CN111943233B - Method for preparing sodium carbonate and co-producing hydrochloric acid by sodium chloride catalytic thermal decomposition method - Google Patents

Method for preparing sodium carbonate and co-producing hydrochloric acid by sodium chloride catalytic thermal decomposition method Download PDF

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CN111943233B
CN111943233B CN202010707845.XA CN202010707845A CN111943233B CN 111943233 B CN111943233 B CN 111943233B CN 202010707845 A CN202010707845 A CN 202010707845A CN 111943233 B CN111943233 B CN 111943233B
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sodium carbonate
hydrochloric acid
sodium chloride
thermal decomposition
preparing
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CN111943233A (en
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梅艳钢
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Taiyuan Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D7/00—Carbonates of sodium, potassium or alkali metals in general
    • C01D7/02—Preparation by double decomposition
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/035—Preparation of hydrogen chloride from chlorides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention discloses a method for preparing chlorineA method for preparing sodium carbonate and co-producing hydrochloric acid by a sodium chloride catalytic thermal decomposition method relates to the field of sodium carbonate preparation methods and processes. The method comprises loading sodium chloride onto carbon catalyst carrier by soaking in solution, heating to a certain temperature, and introducing CO 2 And water vapor, the chlorine is preferentially released as HCl gas under the action of the water vapor by utilizing the catalytic decomposition action of sodium chloride on the carbon catalyst carrier, and the HCl is absorbed by water to obtain hydrochloric acid. Sodium and CO on activated carbon 2 Reacting, converting into sodium carbonate, passing through CO 2 And soaking the sodium carbonate into the solution after washing, filtering, heating and crystallizing to obtain the sodium carbonate, thereby realizing the co-production of the sodium carbonate and the hydrochloric acid. The invention realizes the one-step method for preparing sodium carbonate by NaCl catalytic thermal decomposition and coproducing dilute hydrochloric acid, and is novel Na 2 CO 3 The preparation process has good industrial application prospect; the additional economic benefit is better; and combustible gas is produced as a byproduct.

Description

Method for preparing sodium carbonate and co-producing hydrochloric acid by sodium chloride catalytic thermal decomposition method
Technical Field
The invention relates to the field of a sodium carbonate preparation method and a process, in particular to a method for preparing sodium carbonate and co-producing hydrochloric acid by a sodium chloride catalytic thermal decomposition method.
Background
Sodium carbonate is an important chemical raw material and is widely applied to the fields of metallurgy, glass manufacturing, detergent preparation and the like. Common raw materials for preparing sodium carbonate are sodium chloride and carbon dioxide, and the sodium chloride provides a cheap sodium source for preparing the sodium carbonate. The sodium carbonate is prepared by a Soxhlet alkali preparation method and a Hough alkali preparation method, firstly, ammonia gas reacts with water and carbon dioxide to generate ammonium bicarbonate, then the ammonium bicarbonate with low solubility is preferentially separated out in a sodium salt system, and then the sodium bicarbonate is decomposed to obtain a sodium carbonate product. The process needs a large amount of ammonia gas, and has the defects of long process flow and complex working procedure. Other sodium carbonate production and preparation processes also have some problems, for example, CN 106564916B discloses a method for recovering sodium carbonate by using chromium slag, the process adopts pressurized hydrothermal treatment for alkali-containing chromium slag, mainly emphasizes on dealkalization treatment for chromium slag, and Na exists 2 CO 3 Low production amount, harmful substances in the product, and the like.
Hydrochloric acid is an inorganic strong acid and widely applied to the fields of light industry, textile, petroleum, organic synthesis and the like, and two preparation methods of industrial hydrochloric acid are mainly adopted, wherein one method is to obtain Cl by electrolyzing saline solution 2 Then through and H 2 After burning, the hydrochloric acid is obtained after being absorbed by water, and the other hydrochloric acid production process is a byproduct in the chlorination process of organic matters.
The above process can realize HCl and Na 2 CO 3 But the processes have the problems of low efficiency, complex flow, high energy consumption and large environmental pollution. The sodium chloride contains chlorine element and sodium element at the same time, and is a main raw material for preparing sodium carbonate and hydrochloric acid. Therefore, the development of the process for co-producing sodium carbonate and hydrochloric acid by using sodium chloride can improve the atomic utilization efficiency of sodium and chlorine, perfect the production process of sodium carbonate and hydrochloric acid, and has important significance for promoting the production of sodium carbonate and hydrochloric acid.
Disclosure of Invention
The invention provides a method for preparing sodium carbonate and co-producing hydrochloric acid by a sodium chloride catalytic thermal decomposition method, aiming at solving the problems of low efficiency, complex flow, high energy consumption, large environmental pollution and low utilization efficiency of sodium and chlorine atoms in the preparation process of sodium carbonate and hydrochloric acid in the prior art.
The invention is realized by the following technical scheme: a method for preparing sodium carbonate and co-producing hydrochloric acid by a sodium chloride catalytic thermal decomposition method comprises the following steps:
(1) Loading NaCl on a carbon catalyst carrier by a solution impregnation method;
(2) Mixing water vapor and CO at 300-700 deg.C 2 Introducing a NaCl loaded carbon catalyst carrier for activation and decomposition;
(3) After the reaction is finished, the generated gas is divided into combustible gas and non-combustible gas, the non-combustible gas comprises HCl, the HCl is chilled by water and then absorbed to obtain hydrochloric acid with the mass fraction of 0-1%, and the residual combustible gas after absorption is recycled;
(4) Subjecting the solid-phase residue after the reaction to CO 2 Washing with pressurized water and filtering to obtain Na 2 CO 3 Heating, concentrating, and crystallizing to obtain Na 2 CO 3 And (5) producing the product.
The invention considers NaCl conversion from the atom economy, and utilizes the catalytic thermal decomposition effect of the carbon catalyst carrier on NaCl to carry out NaCl in water vaporIn the presence of HCl, the HCl is converted into gas-phase HCl, quickly escapes out of the surface of a solid phase, and is finally chilled and absorbed by water to obtain dilute hydrochloric acid; na in NaCl is converted into Na 2 CO 3 On activated carbon, na 2 CO 3 Is saturated with CO 2 Washing with water, leaching to obtain solution, evaporating, concentrating, and crystallizing to obtain Na 2 CO 3 And (5) producing the product. The specific working process is as follows: sodium chloride is impregnated and loaded on a carbon catalyst carrier by adopting solution, and CO is introduced after the sodium chloride is heated to a certain temperature 2 And water vapor, the chlorine is preferentially released as HCl gas under the action of the water vapor by utilizing the catalytic decomposition action of sodium chloride on the carbon catalyst carrier, and the HCl is absorbed by water to obtain hydrochloric acid. Sodium and CO on activated carbon 2 Reacting, converting into sodium carbonate, passing through CO 2 And soaking the sodium carbonate into the solution after washing, filtering, heating and crystallizing to obtain the sodium carbonate, thereby realizing the co-production of the sodium carbonate and the hydrochloric acid. The gas products in the step (3) are mainly CO and H 2 、HCl、CO 2 、CH 4 Etc., so that HCl is removed to form hydrochloric acid and the remainder, other than CO 2 All the combustible gases are combustible gases, so the by-product combustible gases can be recycled.
Preferably, the carbon catalyst carrier in the step (1) adopts activated carbon, petroleum coke, biomass, lignite, bituminous coal and coke; naCl loading was 0-20 wt%.
Further, in the step (2), steam and CO are added 2 The ratio is 0.2-3.
Further, in step (4), CO 2 The pressure is 0-5 MPa, the leaching temperature is 20-100 ℃, and the liquid-solid ratio is 5-50.
Compared with the prior art, the invention has the following beneficial effects: the invention provides a method for preparing sodium carbonate and hydrochloric acid by using a sodium chloride catalytic thermal decomposition method, which prepares Na by using NaCl as a raw material through a one-step thermal catalytic decomposition method 2 CO 3 Simplify Na 2 CO 3 Preparation process and technique for producing Na 2 CO 3 Meanwhile, cl in NaCl is converted into HCl, so that the raw materials are completely utilized, and the additional economic benefit is better; can be combined with thermal conversion of carbonaceous materialAnd (4) producing combustible gas as a byproduct. The invention realizes the one-step method for preparing sodium carbonate by NaCl catalytic thermal decomposition and coproducing dilute hydrochloric acid, and is novel Na 2 CO 3 The preparation process has good industrial application prospect.
Drawings
FIG. 1 is a process flow diagram of a method for preparing sodium carbonate and co-producing hydrochloric acid by a sodium chloride catalytic thermal decomposition method provided by the invention.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the invention is not limited to the examples.
Example 1
In the embodiment, biomass activated carbon is used as a catalyst, 15 wt% NaCl is loaded on the activated carbon by a solution impregnation method, 500g of a sample is placed in a tubular furnace, the temperature is programmed to 550 ℃, and CO is introduced 2 Performing catalytic activation with water vapor, reacting for 30 min, stopping heating, chilling gas phase product with water, measuring HCl content in water, cooling solid phase, and passing through CO 2 Hydrothermal pressure leaching to obtain Na-containing 2 CO 3 Heating, concentrating, and crystallizing to obtain Na 2 CO 3 The method comprises the following specific steps:
(1) Loading NaCl on a biomass activated carbon catalyst by a solution impregnation method, wherein the NaCl loading capacity is 15 wt%;
(2) 500g of sample is placed in a tube furnace, the temperature is raised to 550 ℃ at the heating rate of 10 ℃/min, and water vapor and CO are added 2 Introducing NaCl-loaded active carbon for activation and decomposition, and mixing water vapor and CO 2 The volume ratio is 1, the gas flow is 2L/min, and the temperature is reduced to the room temperature after the gas flow is kept for 30 min;
(3) Chilling the reacted gas-phase product with water and absorbing the gas-phase product to obtain low-concentration HCl with the mass fraction of 0-1%, recycling the residual combustible gas, and determining the HCl content and the conversion rate by a titration method;
(4) Subjecting the solid-phase residue after reaction to CO 2 Washing with pressurized water and filtering to obtain Na 2 CO 3 Solution, CO 2 The pressure of the pressure leaching is 3 MPa, and the temperature of the leaching is highThe temperature is 20 ℃, and the liquid-solid ratio is 5; heating, concentrating and crystallizing the solution to obtain Na 2 CO 3 And (5) producing the product.
The final HCl conversion by acid-base titration and ICP measurement was 65%, na 2 CO 3 The yield of (b) was 55%.
Example 2
In the embodiment, the shenmu bituminous coal is used as a catalyst, 10 wt% NaCl is loaded on the shenmu bituminous coal by a solution impregnation method, 500g of a sample is placed in a tubular furnace, the temperature is programmed to 300 ℃, and CO is introduced 2 Performing catalytic activation with water vapor, reacting for 30 min, stopping heating, chilling gas-phase product with water, measuring HCl content in water, cooling solid phase, and passing through CO 2 Hydrothermal pressure leaching to obtain Na-containing 2 CO 3 Heating, concentrating, and crystallizing to obtain Na 2 CO 3 The product comprises the following specific steps:
(1) Loading NaCl on the Shenmu bituminous coal catalyst by a solution impregnation method, wherein the loading amount of the NaCl is 10 wt%;
(2) Removing 500g of sample, placing in a tube furnace, heating to 500 deg.C at a heating rate of 10 deg.C/min, and mixing water vapor and CO 2 Introducing Nauclea officinalis loaded with NaCl to carry out activation decomposition, and adding water vapor and CO 2 The volume ratio is 2, and the gas flow is 2L/min. Keeping for 30 min, and cooling to room temperature;
(3) Chilling the reacted gas-phase product with water and absorbing the gas-phase product to obtain low-concentration HCl with the mass fraction of 0-1%, recycling the residual combustible gas, and determining the HCl content and the conversion rate by a titration method;
(4) Subjecting the solid-phase residue after reaction to CO 2 Washing with pressurized water, and filtering to obtain Na 2 CO 3 Solution of CO 2 The pressure leaching pressure is 5 MPa, the leaching temperature is 80 ℃, and the liquid-solid ratio is 10; heating, concentrating and crystallizing the solution to obtain Na 2 CO 3 And (5) producing the product.
The final HCl conversion by acid-base titration and ICP measurement was 89%, na 2 CO 3 The yield of (3) was found to be 76%.
Example 3
The embodiment uses graphite asCatalyst, 10 wt% NaCl is loaded on graphite by solution impregnation method, 500g of sample is placed in a tubular furnace, temperature is programmed to 700 ℃, CO is introduced 2 Performing catalytic activation with water vapor, reacting for 30 min, stopping heating, chilling gas phase product with water, measuring HCl content in water, cooling solid phase, and passing through CO 2 Hydrothermal pressure leaching to obtain Na-containing 2 CO 3 Heating, concentrating, and crystallizing to obtain Na 2 CO 3 And (5) producing the product. The method comprises the following specific steps:
(1) Loading NaCl on the graphite catalyst by a solution impregnation method, wherein the loading amount of the NaCl is 5 wt%;
(2) Removing 500g of sample, placing in a tube furnace, heating to 500 deg.C at a heating rate of 10 deg.C/min, and mixing water vapor and CO 2 Introducing graphite loaded with NaCl for activation and decomposition, and mixing water vapor and CO 2 The volume ratio is 1, and the gas flow is 2L/min. Keeping for 30 min, and cooling to room temperature;
(3) Chilling the reacted gas-phase product with water and absorbing the gas-phase product to obtain low-concentration HCl with the mass fraction of 0-1%, recycling the residual combustible gas, and determining the HCl content and the conversion rate by a titration method;
(4) Subjecting the solid-phase residue after the reaction to CO 2 Washing with pressurized water, and filtering to obtain Na 2 CO 3 Solution of CO 2 The pressure leaching pressure is 0.1 MPa, the leaching temperature is 80 ℃, and the liquid-solid ratio is 10; heating, concentrating and crystallizing the solution to obtain Na 2 CO 3 And (5) producing the product.
The final HCl conversion by acid-base titration and ICP measurements was 45%, na 2 CO 3 The yield of (b) was 37%.
Comparative example
This example compares to example 1 with the replacement of the biomass activated carbon catalyst with inert quartz under other conditions such as: naCl load, thermocatalytic decomposition temperature, water vapor ratio, CO 2 The pressure of the pressurized leaching and the like are kept consistent, and the specific steps are as follows:
(a) Loading NaCl on quartz by a solution impregnation method, wherein the loading amount of the NaCl is 15 wt%;
(b) Get away and get500g sample is put into a tube furnace, the temperature is raised to 550 ℃ at the heating rate of 10 ℃/min, and water vapor and CO are added 2 Introducing NaCl-loaded quartz for activation and decomposition, and mixing water vapor and CO 2 The volume ratio is 1, the gas flow is 2L/min, and the temperature is reduced to the room temperature after the gas flow is kept for 30 min;
(c) Chilling the reacted gas-phase product by water, absorbing the gas-phase product, and measuring the content of HCl by a titration method;
(d) Subjecting the solid-phase residue after reaction to CO 2 Filtering after washing with pressurized water, CO 2 The pressure leaching pressure is 3 MPa, the leaching temperature is 20 ℃, and the liquid-solid ratio is 5.
The final HCl conversion rate determined by acid-base titration and ICP is 0 2 CO 3 The yield of (A) was 0.
The scope of the invention is not limited to the above embodiments, and various modifications and changes may be made by those skilled in the art, and any modifications, improvements and equivalents within the spirit and principle of the invention should be included in the scope of the invention.

Claims (5)

1. A method for preparing sodium carbonate and co-producing hydrochloric acid by a sodium chloride catalytic thermal decomposition method is characterized by comprising the following steps: the method comprises the following steps:
(1) Loading NaCl on a carbon catalyst carrier by a solution impregnation method;
(2) Mixing water vapor and CO at 300-700 deg.C 2 Introducing a NaCl loaded carbon catalyst carrier for activation and decomposition;
(3) After the reaction is finished, the generated gas is divided into combustible gas and non-combustible gas, the non-combustible gas comprises HCl, the HCl is chilled by water and then absorbed to obtain hydrochloric acid with the mass fraction of 0-1%, and the residual combustible gas after absorption is recycled;
(4) Subjecting the solid-phase residue after reaction to CO 2 Washing with pressurized water and filtering to obtain Na 2 CO 3 Heating, concentrating, and crystallizing to obtain Na 2 CO 3 And (5) producing the product.
2. The method for preparing sodium carbonate and co-producing hydrochloric acid by catalytic thermal decomposition of sodium chloride according to claim 1, wherein: the carbon catalyst carrier in the step (1) adopts active carbon, petroleum coke, biomass, lignite, bituminous coal and coke.
3. The method for preparing sodium carbonate and co-producing hydrochloric acid by catalytic thermal decomposition of sodium chloride according to claim 1, wherein: in the step (1), the NaCl loading is 0-20 wt%.
4. The method for preparing sodium carbonate and co-producing hydrochloric acid by catalytic thermal decomposition of sodium chloride according to claim 1, wherein: in the step (2), steam and CO 2 The ratio is 0.2-3.
5. The method for preparing sodium carbonate and co-producing hydrochloric acid by catalytic thermal decomposition of sodium chloride according to claim 1, wherein: in step (4), CO 2 The pressure is 0-5 MPa, the leaching temperature is 20-100 ℃, and the liquid-solid ratio is 5-50.
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