CN103638808A - Method for enriching carbon dioxide in sugar refinery flue gas by utilizing carbonic anhydrase to catalyze lime milk - Google Patents
Method for enriching carbon dioxide in sugar refinery flue gas by utilizing carbonic anhydrase to catalyze lime milk Download PDFInfo
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- CN103638808A CN103638808A CN201310573446.9A CN201310573446A CN103638808A CN 103638808 A CN103638808 A CN 103638808A CN 201310573446 A CN201310573446 A CN 201310573446A CN 103638808 A CN103638808 A CN 103638808A
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- carbonic anhydrase
- gas
- flue gas
- carbon dioxide
- sugar refinery
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Abstract
A disclosed method for enriching carbon dioxide in sugar refinery flue gas by utilizing carbonic anhydrase to catalyze lime milk comprises: adding carbonic anhydrase into a calcium hydrate emulsion, adding into a gas-liquid reactor, introducing boiler flue gas, controlling the gas pressure at 0.01-0.10 MPa, keeping the temperature of the reactant system at 25-65 DEG C, carbonating the reactant system to have a pH value of 5.0-7.0, heating the reactant system to 75-100 DEG C for releasing CO2 gas, settling, collecting precipitation, calcining to release CO2 gas. According to the method provided by the invention, the addition of carbonic anhydrase helps to save carbonization time; and the enriched released CO2-containing mixed gas can be used to clear a crude sugar solution, so that CO2 in flue gas is subjected to resource utilization as well as the pollution source is thoroughly solved, also the discharge amount of CO2 and heat energy in flue gas is reduced, and the ecological environment is protected.
Description
Technical field
The present invention relates to utilize carbon dioxide in carbonic anhydrase catalysis milk of lime enriched flue gas, belong to the technology of flue gas economic utilization in biological environmental production field.
Background technology
The impurity that raw sugar raw sugar liquid that dissolve or that extract from the raw materials such as beet or sugarcane contains 2-20%, sugar refinery utilizes carbonatation process and sulfurous method clarification process.Carbonatation process adds milk of lime in raw sugar liquid, then passes into CO
2, utilize CO
2adsorb non-sugar impurity with the milk of lime precipitation of calcium carbonate generating that reacts.Syrup colour by its clarification is low, and the purity of crystallization products obtained therefrom white granulated sugar is high, quality better.The essence of carbonatation process is exactly to form the calcium carbonate of nascent state in order to adsorb the non-sugar impuritiess such as suspension, colloid thing, reaches the object of clarification raw sugar liquid.The formation of calcium carbonate is mainly CO at present
2with reacting of calcium hydroxide.
The fining agent CO using in carbonatation process technique
2mainly to prepare by calcined limestone in limekiln, CO
2volumetric concentration is 30-38%, and this reaction is the endothermic reaction, need consume 10% coke combustion-supporting during calcining.In addition the CO that, calcining makes
2except a part is used as fining agent utilization, all the other are all discharged to atmosphere, and after calcining, superfluous lime mud belongs to solid waste.So the limekiln that carbonatation process technique adopts not only operating cost is high, and pollutes the environment, environment protecting is poor.
The material that contains a large amount of contaminated environment in the flue gas discharging after the fuel such as combustion of industrial boiler coal, crude oil, natural gas, waste fiber, the composition of these contaminated environment is discharged in atmosphere, can damage the ozone layer, cause the formation of acid rain, the change of the generation of breathing problem and plant metabolism process.The mode of the boiler flue of sugar enterprise's processing is at present generally water film dedusting method, and water film dedusting method can only be removed dust, and after processing, flue gas still contains CO
2and SO
2deng composition, CO wherein
2content be 8-18%(percent by volume), it is directly discharged in atmosphere, not only wasted resource but also contaminated environment.But a large amount of commercial Application confirms, the CO in flue gas
2concentration is lower, and with it, as fining agent, effect is unsatisfactory, and CO in flue gas
2though ratio is low, total amount is larger.The CO of current boiler smoke
2be absorbed with a lot of methods, can be divided into chemical solvent absorption method and pressure swing adsorption method in general.The drawback of chemical solvent absorption method is can produce huge energy consumption in the process of desorption, and absorption efficiency is not high; It is not high that pressure swing adsorption method also exists absorption efficiency, and the high problem of energy consumption.In addition, sugar refining technology is continuous production process, utilizes CO in flue gas
2process time long, affect output and the economic benefit of sugar enterprise.
How to utilize fast the CO in flue gas
2it is exactly problem to be solved by this invention.Carbonic anhydrase (CA) is mainly catalysis CO
2+ H
2o==HCO
3 -+ H
+reversible reaction.This enzyme is prevalent in animal and plant circle.Find for the first time it is in animal cow's serum.Calcium bicarbonate catalysis CO
2hydration very capable, reaction rate can reach 10
6/ s.Research shows: CA has acceleration from large-scale combustors and catches CO
2potentiality.By heat treatment, discharge and utilize CO in calcium bicarbonate that carbonic anhydrase accelerate to generate and calcium carbonate
2thereby enrichment obtains the CO that concentration is higher
2, improved on the other hand the efficiency of clarification process of sugar production process.
Summary of the invention
The object of the invention is to overcome the shortcoming that prior art exists, provide a kind of production efficiency to improve significantly, save the energy, reduce costs, environment protecting utilizes boiler flue to make the process modification method of fining agent preferably.
The object of the invention is achieved through the following technical solutions:
Utilize the method for carbonic anhydrase catalysis milk of lime enrichment sugar refinery carbon dioxide in flue gas: first in calcium hydroxide emulsion, add carbonic anhydrase, then add in gas-liquid reaction device, pass into boiler flue, control gas pressure is 0.01-0.10Mpa, reactant system temperature is 25-65 ℃, reactant system full charge is to pH5.0-7.0, and reactant system is heated to 75-100 ℃ and discharges CO
2gas, sedimentation, collecting precipitation, calcining discharges CO
2gas;
The quality of described carbonic anhydrase be in emulsion calcium hydroxide quality 0.00003% ?0.0003%;
Mass concentration containing effective CaO in described calcium hydroxide emulsion is 5-40%.
Preferably, described boiler flue is the flue gas producing after boiler combustion coal, oil, natural gas, cellulose or lignin, through dedusting, clear water or soda lye wash, gas-water separation pretreatment, then removes solid, suspended impurity and sulfide, in percent by volume, the CO obtaining
2content is the mist of 8-18%.
Described calcium hydroxide emulsion is that the powder or the lump lime that after limestone calcination, generate add the emulsion that water slake generates.
The quality of described carbonic anhydrase is the 0.0001%-0.0002% of calcium hydroxide quality in emulsion.
Described calcining is that calcium carbonate is decomposed into CaO and CO under temperature 800-950 ℃ condition
2.
Prior art is CO
2first generate carbonic acid with water, then and Ca (OH)
2generate calcium carbonate, due to CO in flue gas
2concentration is lower, and course of reaction is slower, and course of reaction is as follows:
The present invention adds the hydration reaction of carbonic anhydrase catalysis carbon dioxide, forms in addition after calcium carbonate, continues to pass into CO
2, make part calcium carbonate and CO
2form calcium bicarbonate, because calcium bicarbonate is unstable, reversible reaction can occur and be decomposed into calcium carbonate, carbon dioxide and water, course of reaction is as follows:
In addition, calcium carbonate can be decomposed into carbon dioxide and calcium oxide under hot state, and calcium oxide again slake becomes milk of lime and recycles.
The present invention compared with prior art tool has the following advantages and effect:
(1) hydration reaction of carbonic anhydrase catalysis carbon dioxide for the present invention, when accelerating reaction rate, strengthens the ability of milk of lime absorbing carbon dioxide greatly, has improved economic benefit and social benefit.
(2) the present invention utilizes character that the excessive full charge of calcium carbonate the generates calcium bicarbonate carbon dioxide in absorption from flue gas in a large number, reduces the discharge of its greenhouse gases.
(3) the invention solves under current technology containing CO
2the key issue that concentration is low, heating calcium bicarbonate and calcination of calcium carbonate can discharge the CO of enrichment
2, react with calcium bicarbonate in syrup and generate calcium carbonate and can effectively adsorb the non-sugar impurity in raw sugar liquid, reach raw sugar liquid clarification object.
(4) CaO reusable edible in the present invention, freight volume and the storage place that can reduce limekiln lime stone used, reduce dust discharge amount, and environment protecting is good.
The specific embodiment
For understanding better the present invention, below in conjunction with embodiment, the present invention will be further described, but embodiments of the present invention are not limited to this.
Below by 2 groups of experiments, compare (wherein 1 group is not added enzyme, and another 1 group add carbonic anhydrase) in each embodiment, object is relatively to add carbonic anhydrase whether can shorten CO in flue gas
2with the time of calcium hydroxide reaction generation calcium bicarbonate,
Embodiment 1
Boiler flue is taken from the flue gas producing after the boiler combustion coal in sugar refinery, through dedusting, clear water or soda lye wash, gas-water separation pretreatment, then removes solid, suspended impurity and sulfide, obtains mainly containing N
2, CO
2, CO and O
2deng mist, CO wherein
2content is 14-18%(percent by volume), gas pressure 0.01-0.10MPa.
Get respectively 2 groups of lime slurry 1000kg, effective CaO mass concentration is all 5%, does not then add and add respectively the carbonic anhydrase (model: 9001-03-0) 0.000024kg, stirs of taking advantage of easy biological Co., Ltd in commercially available Shanghai.Under similarity condition, add respectively in gas-liquid reaction device, pass into boiler flue, reactant system temperature is 25 ± 1 ℃, reactant system full charge is respectively 12.3min and 10.1min to a pH value 5.5 ± 0.1 o'clock required time, and known interpolation carbonic anhydrase can not shorten for 17.9% time than not adding carbonic anhydrase.In addition, these 2 groups of full charges are heated to respectively 75 ℃ to the reactant system of pH value 5.5 ± 0.1, and in system, calcium bicarbonate decomposition discharges containing CO
2volume fraction is all that (remaining gas is mainly N for the mist of 65-68%
2and O
2), then sedimentation, collects precipitation of calcium carbonate, 850 ± 5 ℃ of calcinings, discharges containing CO
2volume fraction is all that (remaining gas is mainly N for the mist of 35-37%
2).
The CO of sugar enterprise's tradition use
2gas concentration is 34-38%, and flue gas concentration is 8-18%, if utilize flue gas will reach same clarifying effect, the flue gas that just must pass into more volumes is gone full charge, this just needs the more time, and cause full charge apparatus overload and overflow, solution is to improve the concentration of flue gas.With traditional CO
2gas overcarbonation calcium carbonate generates calcium bicarbonate, then decomposes and discharges CO
2gas also can, but the time needing is longer.Sugaring is a continuous production process, need to generate time of calcium bicarbonate shortlyer just can reach quantity-produced requirement, the shortening of time means increasing substantially of whole production line efficiency, and the present embodiment can be saved time of 17.9% has very important impact to production efficiency.
Embodiment 2
Boiler flue is taken from the flue gas producing after the boiler combustion oil in sugar refinery, through dedusting, clear water or soda lye wash, gas-water separation pretreatment, then removes solid, suspended impurity and sulfide, obtains mainly containing N
2, CO
2, CO and O
2deng mist, CO wherein
2content is 12-16%(percent by volume), gas pressure 0.01-0.10MPa.
Get respectively 2 groups of lime slurry 1000kg, wherein effective CaO mass concentration percentage is about 40%, then do not add respectively and add the Shanghai of buying from market and take advantage of the carbonic anhydrase (model: 9001-03-0) be about 0.000015kg of easy biological Co., Ltd, stir, under similarity condition, then add respectively in gas-liquid reaction device, pass into boiler flue, reactant system temperature is 50 ± 1 ℃, reactant system full charge is respectively 35.8min and 20.2min to a pH value 6.5 ± 0.1 o'clock required time, known interpolation carbonic anhydrase can not shorten for 43.6% time than not adding carbonic anhydrase.In addition, these 2 groups of full charges are heated to respectively 100 ℃ to the reactant system of pH value 6.5 ± 0.1, and in system, calcium bicarbonate decomposition discharges containing CO
2volume fraction is about the mist of 83-85%, and (remaining gas is mainly N
2and O
2), then sedimentation, collects precipitation of calcium carbonate, 850 ± 5 ℃ of calcinings, discharges containing CO
2volume fraction is that (remaining gas is mainly N for the mist of 34-37%
2).
Embodiment 3
Boiler flue is taken from the flue gas producing after the boiler combustion natural gas in sugar refinery, through dedusting, clear water or soda lye wash, gas-water separation pretreatment, then removes solid, suspended impurity and sulfide, obtains mainly containing N
2, CO
2, CO and O
2deng mist, CO wherein
2content is 10-14%(percent by volume), gas pressure 0.01-0.10MPa.
Get respectively 2 groups of lime slurry 1000kg, wherein effective CaO mass concentration percentage is about 25%, then do not add respectively and add the Shanghai of buying from market and take advantage of the carbonic anhydrase (model: 9001-03-0) be about 0.000025kg of easy biological Co., Ltd, stir, under similarity condition, then add respectively in gas-liquid reaction device, pass into boiler flue, reactant system temperature is 65 ± 1 ℃, reactant system full charge is respectively 22.6min and 12.1min to a pH value 7.0 ± 0.1 o'clock required time, known interpolation carbonic anhydrase can not shorten for 46.5% time than not adding carbonic anhydrase.In addition, these 2 groups of full charges are heated to respectively 85 ℃ to the reactant system of pH value 7.0 ± 0.1, and in system, calcium bicarbonate decomposition discharges containing CO
2volume fraction is about the mist of 53-55%, and (remaining gas is mainly N
2and O
2), then sedimentation, collects precipitation of calcium carbonate, 900 ± 5 ℃ of calcinings, discharges containing CO
2volume fraction is that (remaining gas is mainly N for the mist of 33-36%
2).
Embodiment 4
Boiler flue is taken from the flue gas producing after the boiler combustion cellulose in sugar refinery and lignin, through dedusting, clear water or soda lye wash, gas-water separation pretreatment, then removes solid, suspended impurity and sulfide, obtains mainly containing N
2, CO
2, CO and O
2deng mist, CO wherein
2content is 8-12%(percent by volume), gas pressure 0.01-0.10MPa.
Get respectively 2 groups of lime slurry 1000kg, wherein effective CaO mass concentration percentage is about 35%, then do not add respectively and add the Shanghai of buying from market and take advantage of the carbonic anhydrase (model: 9001-03-0) be about 0.0007kg of easy biological Co., Ltd, stir, under similarity condition, then add respectively in gas-liquid reaction device, pass into boiler flue, reactant system temperature is 55 ± 1 ℃, reactant system full charge is respectively 28.7min and 16.6min to a pH value 5.0 ± 0.1 o'clock required time, known interpolation carbonic anhydrase can not shorten for 42.2% time than not adding carbonic anhydrase.In addition, these 2 groups of full charges are heated to respectively 95 ℃ to the reactant system of pH value 5.0 ± 0.1, and calcium bicarbonate decomposition discharges containing CO
2volume fraction is about the mist of 85-88%, and (remaining gas is mainly N
2and O
2), then sedimentation, collects precipitation of calcium carbonate, 870 ± 5 ℃ of calcinings, discharges containing CO
2volume fraction is that (remaining gas is mainly N for the mist of 35-37%
2).
The hydration reaction of carbonic anhydrase catalysis carbon dioxide for the present invention, has significantly accelerated CO in milk of lime enriched flue gas
2reaction rate.As can be seen from the above embodiments, first in calcium hydroxide emulsion, add carbonic anhydrase, then add in gas-liquid reaction device, pass into boiler flue, control gas pressure is 0.01-0.10Mpa, reactant system temperature is 25-65 ℃, and reactant system full charge, to pH5.0-7.0, is added carbonic anhydrase and can not saved the 17.9%-46.5% time than not adding carbonic anhydrase.By CO in flue gas
2the calcium bicarbonate solution heating generating with calcium hydroxide reaction can discharge containing CO
2volume fraction is the mist of 55-88%, and precipitation of calcium carbonate is collected in then sedimentation, and calcining precipitation can discharge containing CO
2volume fraction is the mist of 34-38%.Enrichment discharge containing CO
2the mist that concentration is higher can be used for clarifying raw sugar liquid, avoids low concentration CO
2the appearance that the full charge time is long, Sucrose loses the problems such as large, easy tank boil-overs existing during gas full charge liquid glucose; By resourcebility of the present invention, utilize CO in flue gas
2time thoroughly solved pollution sources, and can reduce CO in flue gas
2with the discharge capacity of heat energy, protected ecological environment.
Claims (5)
1. utilize the method for carbonic anhydrase catalysis milk of lime enrichment sugar refinery carbon dioxide in flue gas, it is characterized in that: first in calcium hydroxide emulsion, add carbonic anhydrase, then add in gas-liquid reaction device, pass into boiler flue, control gas pressure is 0.01-0.10Mpa, reactant system temperature is 25-65 ℃, and reactant system full charge is to pH5.0-7.0, and reactant system is heated to 75-100 ℃ and discharges CO
2gas, sedimentation, collecting precipitation, calcining discharges CO
2gas;
The quality of described carbonic anhydrase be in emulsion calcium hydroxide quality 0.00003% ?0.0003%;
Mass concentration containing effective CaO in described calcium hydroxide emulsion is 5-40%.
2. the method for utilizing carbonic anhydrase catalysis milk of lime enrichment sugar refinery carbon dioxide in flue gas according to claim 1, it is characterized in that: described boiler flue is the flue gas producing after boiler combustion coal, oil, natural gas, cellulose or lignin, through dedusting, clear water or soda lye wash, gas-water separation pretreatment, then remove solid, suspended impurity and sulfide, in percent by volume, the mist that the CO2 content obtaining is 8-18%.
3. the method for utilizing carbonic anhydrase catalysis milk of lime enrichment sugar refinery carbon dioxide in flue gas according to claim 1, is characterized in that: described calcium hydroxide emulsion is that the powder or the lump lime that after limestone calcination, generate add the emulsion that water slake generates.
4. the method for utilizing carbonic anhydrase catalysis milk of lime enrichment sugar refinery carbon dioxide in flue gas according to claim 1, is characterized in that: the quality of described carbonic anhydrase is the 0.0001%-0.0002% of calcium hydroxide quality in emulsion.
5. the method for utilizing carbonic anhydrase catalysis milk of lime enrichment sugar refinery carbon dioxide in flue gas according to claim 1, is characterized in that: described calcining is that calcium carbonate is decomposed into CaO and CO under temperature 800-950 ℃ condition
2.
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| CN106999842A (en) * | 2014-08-27 | 2017-08-01 | 二氧化碳处理公司 | Use the CO2 catching methods of the hot vibrios carbonic anhydrase of ammonification |
| CN113877414A (en) * | 2021-10-25 | 2022-01-04 | 西安热工研究院有限公司 | Flue gas CO capture based on magnetic activated carbon immobilized carbonic anhydrase2System and method |
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| CN113877414A (en) * | 2021-10-25 | 2022-01-04 | 西安热工研究院有限公司 | Flue gas CO capture based on magnetic activated carbon immobilized carbonic anhydrase2System and method |
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