CN102351216A - Preparation process for soda ash capable of combined production of white carbon black - Google Patents
Preparation process for soda ash capable of combined production of white carbon black Download PDFInfo
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- CN102351216A CN102351216A CN2011101939009A CN201110193900A CN102351216A CN 102351216 A CN102351216 A CN 102351216A CN 2011101939009 A CN2011101939009 A CN 2011101939009A CN 201110193900 A CN201110193900 A CN 201110193900A CN 102351216 A CN102351216 A CN 102351216A
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- carbon black
- white carbon
- soda ash
- silicate powder
- calucium silicate
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Abstract
The invention provides a preparation process for soda ash capable of combined production of white carbon black. According to the method, calcium silicate is employed to substitute lime and to react with crystallization mother liquor produced in the process of preparing soda ash by using the ammonia-soda method so as to regenerate ammonia; meanwhile, hydrate silica slurry is formed, and combined production of white carbon black and soda ash is realized, thereby limitedly reduce comprehensive production cost for soda ash and white carbon black. The preparation process provided in the invention opens up a novel technical route for preparation processes for white carbon black, is a novel milestone in the technology for preparing white carbon black and has critical significance to energy saving, emission reduction and development of circular economy in the chemical industry.
Description
Technical field
The invention discloses a kind of soda ash preparation technology of co-producing white carbon black; Be a kind ofly to adopt Calucium Silicate powder to substitute quicklime regeneration solvay soda process to prepare the ammonia in the soda ash process; Form the WHITE CARBON BLACK slurry simultaneously, realize the coproduction of soda ash and WHITE CARBON BLACK, belong to the Chemicals preparing technical field.
Technical background
Soda ash be a kind of basis chemical raw material, be mainly used in light industry, building materials, chemical industry.Glass industry is the maximum consumer sector of soda ash, and glass per ton consumes 0.2 ton of soda ash.World's soda ash output surpasses 4,000 ten thousand tons at present, and Chinese soda ash output is near 2,000 ten thousand tons.The maximum technology of preparing of current employing is that soda ash is produced in solvay soda process, needs in a large amount of lime in the preparation process and ammonium chloride, reaches the purpose of ammonifying again.
2NH
4Cl+CaO＝4NH
3↑+2CaCl
2
WHITE CARBON BLACK is a kind of inorganic fine chemical product of classics, is mainly used in goods fields such as plastics, rubber, paint, coating.The production capacity of domestic WHITE CARBON BLACK is above 1,200,000 tons.The main production of WHITE CARBON BLACK is to adopt soda ash and silica sand to prepare water glass; Prepare WHITE CARBON BLACK with sulfuric acid reaction again after the water glass dilution, prepare WHITE CARBON BLACK per ton and will consume 0.5 ton of 98% sulfuric acid, 0.6 ton of yellow soda ash; It is 1.5 tons that energy consumption is amounted to the mark coal, (20%) 3.55 ton of discharging sodium sulfate waste liquid.(m is a modulus in the following reaction formula, generally between 2.8-3.3)
Na
2CO
3+mSiO
2＝Na
2O.mSiO
2
Na
2O.mSiO
2+H
2SO
4+H
2O＝mSiO
2.H
2O↓+Na
2SO
4+H
2O
The preparation of WHITE CARBON BLACK is a high energy consumption, expensive product.Develop new Preparation of White Carbon Black Technology, the energy consumption and the material consumption that reduce WHITE CARBON BLACK have important economic value.
Summary of the invention:
The objective of the invention is to overcome the deficiency of prior art and provide a kind of technological design reasonable; The employing Calucium Silicate powder is a raw material; Utilize soda ash to prepare ammonium chloride and Calucium Silicate powder reaction that process forms, reach again the purpose of ammonifying, simultaneously co-producing white carbon black; The preparation technology of the preparation technology of WHITE CARBON BLACK and soda ash is integrated, i.e. the soda ash preparation technology of co-producing white carbon black.The present invention effectively reduces the comprehensive production cost of WHITE CARBON BLACK and soda ash, makes the technology of preparing of WHITE CARBON BLACK bring up to a new state of the art.
The soda ash preparation technology of a kind of co-producing white carbon black of the present invention may further comprise the steps:
The first step: Calucium Silicate powder is carried out wet grinding, obtain the Calucium Silicate powder slurry;
Second step: adopt solvay soda process to prepare soda ash, crystalline mother solution that obtains and said Calucium Silicate powder slurry reaction obtain ammonia and hydrated SiO 2 slurry;
The 3rd step: said hydrated SiO 2 slurry is carried out press filtration, washing, obtain hydrated SiO 2 filter cake filter cake;
The 4th step:, obtain the WHITE CARBON BLACK product to said hydrated SiO 2 filter cake pulp processing, spraying drying.
Among the soda ash preparation technology of a kind of co-producing white carbon black of the present invention, the purity of said Calucium Silicate powder is greater than 96%, and whiteness is greater than 98%, and Calucium Silicate powder is ground to granularity less than 5 microns, and the minimum content of ground slurry mesosilicic acid calcium is greater than 20%.
Among the soda ash preparation technology of a kind of co-producing white carbon black of the present invention, said crystalline mother solution and Calucium Silicate powder slurry react in ammonia still, and ammonifying returns solvay soda process and prepares the soda ash system again; The add-on of said Calucium Silicate powder slurry is that the normal 0.98-1.05 of ammonium chloride in the crystalline mother solution extraordinarily goes into by the equivalent of contained quicklime wherein.
The present invention is owing to adopt technique scheme; Adopt Calucium Silicate powder and soda ash to prepare the purpose that ammonium chloride solution in the process crystalline mother solution reacts, reaches ammonifying; Form the WHITE CARBON BLACK product simultaneously; The process that is ammonia regeneration also is a process of preparation WHITE CARBON BLACK, does not have the consumption of hydrochloric acid material, effectively reduces the production cost of WHITE CARBON BLACK.Overcome the employing Calucium Silicate powder directly and hydrochloric acid reaction, prepared WHITE CARBON BLACK per ton and consume 4 tons of 31% technical hydrochloric acids, caused the Preparation of White Carbon Black defect of high cost.
Technology principle of the present invention:
1, the ultrafining treatment of Calucium Silicate powder
Calucium Silicate powder can adopt the wollastonite of high purity, high whiteness, also can adopt the Calucium Silicate powder of chemosynthesis, and the chemosynthesis Calucium Silicate powder comprises calcium metasilicate and calcium orthosilicate, and perhaps both coexistence bodies are CaO.mSiO
2(m numerical value is in the scope of 0.5-1).Calucium Silicate powder need carry out the grinding superfine processing before participating in reaction, be mixed with superfine Calucium Silicate powder slurry, can accelerate with the speed of response of ammonium chloride and calcium ion in the Calucium Silicate powder particle is thoroughly exchanged.
2, being integrally formed of the regeneration of ammonia and hydrated SiO 2 slurry
Soda ash prepares that crystalline mother solution is transported to the ammonia regeneration system in the process, and comes out to get into ammonia still, manipulation of regeneration after the hot slurry heat exchange at the bottom of the ammonia still.After crystalline mother solution heat exchange temperature raises, in the system not the crystallization bicarbonate radical of separating out can decompose rapidly, the carbonic acid gas that discharges returns the acidifying system.
NH
+ 4+HCO
- 3＝NH
3+CO
2↑+H
2O
After the hot slurry heat exchange of coming out at the bottom of Calucium Silicate powder slurry after the milled processed and the ammonia still, get into ammonia still.In ammonia still mesosilicic acid calcium and ammonium chloride reaction, form ammonia, and fractionation, the hydrated SiO 2 slurry of formation goes out from the ammonia still underflow; The ammonia that cat head comes out removes the ammonia absorption tower of soda ash preparation system.
2NH
4Cl+CaOmSiO
2＝2NH
3↑+mSiO
2.H
2O↓+CaCl
2
3, slurry filter-press water-washing, drying
The hydrated SiO 2 slurry that comes out at the bottom of the ammonia still gets into pressure filter and carries out press filtration, washing, obtains the hydrated SiO 2 filter cake.With the pulp of hydrated SiO 2 filter cake, spray drying treatment obtains the WHITE CARBON BLACK product.But prepare about 0.566 ton of soda ash co-producing white carbon black per ton.
The bright processing parameter of this law is confirmed:
1, the ultrafining treatment of Calucium Silicate powder
Calucium Silicate powder can adopt the wollastonite of high purity, high whiteness, also can adopt the Calucium Silicate powder of chemosynthesis.The content of design requirements Calucium Silicate powder raw material mesosilicic acid calcium is greater than 98%, and whiteness is greater than 98%.Calucium Silicate powder granularity after the grinding superfine processing is less than 5 microns.The content of silicon-dioxide is greater than 10% in the ground slurry.
2, the formation of the regeneration of ammonia and hydrated SiO 2 slurry
Soda ash prepares that crystalline mother solution is transported to the ammonia regeneration system in the process; After the heat exchange with milled processed after the Calucium Silicate powder slurry in ammonia still, react, form ammonia and fractionation; The hydrated SiO 2 slurry that forms goes out from the ammonia still underflow, and the ammonia that cat head comes out removes the ammonia absorption tower of soda ash preparation system.Calucium Silicate powder amount in the Calucium Silicate powder slurry that design requirements adds is the normal 0.98-1.05 of ammonium chloride in the crystalline mother solution that adds times; The leaching yield of calcium ion is greater than 98% in the Calucium Silicate powder.
3, press filtration, washing, drying are prepared into the WHITE CARBON BLACK product
With the hydrated SiO 2 slurry filter-press water-washing that ammonia still comes out, the WHITE CARBON BLACK filter cake pulp once more that obtains, spray drying treatment obtains the WHITE CARBON BLACK product.During spraying drying in the hydrated SiO 2 slurry dioxide-containing silica greater than 18%; WHITE CARBON BLACK product moisture content requirement is lower than 5%.
The meliority of the present invention's technology:
The present invention adopts Calucium Silicate powder replace lime regeneration soda ash to prepare the ammonia of process, realizes the coproduction of soda ash and WHITE CARBON BLACK, and its meliority shows as:
1, the present invention organically utilizes soda ash to prepare the crystalline mother solution ammonium chloride and the Calucium Silicate powder reaction of process; In ammonifying again; Prepare the hydrated SiO 2 slurry, accomplished the integrated of soda ash, white carbon black production technology, effectively reduced the comprehensive production cost of product.
2, Calucium Silicate powder is carried out the super-refinement wet grinding and handle, the granularity of calcium orthosilicate is ground to below 5 microns, accelerated the carrying out of reaction, improved the leaching yield of calcium ion in the Calucium Silicate powder.
3, the present invention adopts the Calucium Silicate powder particle of ultrafining treatment and the hydrogen ion effect that ammonium chloride discharges; Calcium ion in the Calucium Silicate powder is cemented out; The metasilicic acid generation condensation, the dehydration that form simultaneously; Form the hydrated SiO 2 fine particle of high-ratio surface, make the WHITE CARBON BLACK product that forms have better reinforcing property.
Significance of the present invention
The present invention adopts the Calucium Silicate powder replace lime, and regeneration soda ash prepares the ammonia of process, has realized the coproduction of soda ash and WHITE CARBON BLACK, and it is significant that chemical industry such as soda ash, WHITE CARBON BLACK are prepared industry.
1, new milestone in the Preparation of White Carbon Black Technology
China is the big country that produces soda ash, WHITE CARBON BLACK, and the WHITE CARBON BLACK production capacity is above 1,200,000 tons/year.WHITE CARBON BLACK is as a kind of fine inorganic Chemicals, and there is the classical technical problem that sulfuric acid consumption is big, the sodium sulfate discharge of wastewater is big, energy consumption is high in production process.Technology of the present invention is killed two birds with one stone; Produce in the ammonia regeneration process at soda ash, prepare cheap hydrated SiO 2 slurry, make that the preparation cost of WHITE CARBON BLACK product obviously descends (seeing the following form); Accomplish minimization of cost, the product quality optimizing of WHITE CARBON BLACK product; Reduced the comprehensive production cost of product to greatest extent, great to the influence of soda ash, WHITE CARBON BLACK industry, be milestone new in the Preparation of White Carbon Black Technology.
Adopt classical Preparation of White Carbon Black technology material consumption energy consumption table look-up
| Consume title | Silica sand | Soda ash | Sulfuric acid | Energy consumption (amounting to the mark coal) |
| Consumption/ton | 1 | 0.6 | 0.5 | 1.4 |
| Unit price/unit | 150 | 2300 | 600 | 1000 |
| Add up to | 150 | 1380 | 300 | 1400 |
Adding up to wastage in bulk or weight is 3230 yuan/ton
Adopt the energy consumption material consumption table look-up of Technology of the present invention
| Consume title | Calucium Silicate powder | Energy consumption (amounting to the mark coal) |
| Consumption/ton | 2.0 | 0.8 |
| Unit price/unit | 500 | 1000 |
| Add up to | 1000 | 800 |
Adding up to the consumption total value is 1800 yuan/ton
Joint process is included into the preparation cost of WHITE CARBON BLACK with the consumption of Calucium Silicate powder, and soda ash prepares in the process again that the lime cost of ammonifying is zero, and it is 0.5 ton that soda ash per ton reduces the lime consumption amount, 400 yuan of/ton calculating of lime price ammonia, and cost descends 200 yuan/ton.
2, huge to the energy-saving and emission-reduction of chemical industry, the contribution of developing a circular economy
Increasing the weight of day by day of world energy sources and crisis of resource, energy-saving and emission-reduction, developing a circular economy becomes the theme that chemical industry prepares industry development.The bright technology of this law is to be the main body with preparation soda ash; The hydrated SiO 2 pulp preparation that forms of in the process of ammonia regeneration, will regenerating becomes high-grade WHITE CARBON BLACK product, and the process of coproduction itself is exactly an invented technology technology with crystalline mother solution degree of depth recycling treatment and energy-saving and emission-reduction.
1., no discharging of waste liquid amount
Adopt classical white carbon black production technology, produce WHITE CARBON BLACK discharging sodium sulfate waste liquid (10%) about 6.0 tons per ton, dilute sulphuric acid waste liquor of sodium (1%-2%) is about 10, and environmental protection pressure is big; Adopt this invented technology technology to produce WHITE CARBON BLACK, the waste liquid of process discharging is exactly the waste liquid that soda ash prepares the process discharging in fact, and the waste liquid of white carbon black production discharging can be summed up as zero.
2., energy-saving and emission-reduction are remarkable
Adopting Technology of the present invention to prepare WHITE CARBON BLACK compares with the fabricating technology of classics; Energy consumption has reduced by 0.6 ton of mark coal, and power consumption has descended more than 42%, calculates by producing 1000000 tons of WHITE CARBON BLACKs per year; The annual saving marked 600,000 tons in coal, 1,800,000 tons of less Carbon emissions.Soda ash, WHITE CARBON BLACK are as the important foundation industrial chemicals in the chemical industry, and production capacity is big, and the status is heavy, and the successful realization of this technology and applying will be to the energy-saving and emission-reduction of WHITE CARBON BLACK industry, the huge contribution of developing a circular economy.
Embodiment
Production line with 300,000 tons of soda ash of year coproduction, 170,000 tons of WHITE CARBON BLACKs is an example, and concrete technical process and the technical parameter technological to the present invention describe.
1, basic material consumption amount:
The sodium-chlor consumption is: 40. ten thousand tons/year
Calucium Silicate powder: 34 tons/year, purity is greater than 98.0%, and whiteness is greater than 98%.
The WHITE CARBON BLACK drying is used industrial coal: 8.5 ten thousand tons.
2, the ultrafining treatment of Calucium Silicate powder
Process of lapping Calucium Silicate powder consumption is 42.5 tons/hour, grinds and adopts large-scale vertical stirring ball mill wet grinding, and the content of silicon-dioxide is 18% in the ground slurry; Calucium Silicate powder particle diameter after the milled processed is at 0.5 micron-1 micron; The ground slurry total amount is 118 tons/hour.
2, the formation of the regeneration of ammonia and hydrated SiO 2 slurry
The ammonium chloride content that soda ash prepares in the process separation mother liquor is 23.28%, adopts saturation steam heating, the ammonia still process of 0.25MPa.300,000 tons of isolating crystalline mother solution total amounts of soda ash production process are 189 tons/hour; Be transported to the ammonia regeneration system; After the heat exchange with milled processed after the Calucium Silicate powder slurry in ammonia still, react, form ammonia and fractionation; The hydrated SiO 2 slurry that forms goes out from the ammonia still underflow, and the ammonia that cat head comes out removes the ammonia absorption tower of soda ash preparation system.The leaching yield of calcium ion is 99.5% in the design requirements Calucium Silicate powder.The amount of slurry of coming out at the bottom of the ammonia still is 263 tons/hour, and dioxide-containing silica is 8.08%.
3, press filtration, washing, drying are prepared into the WHITE CARBON BLACK product
To the hydrated SiO 2 slurry filter-press water-washing that at the bottom of ammonia still, comes out, the WHITE CARBON BLACK filter cake that obtains, filter cake is pulp once more, and spray drying treatment obtains the WHITE CARBON BLACK product.During spraying drying in the hydrated SiO 2 slurry dioxide-containing silica be 19%; WHITE CARBON BLACK product moisture content requirement is 4.5% after the spraying drying.WHITE CARBON BLACK output is 21.25 tons/hour.The spraying drying coal consumption is 10.6 tons/hour.
The percentage composition that the present invention relates to gas all refers to volumn concentration, and the percentage composition that relates to solid and liquid all refers to the quality percentage composition.
Claims (3)
1. the soda ash preparation technology of a co-producing white carbon black may further comprise the steps:
The first step: Calucium Silicate powder is carried out wet grinding, obtain the Calucium Silicate powder slurry;
Second step: adopt solvay soda process to prepare soda ash, crystalline mother solution that obtains and said Calucium Silicate powder slurry reaction obtain ammonia and hydrated SiO 2 slurry;
The 3rd step: said hydrated SiO 2 slurry is carried out press filtration, washing, obtain hydrated SiO 2 filter cake filter cake;
The 4th step:, obtain the WHITE CARBON BLACK product to said hydrated SiO 2 filter cake pulp processing, spraying drying.
2. the soda ash preparation technology of a kind of co-producing white carbon black according to claim 1; It is characterized in that: the purity of said Calucium Silicate powder is greater than 96%; Whiteness is greater than 98%, and Calucium Silicate powder is ground to granularity less than 5 microns, and the minimum content of ground slurry mesosilicic acid calcium is greater than 20%.
3. the soda ash preparation technology of a kind of co-producing white carbon black according to claim 1, it is characterized in that: said crystalline mother solution and Calucium Silicate powder slurry react in ammonia still, and ammonifying returns solvay soda process and prepares the soda ash system again; The add-on of said Calucium Silicate powder slurry is that the normal 0.98-1.05 of ammonium chloride in the crystalline mother solution extraordinarily goes into by the equivalent of contained quicklime wherein.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101939009A CN102351216A (en) | 2011-07-12 | 2011-07-12 | Preparation process for soda ash capable of combined production of white carbon black |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101939009A CN102351216A (en) | 2011-07-12 | 2011-07-12 | Preparation process for soda ash capable of combined production of white carbon black |
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|---|---|
| CN102351216A true CN102351216A (en) | 2012-02-15 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106564924A (en) * | 2016-09-27 | 2017-04-19 | 内蒙古工业大学 | Method for preparing white carbon black and co-producing calcium chloride by using calcium silicate one-step method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB756875A (en) * | 1953-06-05 | 1956-09-12 | Columbia Southern Chem Corp | Improvements in or relating to the production of finely divided silica |
| CN1061760A (en) * | 1990-10-10 | 1992-06-10 | 索尔维公司 | The method of decomposition of aqueous ammonium chloride solution and the method for producing yellow soda ash |
-
2011
- 2011-07-12 CN CN2011101939009A patent/CN102351216A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB756875A (en) * | 1953-06-05 | 1956-09-12 | Columbia Southern Chem Corp | Improvements in or relating to the production of finely divided silica |
| CN1061760A (en) * | 1990-10-10 | 1992-06-10 | 索尔维公司 | The method of decomposition of aqueous ammonium chloride solution and the method for producing yellow soda ash |
| BE1004600A3 (en) * | 1990-10-10 | 1992-12-22 | Solvay | Aqueous ammonium chloride solution decomposition method and sodiumcarbonate production method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106564924A (en) * | 2016-09-27 | 2017-04-19 | 内蒙古工业大学 | Method for preparing white carbon black and co-producing calcium chloride by using calcium silicate one-step method |
| CN106564924B (en) * | 2016-09-27 | 2018-08-03 | 内蒙古工业大学 | The method for preparing white carbon black co-product calcium chloride using calcium silicates one-step method |
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Application publication date: 20120215 |