CN1115267A - Ba mud, its coproducts such as barium sulfate, magnesium carbonate, refined salt or ammonium chloride, Ba brick and other products - Google Patents

Abstract

The Ba-mud rich in barium chloride and halogen floc rich in magnesium sulfate, as well as other raw materials are used to join production of barium sulfate, magnesium carbonate, refined salt or ammonium chloride. The Ba-mud rich in other water-soluble or acid-soluble barium compounds reacts on organic acid, soluble organic acid salt, inorganic acid, soluble inorganic salt, soda ash, caustic soda, lime kiln gas and lime solution to production of various organic or inorganic barium salt or barium compound. The residual mud is mixed with cement, Ba-dregs, and sand to make hard brick preventing atomic radioactivity.

Description

Barium mud coproduced with barium sulfate, magnesium carbonate, refined salt or ammonium chloride, barium brick and other products

The invention belongs to the field of chemical environment-friendly comprehensive utilization.

The invention aims to treat industrial waste residue, eliminate pollution and excavate environment-friendly productivity by a comprehensive utilization method. Saving treatment cost and creating better economic benefit and social benefit.

The advantages of the invention are many, and the main advantages are: barium salts and most barium compounds are highly toxic substances. Some barium salts (e.g., barium chloride) are lethal at 0.4 g. Scientific research in recent years shows that people who contact the barium compound for a long time deposit a large amount of barium compound in the body, and the barium compound can cause paralysis although not lethal.

China has a plurality of barium product manufacturers, most of which take barite as a raw material to prepare various barium products through the procedures of roasting reduction, acidolysis leaching, reaction evaporation and the like, but almost all the manufacturers simultaneously produce waste residues containing a large amount of toxic barium compounds, namely barium mud and barium residues.

At present, most of the treatment of barium mud and barium slag is limited to intensive management, namely, the barium mud and the barium slag are simply and nontoxic treated and then discharged to a closed place, and a specially-assigned person is arranged to take care of the barium mud and the barium slag day and night. Thus not only a great deal of treatment, cleaning and management cost is spent, but also the residual toxicity in the sludge is blown by wind and rain, flows into rivers, lakes, seas, canals and ponds, pollutes the water quality and endangers the aquatic resources; the infiltration of the soil into the farmland deteriorates the soil quality and damages crops and vegetation, and once the soil is mixed into drinking water, the light people affect the health of residents, and the heavy people cause poisoning and death.

The invention adopts a chemical environmental protection comprehensive utilization method, firstly toxic barium compounds in mud are converted into non-toxic barium products, then the useful components in mother liquor are co-produced with various products, and finally the residual barium mud, barium slag, cement and water are mixed and beaten into barium bricks with the function of preventing atomic radiation. The benefits of this are:

and(I) a large amount of treatment, cleaning and management cost is saved.

And (II) changing the harm into the benefit, changing waste into valuable and providing a plurality of useful products for the market.

(III) considerable economic benefits can be obtained

And (IV) the barium mud and the barium slag are completely eliminated and are completely converted into products.

In order to achieve the purpose, the characteristics of the invention are shown, the inventor carries out detailed investigation, detection and analysis and repeated small tests and simulation production tests on the yield, performance and chemical components of barium mud produced in an inorganic salt field barium chloride workshop of a Tianjin chemical plant in which the inventor is positioned, and particularly provides a concrete content of the invention, namely the co-production of barium mud with barium sulfate, magnesium carbonate, refined salt or ammonium chloride and barium bricks.

Raw materials used in the first step:

1. barium mud: the waste mud of barium product is prepared by taking barite as a raw material. The black ink stick contains water content over 60%, water soluble and acid soluble barium salt or barium compound and silt. Wherein the barium compound can be used as the co-production raw material when the content of barium compound reaches 5 percent. The barium mud produced by Tianjin chemical plant actually contains 10-15% of effective barium compounds.

2. Marinating: salinization in salt fieldA by-product in industry. Also known as crude magnesium sulfate. The crystal water contains seven crystal water at normal temperature, and the molecular formula is as follows: MgSO (MgSO)_4.7H₂And O. Refined magnesium sulfate heptahydrate can be prepared, but the process is complex, the cost is high, and the market competitiveness is not strong, so that the magnesium sulfate heptahydrate is mostly waste at present. The bittern may also be replaced by refined magnesium sulfate heptahydrate, anhydrous sodium sulfate, etc. But the price is expensive, and the product cost is higher than the selling price, so the price is not available.

3. Soda ash: sodium carbonate (Na)₂CO₃) The waste alkali liquor can also be used.

4. Ammonium carbonate: namely ((NH)₄)₂CO₃) Ammonium bicarbonate (NH)₄HCO₃) Also, the method can be used.

5. Cement: no. 425 ordinary portland cement.

6. Barium residue: also takes barite as the waste of barium product. Is a high-melting point substance which can not be melted when the barite is roasted. The civil house is used as coarse sand.

(II) product simple price:

1. barium sulfate: also known as precipitated barium sulfate. White powder, specific gravity 4.499(15 deg.C), melting point 1580 deg.C, and insoluble in water and acid. The pigment is mainly used for pigments and rubber, papermaking, printing ink and paint fillers. And acid-resistant daub can be prepared. The high purity product can be used as barium meal for X-ray gastrointestinal fluoroscopy and radiography, and is called barium gypsum.

2. Magnesium carbonate: also known as light magnesium carbonate. White powder. The decomposition starts at 300 ℃, the carbon dioxide is released after the decomposition is dissolved in strong acid, and the water is difficult to dissolve. It is mainly used as paint, paper making, asbestos, toothpaste and cosmetic filler. Is a reinforcing agent of rubber, and can improve the heat resistance and the wear resistance of the rubber. It can be used to prepare high-grade insulating powder with asbestos for insulating boiler and steam pipeline.

3. Refined salt: also called re-produced salt, white fine crystal, specific gravity 2.16, melting point 800 ℃, easy to dissolve in water. It is mainly used in the industry of dyeing and weaving for civil food and food, dye, etc.

4. Ammonium chloride: white fine crystals. The specific gravity is 1.54, and the water and ethanol are easily dissolved. It is mainly used as agricultural fertilizer and chemical raw material, electroplating and battery industry. Can also be used as a solder.

5. Barium brick: a black and gray brick containing barium compound. Is a special brick for preventing radioactive rays from overflowing in buildings such as an X-ray room of a hospital, a nuclear physics research room, an isotope storage room and the like.

(III) the production principle:

1. preparing barium sulfate:

soluble barium ions in the barium mud react with sulfate ions in the bittern floc after being leached and clarified by adding water to generate insoluble barium sulfate precipitation, and the reaction formula is as follows:

if the content of acid-soluble barium compounds in the mud is large, a proper amount of hydrochloric acid can be added into the mud firstly to convert the acid-soluble barium compounds into soluble barium chloride. Such as:

the content of acid-soluble barium compounds inthe barium mud produced by Tianjin chemical plant is not large, so hydrochloric acid can be omitted.

2. Preparation of magnesium carbonate

Barium chloride contained in the barium mud of Tianjin chemical plant reacts with bittern to generate barium sulfate, and the mother solution is magnesium chloride solution. The reaction formula is as follows:

the mother liquor and the sodium carbonate solution react to generate the insoluble magnesium carbonate. The reaction formula is as follows:

the mother liquid can be reacted with ammonium carbonate or ammonium bicarbonate instead of soda ash to produce magnesium carbonate. The reaction formula is as follows:

3. preparation of refined salt or ammonium chloride

The mother liquid of magnesium carbonate prepared from sodium carbonate is sodium chloride solution, and refined salt is obtained by evaporation, washing and drying.

The mother liquid of the ammonium carbonate or ammonium bicarbonate as material for preparing magnesium carbonate is ammonium chloride solution, which is evaporated, washed and stoved to obtain fine ammonium chloride crystal

4. Making of barium brick

Barium sulfate is prepared from barium mud, and the barium mud left after leaching, cement and barium slag (or coarse sand) are mixed with water to form slurry, and the slurry is filled into a mold tobe made into barium hollow bricks or building blocks with any specification.

(IV) the production process comprises the following steps:

1. production of barium sulfate

And (4) transporting the barium mud to a storage tank of a production workshop for storage by using a tank car or a tank car. During production, the barium chloride solution is put into a leaching tank with a stirrer (the weight is determined according to the production scale), water which is 5 times of that of the barium mud is added at the same time, the mixture is stirred for 15 to 30 minutes (until soluble barium compounds in the mud are completely dissolved), the mixture is injected into a filter press 1 in batches for filtration, and the filtered clear liquid, namely the barium chloride solution, is put into an elevated tank 1 for standby. Filtering and leaching again to recover barium chloride.

Putting the marinated floc into a dissolving tank 1, adding 2 times of warm water with the weight of the marinated floc and the temperature of 40 ℃ until the floc is completely dissolved, and pumping the floc into a head tank 2 for later use. The bittern can be discarded.

And respectively pumping the clear solutions in the two elevated tanks into a reaction tank provided with a stirrer according to a certain proportion, and stirring for 20-30 minutes to completely separate out barium sulfate. The formula is as follows:

assuming that the addition amount of the reactant barium chloride solution is "a (1)", the addition amount "X" of the other reactant brine flocculant solution should be: $X=A\frac{M1D2}{M2\mathrm{<figure-callout\; id="1"\; label="D"\; filenames="A9311730500131.png"\; state="\{\{state\}\}">D</figure-callout>}1}$

in the formula: m1-concentration of barium chloride solution (g/l)

M2 magnesium sulfate solution concentration (g/l)

D1 molecular weight of barium chloride

D2-molecular weight of magnesium sulfate the amount Y (g) of barium sulfate formed should be: $Y=A\frac{M1D3}{\mathrm{<figure-callout\; id="1"\; label="D"\; filenames="A9311730500131.png"\; state="\{\{state\}\}">D</figure-callout>}1}$

in the formula: d3-molecular weight of barium sulfate

The barium sulfate slurry after the reaction is completed is injected into the filter press 2 in batches for filtration. Filtering to obtain mother liquor, namely magnesium chloride solution, and pumping into the elevated tank 4 for later use. Filtering, adding 5 times of water into washing tank 1 with stirrer, stirring for 20-30 min, and filtering with filter press 3. Filtering to obtain filtrate, recovering the leached barium mud, filtering after filtration, and loading the filtrate on a drying kang for drying through a branch bucket. After drying, the mixture is crushed into 325 meshes by a crusher 1 and then is put into a woven bag with a plastic lining to obtain the finished product of precipitated barium sulfate. Each bag is 25-50 kg.

2. Production of magnesium carbonate:

dissolving soda ash or ammonium carbonate (or ammonium bicarbonate) in water (2.5 times of boiling water at 100 deg.C; and normal temperature water equal to the weight of ammonium carbonate) in the dissolving tank 2. Pouring the molten mixture into a high-level tank 3 for standby. The standby solutions in the elevated tank 3 and the elevated tank 4 are injected into the reaction tank 2 according to a certain proportion and are stirred for 20-30 minutes, and then magnesium carbonate can be completely precipitated. The formula is as follows:

(1) the formula taking the calcined soda as the raw material comprises the following components:

if the reactant magnesium chloride solution is added in an amount "B (1)", the other reactant soda ash solution is added in an amount "V1 (1)": $\mathrm{<figure-callout\; id="1"\; label="V"\; filenames="A9311730500131.png"\; state="\{\{state\}\}">V</figure-callout>}1=B\frac{M3D4}{M4D3}$ in the formula: m3-concentration of magnesium chloride solution (g/l);

m4-sodium carbonate solution concentration (g/l);

d3 molecular weight of magnesium chloride

D4-molecular weight of sodium carbonate the amount of magnesium carbonate "W1 (g)" produced should be: $\mathrm{<figure-callout\; id="1"\; label="W"\; filenames="A9311730500131.png"\; state="\{\{state\}\}">W</figure-callout>}1=B\frac{M3D5}{D3}$

in the formula: d5-molecular weight of magnesium carbonate

(2) The formula using ammonium carbonate or ammonium bicarbonate as raw material is as follows: assuming that the amount of reactant magnesium chloride solution added is "B (g/l)," the amount of the other reactant ammonium carbonate or ammonium bicarbonate solution added "V2 (1)" should be: $V2=B\frac{M3D6}{M5D3}$ in the formula: m5-concentration of ammonium carbonate or ammonium bicarbonate solution (g/l)

D6 molecular weight of ammonium carbonate or ammonium bicarbonate, the amount of magnesium carbonate "W2 (g)" should be $W2=B\frac{M3D5}{D3}$

And injecting the magnesium carbonate slurry after the reaction into a filter press 4 in batches for filtering, wherein the filtrate is sodium chloride or ammonium chloride solution, and injecting into a halogen storage pool for later use. Filtering, adding 5 times of water into washing tank 2, stirring for 20-30 min, and filtering with filter press 5. Filtering out washing liquid, discarding, filtering, drying in a dryer 2, crushing by a crusher 2, and packaging to obtain the light magnesium sulfate finished product.

3. Production of refined salt or ammonium chloride:

the sodium chloride or ammonium chloride solution is dried in the sun and evaporated, and then is put into an evaporating pot, and is evaporated to 110 ℃ (sodium chloride) or 115 ℃ (ammonium chloride) and then is injected into a washer for washing after crystallization. After washing, the mixture is put into a centrifugal dehydrator for dehalogenation (the mother solution returns to an evaporating pot), and then the refined salt or ammonium chloride finished product can be obtained after drying and packaging.

4. Manufacturing the barium brick:

preparing a plurality of hollow brick moulds in advance (the size is determined according to requirements), simultaneously filling barium mud, cement and barium slag (or coarse sand) into a stirrer according to the proportion of 0.5: 1: 3, adding water into the slurry, then injecting the slurry into the brick moulds one by one, removing the moulds after 24 hours, and curing for 28 days until the highest strength is reached, thus obtaining the finished bricks for sale.

(V) economic benefits

The barium chloride is produced by 2.5 ten thousand tons per year according to the calculation of a Tianjin chemical plant, the barium mud can be produced by 1.25 ten thousand tons (the water content is more than 60 percent) per year according to the proportion of one half, about 10 to 15 percent of the barium chloride remains in the tested mud, and about 1250 to 1875 tons of the barium chloride is carried away by the mud.

Since a reliable way of precipitating barium sulfate has been found, a feasibility report of barium sulfate production (by-product halogen block) from barium mud and halogen floc is written in the fifth month of the year. The analysis result shows that the total consumption of the mud can be balanced with the total output value when the content of barium chloride in the mud reaches 5 percent, and the aimsof saving treatment, cleaning and managing cost of dozens of ten thousand yuan are achieved. The barium chloride content reaches 12 percent, and the yield can be calculated according to the collection rate of 70 percent to produce 0.12 ten thousand tons of barium sulfate, 0.1 ten thousand tons of halogen blocks, the total yield is 154.7 ten thousand yuan, the total consumption is 78.1 ten thousand yuan, and the total profit and tax are 76.6 ten thousand yuan. Under the condition of facilities such as factory buildings, hydropower and the like, the total investment is only 25 ten thousand yuan. If all the products are on the horse, the total interest and tax are more considerable

And (VI) social benefits.

After the invention is completely implemented, barium pollution is completely eliminated. Partial implementation can also enable toxic substances in the waste mud to be substantially eliminated so as to reach the emission standard

(VII) production of other products

The above is an embodiment according to the characteristics of the region where the inventor is located. (the barium mud and the halogen floc exist in the local area) other areas with the barium mud do not necessarily have the halogen floc, but one of the following resources can produce various barium products while treating the barium mud, for example, waste inorganic acid can produce corresponding inorganic acid barium; the waste organic acid can be used for producing corresponding organic acid barium; the lime air, the waste soda ash or the waste soluble carbonate solution can produce barium carbonate; the waste caustic soda solution or the lime water can be used for producing barium hydroxide; the alunite, potassium and magnesium alum can produce barium sulfate; the saltpeter or alkaline earth can produce barium nitrate, etc. Of course, various corresponding raw materials can be used, but the raw materials must be used inconsideration of economic factors. The process is similar to the above and has little difference.

The invention can thoroughly eliminate barium pollution on the premise of creating greater economic benefit, so the inventor thinks that the best mode for implementing the invention is who pollutes and manages. And hopefully, according to the rules of the fourteenth paragraph of the patent laws, the leaders in the field are responsible for the barium mud pollution. Of course, various aspects of funds (including country, group, village and town, street, enterprise, individual operator construction and production or technical transfer) can be attracted.

The description is provided with two drawings

FIG. 1 is a flow diagram of a process apparatus, which is illustrated below:

1. -leaching tank 2-filter press 1

3. Dissolving tank 14 elevated tank 1

6. Elevated tank 26-reaction tank 1

7. Filter press 28 washing tank 1

9-filter press 310-drying kang 1

11-Raymond mill 112-elevated tank 3

13-elevated tank 414-reaction tank 2

15-Filter Press 416-sink 2

17-filter press 518-drying kang 2

19-Remeng grinder 220-halogen storage tank

21-evaporating pot 22-scrubber

23-dehalogenation machine 24-drier

25-mud storage tank 26-mixer

27-brick mould

FIG. 2 is a process flow diagram, which is illustrated in the attached drawings of the abstract of the specification

Claims (4)

1. The invention is technically characterized in that a series of barium products and other products are produced by a chemical environment-friendly comprehensive utilization method. Not only can treat the environment, but also can develop the environment-friendly productivity.
2. 1. A method for treating barium mud pollution.
3. 2. A process for preparing barium sulfate, magnesium carbonate, refined salt or ammonium chloride, barium brick and other organic barium salts and barium compounds from barium mud.
4. 3. Production and sale of new products-barium mud and barium slag barium bricks.

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