A method for preparing white carbon black and co-producing barium chloride and calcium chloride from barium sulfide waste residue

Abstract

The invention relates to the technical field of resource utilization of waste residues in the production process of barium sulfide, and specifically to a method for preparing white carbon black and co-producing barium chloride and calcium chloride from barium sulfide waste residue, wherein the barium sulfide waste residue is weighed, added with water, and then boiled at high temperature for separation; wherein the liquid reacts with a certain amount of hydrochloric acid according to the analysis of silicon dioxide content to generate white carbon black precipitation; wherein the solid reacts with a certain amount of hydrochloric acid to generate barium chloride and calcium chloride liquid; alkali is added to remove impurities and iron to obtain refined barium chloride and calcium chloride solutions; evaporation and concentration are performed, and the concentration of calcium chloride in the evaporation process is controlled to obtain dihydrate barium chloride crystals, and refined calcium chloride solution is obtained by filtration; the refined calcium chloride liquid is continuously evaporated and concentrated to a certain concentration, and then spray-dried to obtain anhydrous calcium chloride products. The invention has a simple process, a short flow, and high product quality purity; the co-production of barium chloride has high added value, and the product has high purity characteristics, and is particularly suitable for the electronics industry.

Description

Technical Field

[0001] The invention relates to the technical field of resource utilization of waste residues in a barium sulfide production process, and in particular to a method for preparing white carbon black and co-producing barium chloride and calcium chloride from barium sulfide waste residues. Background Art

[0002] As a filler for paints and coatings, a reinforcing agent for rubber, a tackifier and thixotropic agent for plastics, and a thickener for synthetic grease and silicone grease, white carbon black has a wide range of uses. At present, the domestic production of white carbon black is produced by the reaction of sodium carbonate with acid. The production of sodium carbonate requires a large amount of soda ash and quartz sand to be melted at high temperature. Therefore, this production method has a complex process and a long process, and is prone to produce a large amount of pollutants.

[0003] Domestic barium salt production enterprises produce a large amount of barium sulfide waste residue during the production process. These waste residues contain a large amount of silicate, generally accounting for 40-60%. As a heavy metal solid waste, barium sulfide waste residue is a source of pollution that causes environmental media pollution.

[0004] At present, domestic barium salt enterprises generally treat barium sulfide waste residue harmlessly and then landfill it or send it to cement plants as a mineralizer to be added to cement, without fully extracting the useful components in it. Therefore, it is of great significance to extract silicate from waste residue to prepare white carbon black. Summary of the invention

[0005] In order to solve the problem of comprehensive utilization of waste residues, the present invention provides a method for preparing white carbon black and co-producing barium chloride and calcium chloride by using barium sulfide waste residues.

[0006] The present invention is achieved through the following technical scheme: a method for preparing white carbon black and co-producing barium chloride and calcium chloride from barium sulfide waste residue, comprising the following steps:

[0007] Step 1): Weigh the barium sulfide waste residue, add water and then cook at high temperature to separate;

[0008] Step 2): reacting the liquid obtained in step 1) with a certain amount of hydrochloric acid according to the analyzed silicon dioxide content to generate white carbon black precipitation;

[0009] Step 3): reacting the solid obtained in step 1) with a certain amount of hydrochloric acid to generate barium chloride and calcium chloride liquids;

[0010] Step 4): Add alkali to the liquid obtained in step 3) to remove impurities and iron, and obtain refined barium chloride and calcium chloride solutions;

[0011] Step 5): evaporate and concentrate the liquid obtained in step 4), control the concentration of calcium chloride during the evaporation process to obtain barium chloride dihydrate crystals, and filter to obtain a refined calcium chloride solution;

[0012] Step 6): The refined calcium chloride liquid obtained in step 5) is further evaporated and concentrated to a certain concentration, and then spray-dried to obtain an anhydrous calcium chloride product.

[0013] As a further improvement of the technical solution of the present invention, in step 1), the high temperature steaming temperature is 120° C. to 180° C., and the time is 120 to 360 minutes.

[0014] As a further improvement of the technical solution of the present invention, in step 2), hydrochloric acid is added to control the pH of the reaction system to be less than 3.

[0015] As a further improvement of the technical solution of the present invention, in step 3), the mass ratio of the solid to the hydrochloric acid is 6-8:1, and the concentration of the hydrochloric acid is 20%.

[0016] As a further improvement of the technical solution of the present invention, in step 3), after adding hydrochloric acid, stirring reaction is carried out, the stirring time is 60 minutes, and the reaction temperature is 50°C~60°C.

[0017] As a further improvement of the technical solution of the present invention, in step 4), the alkali added for removing impurities and iron is barium sulfide.

[0018] As a further improvement of the technical solution of the present invention, in step 6), the refined calcium chloride liquid is further evaporated and concentrated to 70% and then spray-dried, and the spray-drying temperature is 350-500°C.

[0019] The preparation method of the present invention uses hydrochloric acid to react with silicate in waste residue to generate silicate and then dehydrate to form white carbon black. The main reactions involved are:

[0020] BaSiO3+HCl→BaCl2+H2SiO3

[0021] CaSiO3+HCl→CaCl2+H2SiO3

[0022] Compared with the traditional white carbon black production method, the method for preparing white carbon black and co-producing barium chloride and calcium chloride from barium sulfide waste residue of the present invention has the following beneficial effects:

[0023] The raw materials used in the present invention are industrial waste residues, which are easy to obtain and have no production cost pressure, and white carbon black can be produced at low cost. The process of the present invention is simple, the flow is short, and the product quality purity is high; the co-produced barium chloride has high added value, and the product has high purity characteristics, which is particularly suitable for the electronics industry. And the co-produced barium chloride of the present invention comes from waste residues, which can protect the mineral resources and be green and environmentally friendly. After the liquid separated by desiliconization is impurity-removed, the components are barium chloride and calcium chloride. According to the phase diagram and salting-out theory, when the concentration of calcium chloride increases, the solubility of barium chloride drops sharply, and barium chloride crystals are precipitated to obtain a barium chloride product; the calcium chloride solution continues to evaporate and is spray-dried to obtain anhydrous calcium chloride products. The process is environmentally friendly and has certain environmental benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0025] Figure 1 The present invention provides a schematic flow chart of a method for preparing white carbon black and co-producing barium chloride and calcium chloride from barium sulfide waste residue. DETAILED DESCRIPTION

[0026] The technical solution of the present invention is described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] The present invention provides a specific embodiment of a method for preparing white carbon black and co-producing barium chloride and calcium chloride from barium sulfide waste residue, comprising the following steps:

[0028] Step 1): Weigh the barium sulfide waste residue, add water and then cook at high temperature to separate;

[0029] Step 2): reacting the liquid obtained in step 1) with a certain amount of hydrochloric acid according to the analyzed silicon dioxide content to generate white carbon black precipitation;

[0030] Step 3): reacting the solid obtained in step 1) with a certain amount of hydrochloric acid to generate barium chloride and calcium chloride liquids;

[0031] Step 4): Add alkali to the liquid obtained in step 3) to remove impurities and iron, and obtain refined barium chloride and calcium chloride solutions;

[0032] Step 5): evaporate and concentrate the liquid obtained in step 4), control the concentration of calcium chloride during the evaporation process to obtain barium chloride dihydrate crystals, and filter to obtain a refined calcium chloride solution;

[0033] Step 6): The refined calcium chloride liquid obtained in step 5) is further evaporated and concentrated to a certain concentration, and then spray-dried to obtain an anhydrous calcium chloride product.

[0034] In one embodiment provided by the present invention, in step 1), the high temperature cooking temperature is 120°C to 180°C, and the time is 120 to 360 minutes. Preferably, the high temperature cooking temperature is 130°C to 160°C, and the time is 120 to 240 minutes.

[0035] In another embodiment provided by the present invention, in step 2), hydrochloric acid is added to control the pH of the reaction system to be less than 3.

[0036] In one embodiment provided by the present invention, in step 3), the mass ratio of solid to hydrochloric acid is 6-8:1, and the concentration of hydrochloric acid is 20%.

[0037] In another embodiment provided by the present invention, in step 3), after adding hydrochloric acid, stirring reaction is carried out, the stirring time is 60 minutes, and the reaction temperature is 50°C-60°C.

[0038] In one embodiment provided by the present invention, in step 4), the alkali added for removing impurities and iron is barium sulfide.

[0039] In another embodiment provided by the present invention, in step 6), the refined calcium chloride liquid is further evaporated and concentrated to 70% and then spray-dried, and the spray-drying temperature is 350-500° C. Preferably, the spray-drying temperature is 350° C.

[0040] The technical solution of the present invention is described in detail below through specific embodiments.

[0041] Example 1

[0042] (1) Weigh 50 g of barium sulfide waste slag and add 150 g of water. Then heat in a 2-liter autoclave with the steam valve open to ensure the temperature is 140°C for 120 minutes.

[0043] (2) Open the valve and release the liquid in the autoclave. The silica content is 93 g / L. Slowly add 85 g of hydrochloric acid (20%) into the liquid. The pH value is controlled to be less than 3 at the reaction endpoint.

[0044] (3) The precipitate separated by filtration was washed thoroughly and then dried to obtain 13.2 g of white carbon black. The separated liquid was a barium chloride acid solution, and its concentration was 135 g / L.

[0045] (4) Add hydrochloric acid (20%) at a mass ratio of 6:1 to the solid discharged from the autoclave, stir for 60 minutes at a temperature of 50°C to 60°C, and then filter and separate to obtain a crude liquid.

[0046] (5) When the crude liquid separated above is added to a 130 g / L barium sulfide alkali solution, a large amount of precipitation occurs. The end point pH is controlled to be 8. After filtering out the precipitate, refined barium chloride and calcium chloride solutions are obtained.

[0047] (6) Mix the barium chloride acid solution and the refined liquid and evaporate and concentrate them. When the calcium chloride concentration in the evaporation process is controlled to be 30%, separate the barium chloride dihydrate by filtration, wash and dry. The drying temperature is controlled at 50°C to 60°C.

[0048] (7) When the calcium chloride liquid continues to evaporate and concentrate to 70%, it is sent to spray drying to obtain anhydrous calcium chloride product, and the inlet tower temperature is controlled at 350°C.

[0049] Example 2

[0050] (1) Weigh 150 kg of barium sulfide waste slag and add 2 m 3 The water then reaches 5 m 3 In the autoclave, open the steam valve to heat and ensure the temperature is at 140°C for 120 minutes.

[0051] (2) Open the valve and place the mixed liquid in the autoclave into a centrifuge for filtration. The silica content of the filtrate is 89 g / L. 250 kg of hydrochloric acid is slowly added to the liquid. The reaction endpoint is controlled to pH <3 and the reaction time is 60 minutes.

[0052] (3) The precipitate separated by filtration was washed thoroughly and then dried to obtain 83.2 kg of white carbon black. The separated liquid was a barium chloride acid solution, and its concentration was 115 g / L.

[0053] (4) Add hydrochloric acid (20%) at a mass ratio of 6:1 to the solid discharged from the autoclave, stir for 60 minutes at a temperature of 50°C to 60°C, and then filter and separate to obtain a crude liquid.

[0054] (5) When the crude liquid separated above is added to a 140 g / L barium sulfide alkali solution, a large amount of precipitation occurs. The end point pH is controlled to be 8. After filtering out the precipitate, refined barium chloride and calcium chloride solutions are obtained.

[0055] (6) Mix the barium chloride acid solution and the refined liquid and evaporate and concentrate them. When the calcium chloride concentration in the evaporation process is controlled to be 30%, separate the barium chloride dihydrate by filtration, wash and dry. The drying temperature is controlled at 50°C to 60°C.

[0056] (7) When the calcium chloride liquid continues to evaporate and concentrate to 70%, it is sent to spray drying to obtain anhydrous calcium chloride product, and the inlet tower temperature is controlled at 450°C.

[0057] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing white carbon black and co-producing barium chloride and calcium chloride from barium sulfide waste residue, characterized in that: The steps include: Step 1): Weigh the barium sulfide waste residue, add water and then cook at high temperature to separate; the high temperature cooking temperature is 120°C to 180°C, and the time is 120 to 360 minutes; Step 2): reacting the liquid obtained in step 1) with a certain amount of hydrochloric acid according to the analyzed silicon dioxide content to generate white carbon black precipitation; Step 3): reacting the solid obtained in step 1) with a certain amount of hydrochloric acid to generate barium chloride and calcium chloride liquids; Step 4): Add alkali to the liquid obtained in step 3) to remove impurities and iron, and obtain refined barium chloride and calcium chloride solutions; Step 5): evaporate and concentrate the liquid obtained in step 4), control the concentration of calcium chloride during the evaporation process to obtain barium chloride dihydrate crystals, and filter to obtain a refined calcium chloride solution; Step 6): The refined calcium chloride liquid obtained in step 5) is further evaporated and concentrated to a certain concentration, and then spray-dried to obtain an anhydrous calcium chloride product.

2. The method for preparing white carbon black and co-producing barium chloride and calcium chloride from barium sulfide waste residue according to claim 1, characterized in that: In step 2), hydrochloric acid is added to control the pH of the reaction system to be less than 3.

3. The method for preparing white carbon black and co-producing barium chloride and calcium chloride from barium sulfide waste residue according to claim 1, characterized in that: In step 3), the mass ratio of solid to hydrochloric acid is 6-8:1, and the concentration of hydrochloric acid is 20%.

4. The method for preparing white carbon black and co-producing barium chloride and calcium chloride from barium sulfide waste residue according to claim 3, characterized in that: In step 3), after adding hydrochloric acid, stirring reaction is carried out for 60 minutes at a reaction temperature of 50°C to 60°C.

5. The method for preparing white carbon black and co-producing barium chloride and calcium chloride from barium sulfide waste residue according to claim 1, characterized in that: In step 4), the alkali added for removing impurities and iron is barium sulfide.

6. The method for preparing white carbon black and co-producing barium chloride and calcium chloride from barium sulfide waste residue according to claim 1, characterized in that: In step 6), the refined calcium chloride liquid is further evaporated and concentrated to 70% and then spray-dried at a temperature of 350-500°C.

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