CN115924938A - Production process of food-grade potassium carbonate and food-grade potassium bicarbonate - Google Patents
Production process of food-grade potassium carbonate and food-grade potassium bicarbonate Download PDFInfo
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 title claims abstract description 228
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 title claims abstract description 155
- 235000015497 potassium bicarbonate Nutrition 0.000 title claims abstract description 151
- 239000011736 potassium bicarbonate Substances 0.000 title claims abstract description 151
- 229910000028 potassium bicarbonate Inorganic materials 0.000 title claims abstract description 151
- 229910000027 potassium carbonate Inorganic materials 0.000 title claims abstract description 114
- 235000011181 potassium carbonates Nutrition 0.000 title claims abstract description 114
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000005406 washing Methods 0.000 claims abstract description 57
- 239000007787 solid Substances 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000012452 mother liquor Substances 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 239000002912 waste gas Substances 0.000 claims abstract description 15
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 12
- 230000008025 crystallization Effects 0.000 claims abstract description 12
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000011591 potassium Substances 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 61
- 239000007788 liquid Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- 239000010413 mother solution Substances 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims 3
- 239000000126 substance Substances 0.000 abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- 229910052698 phosphorus Inorganic materials 0.000 abstract 1
- 239000011574 phosphorus Substances 0.000 abstract 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 35
- 239000003546 flue gas Substances 0.000 description 35
- 239000007789 gas Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000001694 spray drying Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000011552 falling film Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- 229960003975 potassium Drugs 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000010963 304 stainless steel Substances 0.000 description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000012824 chemical production Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- 230000035764 nutrition Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004267 EU approved acidity regulator Substances 0.000 description 1
- 208000019025 Hypokalemia Diseases 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 235000015872 dietary supplement Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000010855 food raising agent Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229940097322 potassium arsenite Drugs 0.000 description 1
- 208000024896 potassium deficiency disease Diseases 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- HEQWEGCSZXMIJQ-UHFFFAOYSA-M potassium;oxoarsinite Chemical compound [K+].[O-][As]=O HEQWEGCSZXMIJQ-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Abstract
The invention belongs to the field of phosphorus chemical industry, and provides a production process of food-grade potassium carbonate and food-grade potassium bicarbonate, which comprises the following steps: s1, waste gas pretreatment: removing impurities and cooling the waste gas containing carbon dioxide; s2, carbonating: carrying out carbonation reaction on the waste gas pretreated by the S1 and potassium-containing alkali liquor to obtain a mixed solution of potassium carbonate and potassium bicarbonate, and controlling the reaction pH not to exceed 8.5; s3, crystallization separation: cooling, crystallizing and centrifugally separating the mixed solution obtained in the step (2) to obtain potassium carbonate mother liquor containing potassium bicarbonate and potassium bicarbonate solid containing potassium bicarbonate; s4, washing and drying: adding pure water dissolved with carbon dioxide into the potassium bicarbonate solid containing potassium carbonate obtained in the step S3 for washing, and drying the washed potassium bicarbonate solid to obtain food-grade potassium bicarbonate; the invention can recycle and convert the waste gas into high-purity food-grade potassium carbonate and food-grade potassium bicarbonate.
Description
Technical Field
The invention relates to the field of resource utilization, in particular to a production process of food-grade potassium carbonate and food-grade potassium bicarbonate.
Background
The potassium bicarbonate has application in chemical production, food processing, medicine and other fields. In particular, for example, potassium bicarbonate can be used as a raw material for producing potassium carbonate, potassium acetate and potassium arsenite in chemical production, and can also be used as a fire extinguishing agent for petroleum and chemicals. It can also be used in medicine for supplementing potassium, treating hypokalemia, and as nutritional supplement and excipient. Can be used as baking powder, foaming salt, and chemical leavening agent in food industry. Potassium bicarbonate is commonly used as an analytical reagent in analytical chemistry. The acid regulator is used in a laboratory. The potassium bicarbonate is mainly used in the field of consumption of food, is used as a food additive to replace sodium bicarbonate in the fields of baking and acidity regulators, and is used as an agricultural fertilizer, animal husbandry, paper pulp treatment, fire extinguishers and the like. The properties of the fertilizer are similar to those of potassium carbonate, but the proportion of carbon nutrition is higher, and the proportion of potassium nutrition is slightly lower.
Carbon dioxide is a greenhouse gas with the largest global yield at present and is an important factor for climate warming, and according to the report of the international energy agency, the emission amount of the carbon dioxide in the world in 2010 reaches 331.6 million tons, wherein the emission amount of the carbon dioxide in China is about 83.3 million tons. Flue gas generated by burning coal, fuel gas and the like contains a large amount of carbon dioxide, has the characteristics of stability, concentration, large treatment capacity and the like, and is an important direction for realizing the emission reduction target. To mitigate pollution, the flue gas is conventionally absorbed and treated before emission. Currently, regarding the treatment and utilization of flue gas, which mainly uses an alkaline water absorption method for absorbing carbon dioxide and then desorbing and recovering carbon dioxide, as disclosed in (CN 101318651) an apparatus and a method for absorbing and recovering carbon dioxide from flue gas using ammonia water as an absorbent, the apparatus including an absorption tower and a circulation cooler connected to the absorption tower such that a high temperature absorbent is recovered from the absorption tower, cooled to a preset temperature, and then supplied again to the absorption tower to dissipate absorption heat generated when carbon dioxide is absorbed from flue gas. The method can only recover and store the carbon dioxide in the flue gas, and then release and utilize the carbon dioxide, so that the steps are complicated, and the recovery cost is high.
Therefore, how to economically and efficiently absorb and utilize the carbon dioxide in the flue gas and convert the carbon dioxide into waste becomes a problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a production process of food-grade potassium carbonate and food-grade potassium bicarbonate, which can economically and efficiently recycle flue gas and convert the flue gas into high-purity food-grade potassium carbonate and food-grade potassium bicarbonate.
In order to achieve the purpose, the invention adopts the technical scheme that:
a production process of food-grade potassium bicarbonate comprises the following steps:
s1, waste gas pretreatment: washing the waste gas containing carbon dioxide with water, cooling and washing with alkali; the carbon dioxide-containing waste gas may be flue gas generated by burning coal, gas, etc., since the flue gas discharged from a natural gas combustion furnace contains a small amount of solid particle impurities and acidic gas (SO) 2 And NO 2 ) And the temperature is high (about 120 ℃), the reaction can not be directly carried out in a carbonation system, and the reaction needs to be purified and cooled by a flue gas treatment system 2 And NO 2 ) Meanwhile, the flue gas is cooled, so that a cooling coil is arranged in the washing tower or a cooler is arranged on a liquid-phase outlet pipeline of the washing tower, and a person skilled in the art can reasonably select the cooling coil according to actual production requirements; the flue gas after being washed and cooled enters an alkaline washing tower, wherein the alkaline washing liquid is potassium carbonate or potassium bicarbonate or a mixture of the potassium carbonate and the potassium bicarbonate, preferably 5-20% of potassium bicarbonate solution, and more preferably 10% of potassium bicarbonate solution, SO that most of acid gas (SO) is completely washed and removed 2 And NO 2 )。
S2, carbonating: carrying out carbonation reaction on the waste gas pretreated in the step S1 and a potassium-containing alkaline substance to obtain a mixed solution of potassium carbonate and potassium bicarbonate, and controlling the pH value of the reaction to be not more than 8.5;
the washed gas enters a carbonation system, the carbonation system mainly comprises a flue gas compressor, a carbonation tower, a tail gas absorption tower and other equipment, the compressor pressurizes the purified flue gas to 0.06MPa (g), the flue gas enters the carbonation tower to carry out carbonation reaction to obtain a mixed solution of potassium carbonate and potassium bicarbonate, the reaction temperature is 40-80 ℃, preferably 60 ℃, unabsorbed carbon dioxide enters the tail gas absorption tower, 30-48% of potassium-containing alkaline substances in the tail gas absorption tower, such as potassium hydroxide or potassium carbonate solution or a mixture of the potassium hydroxide and the potassium carbonate solution, preferably 45% of potassium hydroxide, the carbon dioxide is fully absorbed to obtain a potassium carbonate dilute solution, and the dilute solution is pumped into the carbonation tower to carry out carbonation reaction; it should be noted that, when the potassium hydroxide concentration is not less than 30%, not more than 48%, and less than 30%, the concentration of potassium hydrogencarbonate produced during carbonation becomes low, which is disadvantageous for crystallization; when the concentration is higher than 48%, the concentration of the generated potassium bicarbonate is increased during carbonation, and crystals are separated out during the carbonation process to block pipelines and equipment;
the inventor creatively discovers that: when the carbonation reaction is carried out, when the pH reaches 8.5, if the flue gas is continuously introduced, the following problems occur: firstly, the concentration of the potassium bicarbonate is slowly increased, and secondly, the potassium bicarbonate has the risk of equipment blockage caused by crystal precipitation due to the increase of the concentration, so when the pH value reaches 8.5, the carbonation reaction is stopped, and the potassium carbonate is obtained: the mass ratio of potassium bicarbonate is about 3:1, carbonizing the mixed solution.
S3, crystallizing: cooling the mixed solution obtained in the step S2 to-20 ℃, and crystallizing to separate out potassium bicarbonate solid containing a small amount of potassium carbonate;
pumping the obtained carbonized mixed solution into a crystallization kettle, introducing cooling water into a jacket of the crystallization kettle, cooling the carbonized mixed solution to-20 ℃, and keeping the temperature for 10-60 min, preferably 30min, wherein the potassium carbonate and the potassium bicarbonate have different solubilities, and the crystallized solid potassium carbonate: the mass ratio of the potassium bicarbonate is 1:19 to 1:13, potassium carbonate in mother liquor: the mass ratio of potassium bicarbonate is about 5:1 to 8:1.
s4, separation: performing centrifugal separation on the mixture obtained in the step S3 to obtain a potassium carbonate mother liquor containing a small amount of potassium bicarbonate and a potassium bicarbonate solid containing a small amount of potassium carbonate;
s5, washing: adding washing water into the potassium bicarbonate solid containing a small amount of potassium carbonate obtained in the step S4 for washing, and drying the washed potassium bicarbonate solid to obtain food-grade potassium bicarbonate; the washing water is pure water in which carbon dioxide is dissolved.
Specifically, food grade carbon dioxide is dissolved in pure water under the condition of 0.1-0.6 MPa (g), preferably 0.2MPa (g), at the temperature of 5-30 ℃, preferably 20 ℃, the conductivity of the pure water is between 1-50 mu s/cm, and CO is reacted with the carbon dioxide and the water 2 +H 2 O＝H 2 CO 3 ，H 2 CO 3 Then ionize to give H + And HCO 3 - Washing potassium bicarbonate solid containing a small amount of potassium carbonate with water dissolved with carbon dioxide, and under the same ion effect, H 2 CO 3 Ionized HCO 3 - The potassium bicarbonate can be prevented from being dissolved, the potassium carbonate can not be prevented from being dissolved, meanwhile, part of potassium carbonate can be converted into the potassium bicarbonate, so that a small amount of potassium carbonate in the potassium bicarbonate is removed in a washing and converting mode, high-purity potassium bicarbonate solid without the potassium carbonate is obtained after washing is completed, and the washed high-purity potassium bicarbonate solid is dried to obtain food-grade potassium bicarbonate. The washing water is pure water dissolved with carbon dioxide, the carbon dioxide pressure is 0.1-0.6 MPa (g), the pressure is lower than 0.1MPa (g), the carbon dioxide solubility is reduced, potassium bicarbonate is dissolved and taken out during washing, the potassium bicarbonate yield is reduced, and when the pressure is higher than 0.6MPa (g), the carbonic acid concentration produced by carbon dioxide and water is not obviously increased, so that the energy consumption of the device is increased; the temperature of the washing water is lower than 5 ℃, the water has the risk of freezing, and the temperature of the washing water is higher than 30 ℃, so that the solubility of carbon dioxide is reduced, potassium bicarbonate can be dissolved and carried out during washing, and the yield of the potassium bicarbonate is reduced.
Preferably, the ratio of the amount of washing water to the mass of the potassium bicarbonate solids (wet basis) is 1:1 to 1:10, preferably 1: and 5, drying the washed high-purity potassium bicarbonate solid to obtain the food-grade potassium bicarbonate.
The inventor creatively proposes the idea of firstly converting flue gas into a mixture of potassium carbonate and potassium bicarbonate, and then separating the mixture to respectively obtain high-purity products; when the mixture is separated, the potassium carbonate and the potassium bicarbonate in the mixture are creatively converted to obtain the high-purity potassium bicarbonate and potassium carbonate respectively, and specifically, the method is carried out by adopting a washing mode of water dissolved with carbon dioxide, so that the high-purity potassium bicarbonate and potassium carbonate can be respectively prepared, other impurities cannot be introduced, the reaction time is short, and the energy consumption is greatly reduced.
Preferably, when drying the potassium bicarbonate solid: the invention relates to a high-purity potassium bicarbonate solid transferring system, which mainly comprises an air heater, a vibrating fluidized bed, a cyclone separator, a bag-type dust remover, a blower and a draught fan; the person skilled in the art can make reasonable selections according to actual production requirements. The air heater heats the air to 140-160 ℃ and then the air enters the vibrated fluidized bed, the flow velocity of the hot air in the fluidized bed is 0.01-0.5 m/s, the bed temperature is 100-120 ℃, the air outlet temperature is 70-90 ℃, the potassium bicarbonate stays in the vibrated fluidized bed for about 5min, the water in the potassium carbonate is evaporated, and the potassium bicarbonate meeting the GB 1886.247-2016 standard is obtained; the tail gas is discharged into the atmosphere after being dedusted by a cyclone separator and a bag-type dust remover, and the aperture of a bag in the bag-type dust remover is 130-160 meshes. And cooling the dried potassium bicarbonate to 40 ℃, and packaging.
The preparation process of the food-grade potassium carbonate comprises the following steps: concentrating the mother liquor obtained by centrifugal separation to obtain the mother liquor containing 20-35% of potassium carbonate and 2-8% of potassium bicarbonate; concentrating at 120-180 ℃ and vacuum degree of-0.02-0.088 MPa (g) until the mass fraction of the potassium carbonate is 40-50%, and then carrying out spray drying, wherein other drying modes can be reasonably selected by a person skilled in the art according to actual production requirements, the drying temperature is 220-260 ℃, and at the high temperature, a small amount of potassium bicarbonate in the mother liquor is decomposed to obtain the potassium carbonate, so that the food-grade potassium carbonate is finally obtained.
Preferably, when the potassium carbonate is dried: the potassium carbonate drying system mainly comprises a heat exchanger, a falling film concentrator, a natural gas burner, a centrifugal spray drying tower, a cyclone separator, a tail gas washing tower, a blower and a draught fan. The mother liquor after solid-liquid separation firstly enters a tail gas washing tower, the tail gas at about 120 ℃ from a centrifugal spray drying tower is washed to enable the tail gas to reach the standard, meanwhile, the heat in the tail gas is utilized to enable the temperature of the mother liquor to be increased to about 40 ℃, then the mother liquor is pumped into a heat exchanger, the steam condensate of a falling film concentrator is utilized to heat the mother liquor again to enable the temperature of the mother liquor to be increased to about 60 ℃, then the mother liquor enters the falling film concentrator, the steam pressure is about 0.2MPa (g), the temperature is about 125 ℃, the vacuum degree of the falling film concentrator is about-0.035 MPa, the material outlet temperature is about 120 ℃, potassium carbonate is concentrated to about 45% by mass fraction, then the mother liquor is pumped into the centrifugal spray drying tower to be in contact with high-temperature gas at 220-260 ℃ from a natural gas burner for drying, meanwhile, a small amount of potassium bicarbonate in the potassium carbonate solution is completely decomposed into potassium carbonate at high temperature, the dried potassium carbonate solid is collected through a cyclone separator, food-grade potassium carbonate meeting the GB 25588-2010 standard is obtained, and is packaged after the temperature is cooled to 40 ℃.
In addition, in order to adjust the yield of the potassium bicarbonate according to market conditions, part or all of the mother liquor concentrated by the falling film concentrator can be injected into a carbonization tower for cyclic carbonation, and potassium carbonate in the mother liquor is converted into the potassium bicarbonate, so that the yield of the potassium bicarbonate is increased.
The invention has the beneficial effects that:
1. the inventor creatively proposes the idea of firstly converting flue gas into a mixture of potassium carbonate and potassium bicarbonate, and then separating the mixture to respectively obtain high-purity products; when the mixture is separated, the potassium carbonate and the potassium bicarbonate in the mixture are creatively converted to obtain the high-purity potassium bicarbonate and potassium carbonate respectively, and specifically, the method is carried out by adopting a washing mode of water dissolved with carbon dioxide, so that the high-purity potassium bicarbonate and potassium carbonate can be respectively prepared, other impurities cannot be introduced, the reaction time is short, and the energy consumption is greatly reduced.
2. In the invention, in order to ensure the separation of potassium carbonate and potassium bicarbonate, the concentration of the produced potassium bicarbonate is higher by controlling the temperature, pH and potassium hydroxide concentration of the carbonation reaction, and the speed of the carbonation reaction and the normal operation of the subsequent crystallization reaction are improved; thereby resulting in a higher purity of the final product.
Drawings
FIG. 1 is a flow chart of the production process of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the present invention is further described with reference to specific embodiments below. Those not specifically indicated in the examples were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents used, or those not indicated together with the manufacturer, are conventional products which are commercially available. All features disclosed in this specification may be combined in any combination, except features or/and steps which are mutually exclusive.
The following examples are presented to enable those skilled in the art to more fully understand the present invention and are not intended to limit the invention in any way.
In the following examples it is to be noted that: 1. potassium hydroxide is produced by an ion membrane method; 2. the materials of the carbonization tower and the tail gas absorption tower are 316L stainless steel, and the materials of the other equipment are 304 stainless steel; 3. all the pipelines in the liquid pipeline are made of 304 stainless steel materials, and the gasket is made of polytetrafluoroethylene; 4. the water is pure water.
In the following examples, the subject was flue gas, and the flue gas composition in this example is shown in table 1:
TABLE 1 flue gas composition analysis after combustion of Natural gas
| Substance(s) | CO 2 | SO 2 | Steam of water | N 2 | O 2 | NO 2 | Granules | Total up to |
| Mass fraction (%) | 12.465 | 0.005 | 9.773 | 72.243 | 5.511 | 0.002 | 0.001 | 100 |
Example 1
The embodiment provides a production process of food-grade potassium carbonate and food-grade potassium bicarbonate, which comprises the following steps:
s1, waste gas pretreatment: washing flue gas with water, removing impurities, cooling, and then removing impurities with alkali by using 15% potassium bicarbonate solution;
s2, carbonating: carrying out carbonation reaction on the flue gas pretreated in the step S1 and a potassium hydroxide collection liquid with the concentration of 45%, wherein the reaction temperature is 60 ℃, the reaction pressure is 0.06MPa (g), a mixed solution of potassium carbonate and potassium bicarbonate is obtained, and the reaction pH is controlled not to exceed 8.5; circularly absorbing the carbon dioxide which is not absorbed by 45 percent potassium hydroxide solution to obtain a potassium hydroxide trapping liquid containing a small amount of potassium carbonate, and continuously using the potassium hydroxide trapping liquid in the carbonation reaction;
s3, crystallization separation: cooling the mixed solution obtained in the step (S2) to 10 ℃, crystallizing and separating out potassium bicarbonate solid containing a small amount of potassium carbonate, and performing solid-liquid separation on the slurry by adopting a centrifugal method to obtain potassium carbonate mother solution containing a small amount of potassium bicarbonate and potassium bicarbonate solid containing a small amount of potassium carbonate;
(1) Preparing food-grade potassium bicarbonate: and (3) washing and drying the solid obtained in the step (S3): dissolving food-grade carbon dioxide into pure water at the temperature of 20 ℃ under the condition of the pressure of 0.2MPa (g), washing the potassium bicarbonate solid containing a small amount of potassium carbonate obtained in the step S3 by using water dissolved with the carbon dioxide to obtain high-purity potassium bicarbonate, wherein the ratio of the amount of the washing water to the mass of the potassium bicarbonate solid (wet basis) is 1: and 1, drying the washed high-purity potassium bicarbonate solid to obtain food-grade potassium bicarbonate.
(2) Preparing food-grade potassium carbonate: and (3) concentrating the potassium carbonate mother liquor containing a small amount of potassium bicarbonate obtained in the step (S3) at the concentration temperature of 150 ℃ under the vacuum degree of-0.05 MPa (g) until the mass fraction of the potassium carbonate is 45%, and then performing spray drying at the spray drying temperature of 240 ℃ to finally obtain the food-grade potassium carbonate.
Example 2
The embodiment provides a production process of food-grade potassium carbonate and food-grade potassium bicarbonate, which comprises the following steps:
s1, waste gas pretreatment: washing flue gas with water, removing impurities, cooling, and then washing with 5% potassium bicarbonate solution with alkali to remove impurities;
s2, carbonating: carrying out carbonation reaction on the flue gas pretreated in the step S1 and a potassium hydroxide collection liquid with the concentration of 40%, wherein the reaction temperature is 50 ℃, the reaction pressure is 0.05MPa (g), a mixed solution of potassium carbonate and potassium bicarbonate is obtained, and the reaction pH is controlled not to exceed 8.5; circularly absorbing the carbon dioxide which is not absorbed by 45 percent potassium hydroxide solution to obtain a potassium hydroxide collecting liquid containing a small amount of potassium carbonate, and continuously using the potassium hydroxide collecting liquid in the carbonation reaction;
s3, crystallization separation: cooling the mixed solution obtained in the step S2 to 0 ℃, crystallizing and separating out potassium bicarbonate solid containing a small amount of potassium carbonate, and performing solid-liquid separation on the slurry by adopting centrifugation to obtain potassium carbonate mother solution containing a small amount of potassium bicarbonate and potassium bicarbonate solid containing a small amount of potassium carbonate;
(1) Preparing food-grade potassium bicarbonate: and (3) washing and drying the solid obtained in the step (S3): dissolving food-grade carbon dioxide into pure water at the temperature of 10 ℃ under the condition of the pressure of 0.3MPa (g), washing the potassium bicarbonate solid containing a small amount of potassium carbonate obtained in the step S3 by using water in which the carbon dioxide is dissolved to obtain high-purity potassium bicarbonate, wherein the ratio of the using amount of the washing water to the mass of the potassium bicarbonate solid (wet basis) is 1: and 5, drying the washed high-purity potassium bicarbonate solid to obtain the food-grade potassium bicarbonate.
(2) Preparing food-grade potassium carbonate: and (4) concentrating the potassium carbonate mother liquor containing a small amount of potassium bicarbonate obtained in the step (3) at 140 ℃ under the vacuum degree of-0.04 MPa (g) until the mass fraction of the potassium carbonate is 43%, and then performing spray drying at 230 ℃ to finally obtain the food-grade potassium carbonate.
Example 3
The embodiment provides a production process of food-grade potassium carbonate and food-grade potassium bicarbonate, which comprises the following steps:
s1, waste gas pretreatment: washing flue gas with water, removing impurities, cooling, and then washing with 20% potassium bicarbonate solution with alkali to remove impurities;
s2, carbonating: carrying out carbonation reaction on the flue gas pretreated in the step S1 and a 35% potassium hydroxide capture liquid at the reaction temperature of 70 ℃ and the reaction pressure of 0.07MPa (g) to obtain a mixed solution of potassium carbonate and potassium bicarbonate, and controlling the reaction pH to be not more than 8.5; circularly absorbing the carbon dioxide which is not absorbed by 45 percent potassium hydroxide solution to obtain a potassium hydroxide collecting liquid containing a small amount of potassium carbonate, and continuously using the potassium hydroxide collecting liquid in the carbonation reaction;
s3, crystallization separation: cooling the mixed solution obtained in the step S2 to-5 ℃, crystallizing and separating out potassium bicarbonate solid containing a small amount of potassium carbonate, and performing solid-liquid separation on the slurry by adopting centrifugation to obtain potassium carbonate mother liquor containing a small amount of potassium bicarbonate and potassium bicarbonate solid containing a small amount of potassium carbonate;
(1) Preparing food-grade potassium bicarbonate: and (4) washing and drying the solid obtained in the step (S3): dissolving food-grade carbon dioxide in pure water at 25 deg.C under 0.5MPa (g); and (3) washing the potassium bicarbonate solid containing a small amount of potassium carbonate obtained in the step S3 by using water dissolved with carbon dioxide to obtain high-purity potassium bicarbonate, wherein the ratio of the amount of washing water to the mass of the potassium bicarbonate solid (wet basis) is 1: and 8, drying the washed high-purity potassium bicarbonate solid to obtain the food-grade potassium bicarbonate.
(2) Preparing food-grade potassium carbonate: and (3) concentrating the potassium carbonate mother liquor containing a small amount of potassium bicarbonate obtained in the step (S3) at the concentration temperature of 160 ℃ and the vacuum degree of-0.07 MPa (g) until the mass fraction of the potassium carbonate is 48%, and then performing spray drying at the spray drying temperature of 250 ℃ to finally obtain the food-grade potassium carbonate.
Example 4
The embodiment provides a production process of food-grade potassium bicarbonate, which comprises the following steps:
s1, waste gas pretreatment: washing flue gas with water, removing impurities, cooling, and then removing impurities with alkali by using 15% potassium bicarbonate solution;
s2, carbonating: carrying out carbonation reaction on the flue gas pretreated in the step S1 and a potassium hydroxide collection liquid with the concentration of 40%, wherein the reaction temperature is 65 ℃, the reaction pressure is 0.055MPa (g), a mixed solution of potassium carbonate and potassium bicarbonate is obtained, and the reaction pH is controlled not to exceed 8.5; circularly absorbing the carbon dioxide which is not absorbed by 45 percent potassium hydroxide solution to obtain a potassium hydroxide collecting liquid containing a small amount of potassium carbonate, and continuously using the potassium hydroxide collecting liquid in the carbonation reaction;
s3, crystallization separation: cooling the mixed solution obtained in the step S2 to 5 ℃, crystallizing and separating out potassium bicarbonate solid containing a small amount of potassium carbonate, and performing solid-liquid separation on the slurry by adopting centrifugation to obtain potassium carbonate mother solution containing a small amount of potassium bicarbonate and potassium bicarbonate solid containing a small amount of potassium carbonate;
(1) And (3) washing and drying the solid obtained in the step (S3): dissolving food-grade carbon dioxide into pure water at 15 ℃ under the condition of 0.25MPa (g) of pressure, washing the potassium bicarbonate solid containing a small amount of potassium carbonate obtained in the step S3 by using water in which the carbon dioxide is dissolved to obtain high-purity potassium bicarbonate, wherein the ratio of the using amount of the washing water to the mass of the potassium bicarbonate solid (wet basis) is 1: and 6, drying the washed high-purity potassium bicarbonate solid to obtain the food-grade potassium bicarbonate.
(2) Concentrating the potassium carbonate mother liquor containing a small amount of potassium bicarbonate obtained in the step S3: and (4) completely sending the concentrated mother liquor to S2 for circulation treatment to finally obtain the food-grade potassium bicarbonate.
Comparative example 1
This comparative example differs from example 1 in that: the solid obtained in S3 was not washed.
Comparative example 2
This comparative example differs from example 1 in that: the solid obtained in S3 was washed with pure water.
Comparative example 3
This comparative example differs from example 1 in that: the carbonation temperature in S2 was 20 ℃.
Comparative example 4
This comparative example differs from example 1 in that: the carbonation temperature in S2 is 90 ℃.
Examples of the experiments
1. The flue gas after water washing in example 1 was analyzed for composition as shown in table 2, and the flue gas after alkali washing was analyzed for composition as shown in table 3:
TABLE 2 flue gas washed component analysis
| Substance(s) | CO 2 | SO 2 | H 2 O | N 2 | O 2 | NO 2 | Granules | Total up to |
| Mass fraction (%) | 13.435 | 0.035 | 2.615 | 77.995 | 5.95 | 0.0015 | 0 | 100 |
TABLE 3 flue gas alkaline wash component analysis
| Substance(s) | CO 2 | SO 2 | H 2 O | N 2 | O 2 | NO 2 | Granules | Total up to |
| Mass fraction (%) | 13.4377 | 0.0002 | 2.634 | 77.998 | 5.93 | 0.0001 | 0 | 100 |
2. The analysis of the composition of the products obtained in example 1 and in comparative examples 1-2 is shown in Table 4 (i.e.the washing comparison of the solids obtained after the crystallization centrifugation in different ways):
TABLE 4 analysis of the effect of washing pattern on the product
3. The analysis of the composition of the products prepared in example 1 and comparative examples 3 to 4 is shown in Table 5:
TABLE 5 analysis of the effect of carbonation temperature on the product
3. The quality of the food-grade potassium bicarbonate and the food-grade potassium carbonate obtained in the embodiment of the invention and the comparative example is shown in tables 6 and 7:
TABLE 6 quality of food grade potassium bicarbonate
TABLE 7 quality of food grade Potassium carbonate
In conclusion, the carbonation reaction process can separate the potassium carbonate and the potassium bicarbonate more completely, so that the concentration of the potassium bicarbonate obtained by the subsequent production is higher, the speed of the carbonation reaction is increased, and the subsequent crystallization reaction is performed normally; in the embodiment, the potassium bicarbonate solid containing a small amount of potassium carbonate is washed by water dissolved with carbon dioxide, so that high-purity potassium bicarbonate and high-purity potassium carbonate can be respectively prepared, other impurities cannot be introduced, the reaction time is short, and the energy consumption is greatly reduced.
The present invention is not limited to the above embodiments, and any structural changes made under the teaching of the present invention shall fall within the protection scope of the present invention, which has the same or similar technical solutions as the present invention.
Claims (10)
1. A production process of food-grade potassium carbonate and food-grade potassium bicarbonate is characterized by comprising the following steps:
s1, waste gas pretreatment: removing impurities and cooling the waste gas containing carbon dioxide;
s2, carbonating: carrying out carbonation reaction on the waste gas pretreated in the step S1 and potassium-containing alkali liquor to obtain a mixed solution of potassium carbonate and potassium bicarbonate, and controlling the reaction pH not to exceed 8.5;
s3, crystallization separation: cooling, crystallizing and centrifugally separating the mixed solution obtained in the step S2 to obtain a potassium carbonate mother solution containing a small amount of potassium bicarbonate and a potassium bicarbonate solid containing a small amount of potassium carbonate;
s4, washing and drying: adding washing water into the potassium bicarbonate solid containing a small amount of potassium carbonate obtained in the step S3 for washing, and drying the washed potassium bicarbonate solid to obtain food-grade potassium bicarbonate; the washing water is pure water in which carbon dioxide is dissolved.
2. The production process of food grade potassium carbonate and food grade potassium bicarbonate according to claim 1, wherein in S1, the pretreatment comprises water washing, temperature reduction and alkali washing; the alkaline washing liquid added during alkaline washing is potassium carbonate or potassium bicarbonate or a mixture of the potassium carbonate and the potassium bicarbonate.
3. The process for producing food grade potassium carbonate and food grade potassium bicarbonate according to claim 1, wherein the carbonation reaction in S2 is carried out at a temperature of 40-80 ℃ and a pressure of 0.04-0.08 MPa.
4. The process for producing food grade potassium carbonate and food grade potassium bicarbonate as claimed in claim 1, wherein unreacted carbon dioxide in carbonation reaction in S2 is recycled and absorbed by potassium-containing alkaline solution to obtain potassium-containing alkaline solution containing a small amount of potassium carbonate, and is continuously used in carbonation reaction.
5. The process for producing food grade potassium carbonate and food grade potassium bicarbonate according to claim 1, wherein the potassium-containing alkaline solution is potassium hydroxide or potassium carbonate solution or a mixture of the two; the concentration is 30-48%.
6. The process for producing food grade potassium carbonate and food grade potassium bicarbonate according to claim 1, wherein in S4, the pressure of carbon dioxide in the washing water is 0.1-0.6 MPa, and the temperature is 5-30 ℃.
7. The process of claim 6, wherein the mass ratio of the washing water to the potassium bicarbonate solid is 1:1 to 1:10.
8. the process of producing food grade potassium carbonate and food grade potassium bicarbonate of claim 1, further comprising s5. Mother liquor concentration: and (4) concentrating the potassium carbonate mother liquor containing a small amount of potassium bicarbonate obtained in the step (S3).
9. The process of claim 8, wherein in S5, the concentrated mother liquor is dried to obtain food grade potassium carbonate;
or returning part or all of the concentrated mother liquor to S2 again for S2-S4 to obtain the potassium bicarbonate.
10. The process for producing food grade potassium carbonate and food grade potassium bicarbonate according to claim 9, wherein the concentration temperature during concentration is 120-180 ℃, and the vacuum degree is-0.02 to-0.088 MPa; the drying temperature is 220-260 ℃ during drying.
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