production. Sodium formate can be used for producing sodium hydrosulfite, oxalic acid and formic acid; in the leather industry as camouflage acid in chrome tanning processes, in catalysts and stable synthesis agents, reducing agents in the printing industry. The industrial production of sodium formate mainly comprises the following steps of carrying out carbonylation reaction on carbon monoxide and sodium hydroxide solution at 160-200 ℃ and under 2Mpa pressure to generate sodium formate, concentrating, crystallizing, separating and drying reaction liquid to obtain a sodium formate product, wherein the reaction formula is as follows:
CO+NaOH→NaCOOH
the reaction only obtains a single sodium formate product, and the cost is higher.
Compared with the prior art, the invention has the innovation points that the precipitated white carbon black is produced by adopting CO to replace sulfuric acid (or other acids), the consumption of the sulfuric acid is saved, two high value-added products of the precipitated white carbon black and formate are obtained simultaneously in the carbonylation synthesis, and the value increase of the product is realized; the method has no wastewater discharge, can fix carbon and reduce emission, and really achieves the purposes of reducing material consumption and waste discharge.
Further, in step S1, CO purification treatment: obtaining a CO purified gas, specifically comprising:
step S110, washing the industrial furnace gas rich in CO with water, alkali and water in sequence to remove harmful impurities and obtain cleaner tail gas;
and S120, further purifying the obtained tail gas by adopting pressure swing adsorption to obtain CO purified gas with the purity of more than or equal to 96 percent.
Further, the CO-rich industrial furnace gas comprises one or more of blast furnace gas, yellow phosphorus electric furnace tail gas, calcium carbide furnace tail gas, coke oven tail gas or coal converted gas;
and/or the presence of a gas in the gas,
the sulfur-containing phosphorus compound, the sulfur-containing compound and the NO in the CO purified gas are less than or equal to 2ppm and less than or equal to 2ppmX≤10ppm，CO2≤0.3％，N2≤3.0％。
Compared with the prior art, the invention has the another innovation point that the CO purified gas is purified by using industrial furnace gas rich in CO, so that the carbon recycling is realized by the production of CO, the purpose of carbon emission reduction is achieved, and the environmental protection pressure is reduced.
Further, in step S2, the carbonylation synthesis: and carrying out carbonylation reaction on the CO purified gas and a silicate solution to obtain a solid-liquid mixture of precipitated white carbon black and formate, and specifically comprising the following steps:
s210, pressurizing the CO purified gas to 2.0-3.0Mpa, and sending the CO purified gas into a reaction kettle filled with silicate solution, wherein the concentration of the silicate solution is 5.0-20.0%;
step S220, controlling the reaction temperature at 160-220 ℃ and the reaction pressure at 2.0-3.0Mpa, and carrying out carbonylation reaction for 10-240 min;
and step S230, detecting the pH value of the reaction material, and ending the reaction when the pH value of the reaction material is less than or equal to 8.
Further, in step S2, the carbonylation synthesis: and carrying out carbonylation reaction on the CO purified gas and a silicate solution to obtain a solid-liquid mixture of precipitated white carbon black and formate, and further comprising the following steps:
and S240, cooling the reaction material after the reaction to 60-90 ℃, and aging for 30-120min to obtain a solid-liquid mixture of precipitated white carbon black and formate.
Further, in the step S210, the purified CO gas is pressurized to 2.0 to 3.0Mpa, and is fed into a reaction kettle filled with a silicate solution, wherein the concentration of the silicate solution is 5.0 to 20.0%, and the method specifically includes:
step S211, adding the silicate solution into the reaction kettle, and stirring;
s212, introducing saturated steam into the reaction kettle, preheating the silicate solution, and simultaneously replacing air at the upper part in the reaction kettle;
s213, after the air in the reaction kettle is replaced to the oxygen content of less than or equal to 0.5 percent and the preheating temperature of the silicate solution is 170-180 ℃, pressurizing the CO purified gas to 2.0-3.0Mpa and sending the CO purified gas into the reaction kettle for carbonylation.
In the invention, the reaction of synthesizing formic acid by carbonyl needs to be triggered at a certain temperature, a reaction kettle is used as a container for reaction, saturated steam is introduced for preheating, and the carbonylation reaction can be triggered by ensuring that CO purified gas is introduced; in the early preheating stage, the air in the reaction kettle is replaced to ensure that the oxygen content is less than or equal to 0.5 percent, so that the explosion risk is avoided when CO purified gas is introduced, and the efficient and rapid implementation of the carbonylation reaction is ensured.
Further, in step S3, the product is separated and prepared: and carrying out solid-liquid separation on the obtained solid-liquid mixture of the precipitated white carbon black and formate, washing and drying the solid phase to obtain a precipitated white carbon black product, and concentrating the liquid phase to obtain a formate product, wherein the method specifically comprises the following steps:
step S310, performing filter pressing separation on the obtained solid-liquid mixture of the precipitated white carbon black and formate by using a membrane filter press to obtain a filter cake and filtrate;
step S320, washing the filter cake in a multi-stage countercurrent washing mode until the conductivity of the final washing liquid is less than or equal to 500 mu S/cm, and obtaining a clean filter cake;
s330, pulping, spraying and drying the clean filter cake to obtain a precipitated white carbon black product;
step S340, concentrating, crystallizing, separating and drying the filtrate and the washing concentrated solution to obtain a formate product; the concentration adopts any one of membrane filtration concentration, MVR evaporation concentration or multi-effect evaporation concentration.
Further, the silicate solution is a sodium silicate solution or a potassium silicate solution;
the formate is sodium formate or potassium formate;
the modulus of the silicate in the silicate solution is 1.0-3.4.
The method is suitable for producing precipitated white carbon black and sodium formate products, and is also suitable for producing precipitated white carbon black and potassium formate products.
An apparatus for producing precipitated silica and formate suitable for use in any one of the above methods for producing precipitated silica and formate, the apparatus comprising:
a reaction kettle having a stirrer, a steam inlet, a silicate solution inlet, a CO gas inlet, a vent, and a discharge outlet.
Further, the reaction kettles comprise a plurality of reaction kettles which are connected in series;
the exhaust port of the non-first-stage reaction kettle is communicated with the CO gas inlet of the previous-stage reaction kettle;
the discharge port of the non-final-stage reaction kettle is connected with the subsequent-stage reaction kettle;
wherein the silicate solution is added from a silicate solution inlet of the first-stage reaction kettle; the CO purified gas is added from a CO gas inlet of the reaction kettle at the last stage; exhausting residual gas from an exhaust port of the first-stage reaction kettle; and discharging the reacted materials from a discharge port of the reaction kettle at the final stage.
The method of the invention can adopt a single reaction kettle to carry out intermittent process production, and also can adopt a plurality of reaction kettles to be combined in series or in parallel to realize continuous process production; the applicability and the adaptability are strong, and the popularization and the application are easy.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present application, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a block diagram of a process for producing precipitated silica and formate according to the present invention.
FIG. 2 is a schematic structural view of a single reactor in example 2 of the present invention.
FIG. 3 is a schematic structural view of a plurality of reaction vessels connected in series in example 3 of the present invention.
Reference numerals:
1. a reaction kettle; 11. a stirrer; 12. a steam inlet; 13. a silicate solution inlet; 14. a CO gas inlet; 15. an exhaust port; 16. a discharge outlet.
Detailed Description
In the following, only certain exemplary embodiments have been described briefly, as those skilled in the art will recognize that the described embodiments may be modified in various different ways without departing from the spirit or scope of the embodiments of the invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.
Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
As shown in fig. 1, an embodiment of the present invention provides a method for producing precipitated silica and formate, including the following steps:
step S1, CO purification treatment: obtaining CO purified gas for later use.
Step S2, carbonylation synthesis: and (4) carrying out carbonylation reaction on the CO purified gas obtained in the step (S1) and a silicate solution to obtain a solid-liquid mixture of precipitated white carbon black and formate.
Step S3, separating and preparing products: carrying out solid-liquid separation on the solid-liquid mixture of the precipitated white carbon black and the formate obtained in the step S2, and washing, drying and the like on a solid phase to obtain a precipitated white carbon black product; and concentrating and drying the liquid phase to obtain a formate product.
Wherein, in step S1, the CO purification process: obtaining a CO purified gas, specifically comprising:
and step S110, recovering the industrial furnace gas rich in CO, and removing harmful impurities to obtain cleaner tail gas through treatments of water washing, alkali washing, water washing and the like in sequence.
The CO-rich industrial furnace gas can be one or more of blast furnace gas, yellow phosphorus electric furnace tail gas, calcium carbide furnace tail gas, coke oven tail gas or coal converted gas.
The purpose of treatments such as water washing, alkali washing, water washing and the like is to remove harmful impurities in CO-rich industrial furnace gas, wherein the harmful impurities are mainly particles, sulfur-containing compounds, phosphorus-containing compounds and NOX、CO2And the like. The harmful impurities are removed, and the adverse effect on the quality of subsequent precipitated white carbon black and sodium formate products is avoided.
And S120, further purifying the tail gas obtained in the step S110 by adopting pressure swing adsorption to obtain CO purified gas with the purity of more than or equal to 96 percent so as to meet the requirement of the subsequent carbonylation synthesis process. Analytic tail gas H generated by pressure swing adsorption2And CO and the like are recovered and used for recycling the heat source gas.
The purified CO gas obtained after the treatment in step S120 contains less than or equal to 2ppm of phosphorus compounds, less than or equal to 2ppm of sulfur compounds, and NOX≤10ppm，CO2≤0.3％，N2≤3.0％。
Step S2, carbonylation synthesis: and carrying out carbonylation reaction on the CO purified gas and a silicate solution to obtain a solid-liquid mixture of precipitated white carbon black and formate, and specifically comprising the following steps:
and S210, pressurizing the CO purified gas with the purity of more than or equal to 96 percent obtained in the step S1 to 2.0-3.0Mpa by a compressor, and then sending the CO purified gas into a reaction kettle 1 filled with silicate solution, wherein the concentration of the silicate solution is 5.0-20.0 percent, and the modulus of the silicate is 1.0-3.4.
Step S220, controlling the reaction temperature in the reaction kettle 1 at 220 ℃ and the reaction pressure at 2.0-3.0Mpa, and controlling the conditions such as stirring strength and the like to carry out carbonylation reaction on CO and silicate solution for 10-240 min.
And step S230, detecting the pH value of the reaction material in the step S220, and finishing the reaction when the pH value of the reaction material is less than or equal to 8.
And S240, cooling the reaction material after the reaction to 60-90 ℃, and aging for 30-120min to obtain a solid-liquid mixture of precipitated white carbon black and formate.
The carbonylation reaction comprises two processes of synthesizing formic acid by carbonyl and reacting formic acid and silicate, and the reaction mechanism is as follows:
(1) oxo synthesis of formic acid
H2O+CO→HCOOHΔH＝-24.547kJ/mol
(2) Reaction of formic acid with silicate
2HCOOH+R2O·mSiO2+xH2O→2RHCOO+mSiO2·nH2O ↓ (white carbon black)
In this embodiment, the silicate solution may be a sodium silicate solution or a potassium silicate solution; correspondingly, the formate formed is sodium formate or sodium formate. That is, R in the chemical reaction formula is Na or K.
The Gibbs free energy value of the oxo-formic acid in the reaction (1) is-5.42 kJ/mol, and the reaction needs to be triggered at a certain initial temperature. The reaction trigger temperature is preferably equal to or more than 160 ℃, the reaction speed is accelerated along with the temperature rise, and the reaction speed is not obviously increased when the temperature exceeds 220 ℃. The reaction is exothermic, the excessive temperature is not favorable for reaction balance, and the reaction temperature is preferably controlled within the range of 170-220 ℃, so that a reasonable reaction rate can be obtained. Since the reaction is exothermic after the reaction is triggered, the heating can be stopped, and the reaction temperature in the reaction vessel 1 can be maintained by the reaction exotherm. When the temperature in the reaction kettle 1 is low, saturated steam can be introduced for heating.
Further, step S210, pressurizing the purified CO gas to 2.0-3.0Mpa, and feeding the pressurized purified CO gas into a reaction kettle containing a silicate solution, wherein the concentration of the silicate solution is 5.0-20.0%, and the method specifically comprises the following steps:
and step S211, adding a silicate solution with the concentration of 5.0-20.0% and the modulus of 1.0-3.4 into the reaction kettle 1, and stirring.
Step S212, introducing saturated steam of 1.0Mpa into the reaction kettle 1, preheating the silicate solution, and simultaneously replacing the air at the upper part in the reaction kettle 1.
S213, after the air in the reaction kettle 1 is replaced to the oxygen content less than or equal to 0.5 percent and the silicate solution is preheated to the temperature of 170-180 ℃, the CO purified gas is pressurized to 2.0-3.0Mpa and then is sent into the reaction kettle 1 to carry out carbonylation reaction with the silicate solution. The reaction can be triggered by introducing CO purified gas, the time required by the reaction triggering is shortened, and the waste of CO is avoided.
In step S3, separating and preparing the product: and (3) performing solid-liquid separation on the solid-liquid mixture of the precipitated white carbon black and the formate obtained in the step (S2), washing and drying the solid phase to obtain a precipitated white carbon black product, and concentrating the liquid phase to obtain a formate product, wherein the method specifically comprises the following steps:
and S310, performing filter pressing separation on the obtained solid-liquid mixture of the precipitated white carbon black and the formate by using a membrane filter press to obtain a filter cake and filtrate.
And S320, washing the filter cake obtained in the step S310 by adopting a multi-stage countercurrent washing mode until the conductivity of the final washing liquid is less than or equal to 500 mu S/cm, and obtaining a clean filter cake meeting the requirement. The water consumption can be saved by adopting a multi-stage countercurrent washing mode.
And S330, pulping, spraying and drying the clean filter cake obtained in the step S320 to obtain a precipitated white carbon black product.
And step S340, concentrating, crystallizing, separating and drying the filtrate obtained in the step S310 and the washing concentrated solution generated in the step S320 to obtain a formate product. Wherein, the concentration step can adopt any one mode of membrane filtration concentration, MVR evaporation concentration or multi-effect evaporation concentration to ensure low energy consumption.
In conclusion, the embodiment adopts the reaction of CO and the silicate solution to generate two products of precipitated white carbon black and formate, so that the use of sulfuric acid (or other acids) is omitted, carbon fixation and emission reduction are realized by utilizing CO, the value increase of the obtained two products is realized, the emission of waste water is reduced, and the effects of consumption reduction, value increase, energy conservation and emission reduction are achieved.
Example 2
The embodiment provides a method for producing precipitated white carbon black and formate, which is applied to intermittent production in a single reaction kettle.
(1) CO purification treatment
Collecting the yellow phosphorus electric furnace tail gas rich in CO, and sequentially washing with water, alkali and water to remove most of particulate matters, sulfur-containing compounds, phosphorus-containing compounds and NO in the tail gasX、CO2And the like; then further purifying by adopting a pressure swing adsorption mode to obtain CO purified gas, wherein the CO purity of the CO purified gas reaches more than 97 percent, the phosphorus-containing compound is less than or equal to 1ppm, the sulfur-containing compound is less than or equal to 1ppm, and NO isX≤5ppm，CO2≤0.2％，N22Less than or equal to 2.0 percent. It resolves tail gas H2And CO and the like are recycled and used for recycling heat source gas, so that energy consumption loss is reduced.
(2) Carbonylation synthesis: a single reaction kettle is used for batch operation production.
As shown in FIG. 2, the reaction vessel 1 has a stirrer 11, a steam inlet 12, a silicate solution inlet 13, a CO gas inlet 14, a vent 15, a discharge outlet 16, and the like. Wherein, the exhaust port 15 is positioned at the upper part of the reaction kettle 1, and the discharge port 16 is positioned at the bottom of the reaction kettle 1.
The effective volume of the reaction kettle 1 is 6m3When in production, firstly, 5m of the mixture is filled into the reaction kettle 133.3-3.4 model sodium silicate solution (namely, sodium silicate solution) with the concentration of 10%, and starting the stirrer 11 to stir the materials. Then, introducing 1.0Mpa saturated steam to preheat the material, replacing the upper air in the reaction kettle 1 at the early stage of preheating until the oxygen content is less than or equal to 0.5%, and preheating the material to 170-180 ℃. After the replacement and preheating temperature meets the requirement, pumping the CO purified gas with the purity of more than 97 percent obtained by purification treatment into the reaction kettle 1 after being pressurized by a compressor, controlling the pressure in the reaction kettle 1 to be 2.0-2.3MPa, carrying out carbonylation reaction on the sodium silicate solution and the CO purified gas in the reaction kettle 1, and discharging during the reactionThe heat is generated, and the temperature in the reaction kettle 1 is maintained at 170-220 ℃. When the temperature is low (such as below 172 deg.C), saturated steam of 1.0MPa is introduced for heating.
After the reaction for 60min, the pH of the reaction mass was measured to be 7, and the reaction was terminated. And (3) decompressing the reaction kettle 1, cooling to 80-90 ℃, and aging for 60min to obtain a solid-liquid mixture containing the precipitated white carbon black and sodium formate.
(3) Product separation preparation
And (3) sending the obtained solid-liquid mixture containing the precipitated white carbon black and sodium formate to a membrane filter press for filter pressing, and carrying out solid-liquid separation to obtain a filter cake and filtrate. And washing the filter cake by using process water in a multi-stage countercurrent mode until the conductivity of the final washing liquid is less than or equal to 500 mu s/cm, and obtaining a clean filter cake. And drying the clean filter cake by a pulping spray to obtain a precipitated white carbon black product. And evaporating, crystallizing, separating and drying the filtrate generated by filter pressing and the washing concentrated solution generated by cleaning the filter cake to obtain a sodium formate product. And (4) sending the condensate generated in the evaporation concentration process back to the multistage countercurrent washing tank or preparing the sodium silicate solution for recycling.
Example 3
The embodiment provides a method for producing precipitated white carbon black and formate, which is applied to continuous production of a plurality of serially connected reaction kettles.
(1) CO purification treatment
Collecting the yellow phosphorus electric furnace tail gas rich in CO, and sequentially washing with water, alkali and water to remove most of particulate matters, sulfur-containing compounds, phosphorus-containing compounds and NO in the tail gasX、CO2And the like; then further purifying by adopting a pressure swing adsorption mode to obtain CO purified gas, wherein the CO purity of the CO purified gas reaches over 96 percent, the phosphorus-containing compound is less than or equal to 2ppm, the sulfur-containing compound is less than or equal to 2ppm, and NOX≤10ppm，CO2≤0.3％，N22Less than or equal to 3.0 percent. It resolves tail gas H2And CO and the like are recycled and used for recycling heat source gas, so that energy consumption loss is reduced.
(2) Carbonylation synthesis: a plurality of reaction kettles are connected in series for continuous production.
As shown in fig. 3, the reactor comprises 3 reaction kettles 1 which are arranged in series, namely a first-stage reaction kettle, a second-stage reaction kettle and a third-stage reaction kettle (i.e. a final-stage reaction kettle).
The exhaust port 15 of the non-first-stage reaction kettle is communicated with the CO gas inlet 14 of the previous-stage reaction kettle through a pipeline. Namely, the exhaust port 15 of the third-stage reaction kettle is communicated with the CO gas inlet 14 of the second-stage reaction kettle through a pipeline; the exhaust port 15 of the second-stage reaction kettle is communicated with the CO gas inlet 14 of the first-stage reaction kettle through a pipeline.
The discharge port 16 of the non-final-stage reaction kettle is communicated with the next-stage reaction kettle through a pipeline. Namely, the discharge port 16 of the first-stage reaction kettle is communicated with the second-stage reaction kettle through a pipeline; the discharge port 16 of the second-stage reaction kettle is communicated with the third-stage reaction kettle through a pipeline.
The silicate solution is added from a silicate solution inlet 13 of the primary reaction kettle. The slurry after the reaction in the first-stage reaction kettle is discharged to the second-stage reaction kettle through the discharge outlet 16 at the bottom for reaction, the slurry after the reaction in the second-stage reaction kettle is continuously discharged to the third-stage reaction kettle for reaction, the slurry reaction in the third-stage reaction kettle reaches the reaction finishing standard, the reaction is finished, and the slurry is discharged from the discharge outlet 16 at the bottom of the third-stage reaction kettle for the next process, namely, the material after the reaction is finished is discharged from the discharge outlet of the last-stage reaction kettle.
The CO purified gas is fed from a CO gas inlet 14 of the third-stage reactor (i.e., the final-stage reactor). The CO purified gas reacts with the materials in the third-stage reaction kettle, and the unreacted CO gas is discharged to the second-stage reaction kettle from an exhaust port 15 at the upper part; the reaction is continued in the second-stage reaction kettle, the CO gas which does not participate in the reaction process is discharged to the first-stage reaction kettle from the exhaust port 15 at the upper part for reaction, and the final residual gas is discharged from the exhaust port 15 at the upper part of the first-stage reaction kettle, namely the residual gas is discharged from the exhaust port 15 of the first-stage reaction kettle. Ensuring the continuity of the reaction and maintaining the stable pressure in each reaction kettle.
A plurality of reation kettle that the series connection set up all are connected with the steam source of heat supply center, can let in saturated steam and heat each reation kettle, maintain reaction temperature.
Specifically, the effective volumes of the first-stage reaction kettle, the second-stage reaction kettle and the third-stage reaction kettle are all 6m3. In production, in one stage3.3-3.4 moulds of sodium silicate solution (namely, sodium silicate solution) with the concentration of 10 percent are filled, and the stirrer 11 is started to stir the materials. Then, introducing 1.0Mpa saturated steam to preheat the materials, replacing the upper air in the first-stage reaction kettle, the second-stage reaction kettle and the third-stage reaction kettle in the early preheating stage until the oxygen content is less than or equal to 0.5%, and preheating the materials to 170-180 ℃. After the replacement and preheating temperatures reach the requirements, pumping CO purified gas with the purity of more than 96 percent obtained by purification treatment into a three-stage reaction kettle after being pressurized by a compressor, controlling the pressure in each reaction kettle to be 2.0-2.4MPa, carrying out countercurrent contact carbonylation reaction on the sodium silicate solution and the CO purified gas in the first-stage reaction kettle, the second-stage reaction kettle and the third-stage reaction kettle, discharging heat during the reaction, and maintaining the temperature in each reaction kettle at 220 ℃. When the temperature in each reaction vessel is low (e.g., below 175 ℃), saturated steam of 1.0MPa is introduced for heating.
And controlling the proportion of adding 10% sodium silicate solution into the first-stage reaction kettle and adding CO purified gas into the third-stage reaction kettle, so that the pH value of the material discharged from the bottom of the third-stage reaction kettle is 6-7. And (3) decompressing the material discharged from the third-stage reaction kettle, cooling to 80-90 ℃, and aging for 60min to obtain a solid-liquid mixture containing precipitated white carbon black and sodium formate.
The reaction kettles arranged in series are adopted to carry out continuous carbonylation reaction, so that the reaction is more sufficient, the utilization rate of the substrate is higher, and the precipitated white carbon black and sodium formate products with higher purity are obtained.
(3) Product separation preparation
The method is the same as the product separation and preparation method in the embodiment 2, and is not described in detail.
Product inspection results and comparisons
Through detection, as shown in table 1, the precipitated silica products obtained in examples 2 and 3 meet the HG/T3061-2009 "rubber compounding agent-precipitated hydrated silica" standard, and specific detection data are shown in table 1.
According to the detection, as shown in table 1, the sodium formate products obtained in example 2 and example 3 meet the HG/T5390-2018 "sodium formate for industrial use", and the specific detection data is shown in table 2.
The precipitated silica product according to example 2 in table 1 has a silica content (dry basis) of 92% and the precipitated silica product according to example 3 has a silica content (dry basis) of 93%; in table 2, the sodium formate (w%) of the sodium formate product of example 2 is 97.5%, and the sodium formate (w%) of the sodium formate product of example 3 is 98.5%, which can be further confirmed: the reaction kettles arranged in series are adopted to carry out continuous carbonylation reaction, and precipitated white carbon black and sodium formate products with higher purity can be obtained.
Table 1 shows the results of testing the precipitated silica products obtained in examples 2 and 3
Figure BDA0003442017410000121
Table 2 shows the results of the examination of the sodium formate products obtained in example 2 and example 3
Figure BDA0003442017410000122

Claims (10)

1. The method for producing the precipitated white carbon black and the formate is characterized by comprising the following steps of:
step S1, CO purification treatment: obtaining CO purified gas;
step S2, carbonylation synthesis: carrying out carbonylation reaction on the CO purified gas and a silicate solution to obtain a solid-liquid mixture of precipitated white carbon black and formate;
step S3, separating and preparing products: and carrying out solid-liquid separation on the obtained solid-liquid mixture of the precipitated white carbon black and the formate, washing and drying the solid phase to obtain a precipitated white carbon black product, and concentrating the liquid phase to obtain a formate product.
2. The method for producing precipitated silica and formate according to claim 1, wherein said step S1, CO purification treatment: obtaining a CO purified gas, specifically comprising:
step S110, washing the industrial furnace gas rich in CO with water, alkali and water in sequence to remove harmful impurities and obtain cleaner tail gas;
and S120, further purifying the obtained tail gas by adopting pressure swing adsorption to obtain CO purified gas with the purity of more than or equal to 96 percent.
3. The method for producing precipitated silica and formate according to claim 2, wherein the method comprises the steps of:
the CO-rich industrial furnace gas comprises one or more of blast furnace gas, yellow phosphorus electric furnace tail gas, calcium carbide furnace tail gas, coke oven tail gas or coal converted gas;
and/or the presence of a gas in the gas,
the phosphorus-containing compound, the sulfur-containing compound and the NO in the CO purified gas are less than or equal to 2ppm and less than or equal to 2ppm respectivelyX≤10ppm，CO2≤0.3％，N2≤3.0％。
4. The method for producing precipitated silica and formate according to claim 1 or 3, wherein the step S2, the carbonylation synthesis: and carrying out carbonylation reaction on the CO purified gas and a silicate solution to obtain a solid-liquid mixture of precipitated white carbon black and formate, and specifically comprising the following steps:
s210, pressurizing the CO purified gas to 2.0-3.0Mpa, and sending the CO purified gas into a reaction kettle filled with silicate solution, wherein the concentration of the silicate solution is 5.0-20.0%;
step S220, controlling the reaction temperature at 160-220 ℃ and the reaction pressure at 2.0-3.0Mpa, and carrying out carbonylation reaction for 10-240 min;
and step S230, detecting the pH value of the reaction material, and ending the reaction when the pH value of the reaction material is less than or equal to 8.
5. The method for producing precipitated silica and formate according to claim 4, wherein the step S2 comprises the following steps: and carrying out carbonylation reaction on the CO purified gas and a silicate solution to obtain a solid-liquid mixture of precipitated white carbon black and formate, and further comprising the following steps:
and S240, cooling the reaction material after the reaction to 60-90 ℃, and aging for 30-120min to obtain a solid-liquid mixture of precipitated white carbon black and formate.
6. The method for producing precipitated silica and formate according to claim 4, wherein the step S210 comprises pressurizing the CO purified gas to 2.0-3.0MPa, and feeding the pressurized CO purified gas into a reaction kettle containing a silicate solution, wherein the silicate solution has a concentration of 5.0-20.0%, and specifically comprises:
step S211, adding the silicate solution into the reaction kettle, and stirring;
s212, introducing saturated steam into the reaction kettle, preheating the silicate solution, and simultaneously replacing air at the upper part in the reaction kettle;
s213, after the air in the reaction kettle is replaced to the oxygen content of less than or equal to 0.5 percent and the preheating temperature of the silicate solution is 170-180 ℃, pressurizing the CO purified gas to 2.0-3.0Mpa and sending the CO purified gas into the reaction kettle for carbonylation.
7. The method for producing precipitated silica and formate according to claim 1, wherein the step S3 is a product separation preparation: and carrying out solid-liquid separation on the obtained solid-liquid mixture of the precipitated white carbon black and formate, washing and drying the solid phase to obtain a precipitated white carbon black product, and concentrating the liquid phase to obtain a formate product, wherein the method specifically comprises the following steps:
step S310, performing filter pressing separation on the obtained solid-liquid mixture of the precipitated white carbon black and formate by using a membrane filter press to obtain a filter cake and filtrate;
step S320, washing the filter cake in a multi-stage countercurrent washing mode until the conductivity of the final washing liquid is less than or equal to 500 mu S/cm, and obtaining a clean filter cake;
s330, pulping, spraying and drying the clean filter cake to obtain a precipitated white carbon black product;
step S340, concentrating, crystallizing, separating and drying the filtrate and the washing concentrated solution to obtain a formate product; the concentration adopts any one of membrane filtration concentration, MVR evaporation concentration or multi-effect evaporation concentration.
8. The method for producing precipitated silica and formate according to claim 1, wherein the method comprises the steps of:
the silicate solution is sodium silicate solution or potassium silicate solution;
the formate is sodium formate or potassium formate;
the modulus of the silicate in the silicate solution is 1.0-3.4.
9. An apparatus for producing precipitated silica and formate according to any one of claims 1 to 8, the apparatus comprising:
a reaction kettle having a stirrer, a steam inlet, a silicate solution inlet, a CO gas inlet, a vent, and a discharge outlet.
10. The apparatus for producing precipitated silica and formate according to claim 9 wherein said reaction vessel comprises a plurality of reaction vessels connected in series;
the exhaust port of the non-first-stage reaction kettle is communicated with the CO gas inlet of the previous-stage reaction kettle;
the discharge port of the non-final-stage reaction kettle is connected with the subsequent-stage reaction kettle;
wherein the silicate solution is added from a silicate solution inlet of the first-stage reaction kettle; the CO purified gas is added from a CO gas inlet of the reaction kettle at the last stage; exhausting residual gas from an exhaust port of the first-stage reaction kettle; and discharging the reacted materials from a discharge port of the reaction kettle at the final stage.
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GB1445575A (en) * 1972-08-24 1976-08-11 Huber Corp J M Method for producing amorphous precipitated siliceous pigments
DE3903664A1 (en) * 1989-02-08 1990-08-09 Huels Chemische Werke Ag Process for the preparation of formic acid from carbon monoxide and water
CN101033183A (en) * 2007-03-02 2007-09-12 张少华 Process for producing sodium formate from carbonic oxide in synthesis ammonia raw material gas
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