CN101007236A - Preparation method of ultra-fine desulfurizer slurry and device thereof - Google Patents

Preparation method of ultra-fine desulfurizer slurry and device thereof Download PDF

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Publication number
CN101007236A
CN101007236A CN 200610165584 CN200610165584A CN101007236A CN 101007236 A CN101007236 A CN 101007236A CN 200610165584 CN200610165584 CN 200610165584 CN 200610165584 A CN200610165584 A CN 200610165584A CN 101007236 A CN101007236 A CN 101007236A
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China
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slurry
desulfurizer
desulfurizer slurry
lime
ultra
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张颉
赵素伟
由长福
陈昌和
祁海鹰
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Tsinghua University
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Tsinghua University
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Abstract

A superfine desulfurizer slurry preparation methods and devices relates to the desulfurizer Preparation in flue gas desulfurization technology. The invention is characterized by: preparing the desulfurizer slurry using block-shaped calcarea lime materials in larger size, using local high temperature reaction heat when block-shaped calcarea lime hydrate and the volume expansion action of lime hydration to break the block-shaped calcarea lime into super-fine calcium hydrate particles. The preparation method can significantly reduce the desulfurizer particle size, not only increase calcium utilization rate of desulfurizer particles and reduce the spray volume of desulfurizer slurry, but also enhance the suspension property of desulfurizer particles in slurry; it can reach higher desulfurization efficiency under lower rate of calcium to sulfur, while increase the security and stability of system operation significantly, thereby achieves semi-dry desulfurization system highly effective and stable operation.

Description

A kind of ultra-fine desulfurizer slurry preparation method and device
Technical field
The present invention relates to a kind of semi-dry desulphurization system and technology of combustion apparatus discharging flue gas, particularly a kind of ultra-fine desulfurizer slurry preparation method and device belong to the flue gas desulfurization technique field.
Background technology
Coal combustion produced pollution thing is the greatest contamination source of causing China's environmental destruction.China's sulfur dioxide (SO2) emissions 90% come spontaneous combustion coal, and total emission volumn surpasses 2,000 ten thousand tons for years, and acid rain district area accounts for 1/3 of area.The task of top priority that has become China's air pollution treatment is administered in coal-fired sulfur dioxide pollution.
Improvement to sulfur dioxide, the external at present main limestone-gypsum wet desulphurization technology that adopts, its major advantage is the desulfuration efficiency height, but has investment and operating cost height, floor space is big, water consumption is big and need a series of problems such as handles again to water.The SO of comprehensive China 2Pollution situation and present economic strength, all adopt to have very high desulfurization efficiency but the expensive wet desulphurization technology of investment operation is difficult to accept, and the high water consumption of wet desulphurization technology also causes very big obstacle to the application of water-deficient area, the vast Midwest of China.
Compare with the wet desulphurization technology, the semi-dry process flue gas desulphurization technology has low cost, low expense, low water consumes and than advantages such as high desulfurization efficiencies, have bright development prospect, is the focus of domestic and international Application and Development.Use more semi-dry process flue gas desulphurization technology in China at present, mostly utilize postdigestive lime (slurry) as desulfurizing agent, the material of separating with desulfurizing agent and outside deduster is used for remove sulfur in smoke gas by strong gas-solid liquid three-phase as the circulation fluidized bed material in fluid bed reacting tower.As Chinese invention patent 00128285.9,02147821.X and 03125276.1 etc., all be to adopt a desulfurization reaction tower that is similar to recirculating fluidized bed, by flue gas, sorbent particle and the haptoreaction of atomized water drop in tower to realize the desulfurization purpose.
Yet, the low and relatively poor problem of operation stability of semi-dry process flue gas desulphurization technology present ubiquity desulfuration efficiency in practical engineering application.One of major reason that causes the problems referred to above is that the reactivity of employed desulfurizing agent is lower.And cause the active low main cause of reactive desulfurizing agent is that the particle diameter of sorbent particle is too big.Because SO 2Mainly occur in the sorbent particle surface with the reaction of desulfurizing agent, the sorbent particle particle diameter is big more, and its specific area is more little, desulfurizing agent and SO 2Contact probability more little, thereby cause the calcium utilization of desulfurizing agent and system's desulfuration efficiency low.For the semi-dry process flue gas desulphurization system, carrying out along with desulphurization reaction, moisture in the desulfurizing agent constantly evaporates, and the desulfurization reaction mechanism on desulfurizing agent surface has the higher ionic reaction of reaction rate of moisture film to change the lower gas-solid reaction of desulphurization reaction speed that the surface does not have moisture film into from surface coverage.Therefore, along with injection flow rate increases, the liquid film thickening on desulfurizing agent surface, the water evaporates time lengthening, desulfuration efficiency can increase to some extent, but can cause the operation stability variation of system simultaneously.In contrast, along with injection flow rate reduces, the water evaporates time shortens, and the ionic reaction ratio descends, and the gas-solid reaction ratio rises, and sorbent particle is rendered as the time lengthening of dry state, and system's operation stability strengthens, but desulfuration efficiency reduces.Therefore the efficient operation of semi-dry desulphurization system and stable operation are a pair of contradiction, and the sorbent particle particle diameter reduce to solve preferably this contradiction, thereby improve the desulfuration efficiency and the operation stability of system.
Summary of the invention
The objective of the invention is at the reactive desulfurizing agent activity of using in the present semi-dry process flue gas desulphurization low, particle diameter is bigger, thereby cause system's operation stability relatively poor, the calcium utilization of desulfurizing agent and the low problem of system's desulfuration efficiency, a kind of ultra-fine desulfurizer slurry preparation method and device are provided, utilize the prepared desulfurizer slurry of the present invention not only can improve the calcium utilization and the straying quatity that reduces desulfurizer slurry of sorbent particle, and can strengthen the suspension characteristic of sorbent particle in slurries, help realizing the efficient stable operation of semi-dry desulphurization system.
The present invention is achieved by the following technical solutions:
A kind of ultra-fine desulfurizer slurry preparation method is characterized in that this method comprises the steps:
1) be that the block lime of 1~100mm is poured in the hydration reactor with particle diameter;
2) in hydration reactor, add with block lime in the ratio of molal quantity of CaO be 10: 1~20: 1 digestion water;
3) keep the hydration reactor static condition, make block lime and water fully carry out the hydration reaction process;
4) in hydration reactor, add the slurrying water again, prepare mass concentration and be 10~20% desulfurizer slurry;
5) start the interior agitator of hydration reactor, the desulfurizer slurry that is evenly suspended;
6) desulfurizer slurry is delivered to slurry can, the solid impurity particle by in the block lime of filter elimination obtains desulfurizer slurry.
Ultra-fine desulfurizer slurry preparation method of the present invention, its feature also is: CaO content is more than 80% in the described block lime.
As further improvement project of the present invention, the time of repose of described hydration reactor is 15~30 minutes; The temperature of digestion water and slurrying water is 5~40 ℃.
The present invention also provides a kind of ultra-fine desulfurizer slurry preparation facilities, it is characterized in that: this device comprises hydration reactor, be arranged on agitator and slurry can in the hydration reactor, described hydration reactor is connected by connecting pipe with slurry can, in the exit of described slurry can filter is set.
Ultra-fine desulfurizer slurry preparation facilities of the present invention, its agitator adopts centrifugal spiral agitator; Its filter adopts filter structure, and mesh size is 0.1~2mm.
The present invention compared with prior art, have the following advantages and the high-lighting effect: the ultra-fine desulfurizer slurry preparation method, has remarkable effect (particle diameter of sorbent particle is about 10 μ m) to reducing the sorbent particle particle diameter, not only can improve the calcium utilization and the straying quatity that reduces desulfurizer slurry of sorbent particle, and can strengthen the suspension characteristic of sorbent particle in slurries, help solving because the too much sticking wall scale problems of bringing of desulfurizer slurry straying quatity and deposition of the pipeline in the desulfurizer slurry course of conveying and atomizer blockage problem, higher desulfuration efficiency can not only be issued to than low calcium-sulphur ratio, the security and stability of the operation of raising system greatly simultaneously, thus the efficient stable of realizing the semi-dry desulphurization system moves.In addition, the pulverulent lime particle that adopts bigger block lime to replace adopting usually in the engineering application carries out the desulfurizer slurry preparation, because block lime size is bigger, its specific area is less, avoided effectively pulverulent lime be exposed in the air the active reduction problem of lime that often occurs.In addition, the powdered granule that adopts bigger block lime to replace adopting usually carries out the desulfurizer slurry preparation, saved the fragmentation and the induction system of lime raw material, simplified systems produce technology and saved floor space, thereby greatly reduced the preparation cost of desulfurizer slurry.
Description of drawings
Fig. 1 is apparatus structure of the present invention and process flow diagram.
The particle diameter of the calcium hydroxide particle in the desulfurizer slurry that Fig. 2 is block for employing and pulverulent lime makes distributes.
Fig. 3 distributes for the particle diameter of the calcium hydroxide particle in the obtained slurries of block lime that adopt the different-grain diameter scope.
Fig. 4 is that the particle diameter of the calcium hydroxide particle in the desulfurizer slurry of different quality concentration distributes.
Among the figure: the 1-hydration reactor; The 2-agitator; The 3-slurry can; The 4-connecting pipe; The 5-filter.
The specific embodiment
Be further described below in conjunction with structure, technological process and the operation principle of accompanying drawing device of the present invention.
Apparatus of the present invention mainly comprise: connecting pipe 4 between the agitator 2 in hydration reactor 1, the hydration reactor, slurry can 3, hydration reactor 1 and the slurry can 3 and the filter 5 that is arranged on the slurry can exit.
Technological process of the present invention is:
At first, with the particle size range of certain mass is that the block lime of 1~100mm is poured hydration reactor 1 into, in hydration reactor 1, add then with block lime in the ratio of molal quantity of CaO be 10: 1~20: 1 digestion water, then hydration reactor 1 is left standstill a period of time, time of repose is generally 15~30 minutes.CaO content is at least 80% in the block lime, mainly adjusts according to the digestible degree of block lime and digestion water, carries out sufficient fine-powdered hydration reaction process to guarantee block lime and water.
Then, in hydration reactor 1, add the slurrying water, prepare mass concentration and be 10~20% desulfurizer slurry, start the agitator 2 in the hydration reactor 1 simultaneously, the desulfurizer slurry that is evenly suspended.At last,,, be transported in the slurry can 3, use when moving for the semi-dry desulphurization system by the connecting pipe 4 between hydration reactor 1 and the slurry can 3 with the even suspension ultra-fine desulfurizer slurry for preparing in the hydration reactor 1.The quantity of slurrying water is determined with the difference of digestion water consumption according to the required Total Water of the desulfurizer slurry of preparation certain mass concentration.Slurrying water and digestion water use water for industrial use usually, and water temperature is a normal temperature, is generally 5~40 ℃.Agitator 2 in the hydration reactor 1 adopts centrifugal helical stir usually.Alr mode can vertically be placed stirring at the central axis of hydration reactor 1, also can place in the lower area side direction of hydration reactor 1 and stir.Consider in the block lime raw material and contain some impurity inevitably, filter 5 is set in the exit of slurry can 3.The form of filter 5 adopts the filter structure of certain mesh size usually, and mesh size is generally 0.1~2mm.
Ultra-fine desulfurizer slurry preparation method's of the present invention principle is as follows: block lime is met water and is digested, and becomes Ca (OH) from CaO 2, emit a large amount of reaction heat (66.5kJ/mol) at local space simultaneously, because Ca (OH) 2Mole volume (33cm 3/ mol) greater than CaO (16.9cm 3/ mol), expanded by heating and the Ca that generates (OH) 2The double action of volumetric expansion make and the lime particle fragmentation form superfine calcium hydroxide suspension.
The present invention is described further to enumerate several specific embodiments below.
Embodiment 1:
Introduce the block lime and the pulverulent lime that adopt Shoudu Iron and Steel Co building materials chemical industry factory to be produced respectively below and carry out contrast experiment's situation that desulfurizer slurry prepares as raw material.With particle diameter is that the block lime of 10~30mm and pulverulent lime that particle size range is 0.2~700 μ m are poured into respectively in the hydration reactor for each 50 kilograms, and CaO content is 86.5% in the lime; Then, add 210 liters of digestion waters in hydration reactor, the ratio of the molal quantity of CaO is 15 in digestion water and the lime; Then, hydration reactor was in static condition 15 minutes, made lime and water fully carry out the hydration reaction process; Then, in hydration reactor, add 75 liters of slurrying waters again, be prepared into mass concentration and be 15% desulfurizer slurry; At last, start the agitator 2 in the hydration reactor 1, the desulfurizer slurry that is evenly suspended, and with desulfurizer slurry by the connecting pipe 4 between hydration reactor 1 and the slurry can 3, be transported in the slurry can 3.The temperature of digestion water and slurrying water is 20 ℃.Table 1 has provided the granularmetric analysis comparing result that adopts calcium hydroxide particle in the desulfurizer slurry that block lime and pulverulent lime make as raw material respectively.Fig. 2 has provided the grading curve that adopts the calcium hydroxide particle in the desulfurizer slurry that block lime and pulverulent lime make respectively.By table 1 and Fig. 2 as seen, block lime is compared with pulverulent lime, though initial size has increased hundreds of times, yet adopt the size ratio of calcium hydroxide particle in the prepared desulfurizer slurry of block lime to adopt the particle diameter of calcium hydroxide particle in the prepared desulfurizer slurry of pulverulent lime to reduce about 1 times.In addition, adopt calcium hydroxide particle in the desulfurizer slurry that block lime makes, have the fine particle fraction of larger amt in the particle size range below 10 μ m.As seen, block lime is compared with pulverulent lime, can reduce calcium hydroxide particle particle diameter in the desulfurizer slurry well.
The comparing result of grain diameter in the desulfurizer slurry that table 1 block lime of employing and pulverulent lime make
Parameter name The pulverulent lime raw material Block lime raw material The improvement degree
Volume average particle size D43 (μ m) 18.89 9.20 51.3%
50% volume share particle diameter D50 (μ m) 18.68 8.89 52.4%
In addition, the suspension effect of the desulfurizer slurry that makes of block lime of the employing described in the embodiment 1 and pulverulent lime differs greatly.Adopt the suspension characteristic of the desulfurizer slurry that block lime prepares better, leave standstill after 2 days and still have suspension characteristic preferably, present the outstanding turbid state of the milky similar to the desulfurizer slurry that has just prepared; And the desulfurizer slurry suspension characteristic that adopts pulverulent lime to prepare is relatively poor, leaves standstill less than 10 minutes, and desulfurizer slurry obviously is divided into the solid sediment of container bottom and the clarified solution on container top.
Embodiment 2:
With particle size range be 1~10mm, 10~30mm, 30~60mm and 60~100mm four kinds of block lime samples each 50 kilograms pour into respectively in the hydration reactor, CaO content is 86.5% in the lime; Then, add 210 liters of digestion waters in hydration reactor, the ratio of the molal quantity of CaO is 15 in digestion water and the lime; Then, hydration reactor was in static condition 15 minutes, made lime and water fully carry out the hydration reaction process; Then, in hydration reactor, add 75 liters of slurrying waters again, be prepared into mass concentration and be 15% desulfurizer slurry.Other preparation condition is with embodiment 1.Table 2 has provided the block lime that the adopts four kinds of different-grain diameter scopes particle diameter comparing result to calcium hydroxide particle in the desulfurizer slurry that makes.Fig. 3 has provided the influence that the calcium hydroxide particle particle diameter in the desulfurizer slurry that the block lime that adopts four kinds of different-grain diameter scopes makes distributes.By table 2 and Fig. 3 as seen, when the particle diameter of block lime was 1~10mm, its specific area was bigger, easily with airborne water vapour and CO 2React and make that lime is active to descend, make that the calcium hydroxide particle particle diameter in the slurries increases; When the particle diameter of block lime was 60~100mm, intergranular interaction force increased in the slurries, made that the calcium hydroxide particle particle diameter in the slurries increases.The result shows, has the optimum grain-diameter scope of block lime, and this optimum grain-diameter scope is 10~30mm.
The comparing result of grain diameter in the desulfurizer slurry that the block lime of table 2 employing different-grain diameter scope makes
Parameter name 1-10mm 10-30mm 30-60mm 60-100mm
Volume average particle size D43 (μ m) 12.27 9.20 9.51 10.95
50% volume share particle diameter D50 (μ m) 10.97 8.89 9.18 10.34
Embodiment 3:
With particle size range is that the block lime of 10~30mm is poured in the hydration reactor for 30 kilograms, and CaO content is 86.5% in the lime; Then, add the digestion water of 167 liters, 126 liters and 83 liters respectively in hydration reactor, the ratio of the molal quantity of CaO is respectively 20,15 and 10 in digestion water and the lime; Then, hydration reactor was in static condition 30 minutes, made lime and water fully carry out the hydration reaction process; Then, in hydration reactor, add the slurrying water of 103 liters, 45 liters and 37 liters again, prepare mass concentration respectively and be 10%, 15% and 20% desulfurizer slurry.Other preparation condition is with embodiment 1.Table 3 has provided the particle diameter comparing result of calcium hydroxide particle in the desulfurizer slurry of above-mentioned three kinds of different quality concentration.Fig. 4 provided above-mentioned three kinds of different quality concentration desulfurizer slurry in the influence that distributes of calcium hydroxide particle particle diameter.By table 3 and Fig. 4 as seen, the slurries mass concentration is high more, and intergranular interaction force has increase slightly in the slurries, makes that the particle diameter of calcium hydroxide particle increases a little in the desulfurizer slurry.
The comparing result of grain diameter in the desulfurizer slurry of table 3 different quality concentration
Parameter name 10% 15% 20%
Volume average particle size D43 (μ m) 10.91 11.50 11.83
50% volume share particle diameter D50 (μ m) 10.04 11.29 11.46
Yet, block lime particle diameter (1~100mm) and slurries mass concentration (10~20%) scope in, lime particle diameter and slurries mass concentration are little to distribution shape, peak value scope and the suspension effect influence of calcium hydroxide particle particle diameter in the desulfurizer slurry that finally prepares, and all are better than the desulfurizer slurry that adopts pulverulent lime to make.

Claims (8)

1. a ultra-fine desulfurizer slurry preparation method is characterized in that this method comprises the steps:
1) be that the block lime of 1~100mm is poured in the hydration reactor with particle diameter;
2) in hydration reactor, add with block lime in the ratio of molal quantity of CaO be 10: 1~20: 1 digestion water;
3) keep the hydration reactor static condition, make block lime and water fully carry out the hydration reaction process;
4) in hydration reactor, add the slurrying water again, prepare mass concentration and be 10~20% desulfurizer slurry;
5) start the interior agitator of hydration reactor, the desulfurizer slurry that is evenly suspended;
6) desulfurizer slurry is delivered to slurry can, the solid impurity particle by in the block lime of filter elimination obtains desulfurizer slurry.
2. ultra-fine desulfurizer slurry preparation method according to claim 1 is characterized in that: CaO content is at least 80% in the described block lime.
3. ultra-fine desulfurizer slurry preparation method according to claim 1 and 2 is characterized in that: the particle diameter of described block lime is 10~30mm.
4. ultra-fine desulfurizer slurry preparation method according to claim 3 is characterized in that: described hydration reactor time of repose is 15~30 minutes.
5, ultra-fine desulfurizer slurry preparation method according to claim 1 is characterized in that: the temperature of described digestion water and slurrying water is 5~40 ℃.
6. implement the ultra-fine desulfurizer slurry preparation facilities of method according to claim 1 for one kind, it is characterized in that: this device comprises hydration reactor (1), be arranged on agitator (2) and slurry can (3) in the hydration reactor, described hydration reactor is connected by connecting pipe (4) with slurry can, and filter (5) is set in the exit of described slurry can.
7. ultra-fine desulfurizer slurry preparation facilities according to claim 6 is characterized in that: described agitator adopts centrifugal spiral agitator.
8. according to claim 6 or 7 described ultra-fine desulfurizer slurry preparation facilities, it is characterized in that: described filter adopts filter structure, and mesh size is 0.1~2mm.
CN 200610165584 2006-12-22 2006-12-22 Preparation method of ultra-fine desulfurizer slurry and device thereof Pending CN101007236A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102059044A (en) * 2010-11-25 2011-05-18 武汉钢铁(集团)公司 Process for preparing calcium-based sorbent through normal pressure dry slaking
CN106178877A (en) * 2016-08-31 2016-12-07 大连华锐重工集团股份有限公司 A kind of coke oven flue waste gas purification waste heat recovery apparatus and technique
CN107185366A (en) * 2017-06-05 2017-09-22 江苏海澜正和环境科技有限公司 A kind of special boiler of power plant fume environment protection abatement equipment and its method
CN108273375A (en) * 2017-12-29 2018-07-13 铜陵铜冠神虹化工有限责任公司 The hot carbonizer flue gas desulfurization device and technique in vulcanized sodium production
CN109365472A (en) * 2018-09-30 2019-02-22 清华大学 A kind of cleaning method of solid waste
CN109513333A (en) * 2018-09-26 2019-03-26 电子科技大学中山学院 A kind of method of alkalinity suspension absorbing carbon dioxide and atmosphere pollution
CN109925904A (en) * 2019-04-01 2019-06-25 清华大学 The method for preparing ultra-fine alkaline absorbent slurries using ultrasonic wave
CN110102209A (en) * 2019-04-09 2019-08-09 桐昆集团浙江恒盛化纤有限公司 A kind of lime under agitation method suitable for fire coal boiler fume governing system

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102059044A (en) * 2010-11-25 2011-05-18 武汉钢铁(集团)公司 Process for preparing calcium-based sorbent through normal pressure dry slaking
CN102059044B (en) * 2010-11-25 2012-09-26 武汉钢铁(集团)公司 Process for preparing calcium-based sorbent through normal pressure dry slaking
CN106178877A (en) * 2016-08-31 2016-12-07 大连华锐重工集团股份有限公司 A kind of coke oven flue waste gas purification waste heat recovery apparatus and technique
CN107185366A (en) * 2017-06-05 2017-09-22 江苏海澜正和环境科技有限公司 A kind of special boiler of power plant fume environment protection abatement equipment and its method
CN108273375A (en) * 2017-12-29 2018-07-13 铜陵铜冠神虹化工有限责任公司 The hot carbonizer flue gas desulfurization device and technique in vulcanized sodium production
CN109513333A (en) * 2018-09-26 2019-03-26 电子科技大学中山学院 A kind of method of alkalinity suspension absorbing carbon dioxide and atmosphere pollution
CN109365472A (en) * 2018-09-30 2019-02-22 清华大学 A kind of cleaning method of solid waste
CN109925904A (en) * 2019-04-01 2019-06-25 清华大学 The method for preparing ultra-fine alkaline absorbent slurries using ultrasonic wave
CN110102209A (en) * 2019-04-09 2019-08-09 桐昆集团浙江恒盛化纤有限公司 A kind of lime under agitation method suitable for fire coal boiler fume governing system

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