CN1869685B - Investigating method for lime activity and its analysing system - Google Patents

Investigating method for lime activity and its analysing system Download PDF

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Publication number
CN1869685B
CN1869685B CN200610054309A CN200610054309A CN1869685B CN 1869685 B CN1869685 B CN 1869685B CN 200610054309 A CN200610054309 A CN 200610054309A CN 200610054309 A CN200610054309 A CN 200610054309A CN 1869685 B CN1869685 B CN 1869685B
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China
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limestone
activity
gas
lime stone
slurry
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CN200610054309A
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CN1869685A (en
Inventor
董凌燕
杜云贵
刘清才
杨剑
刘艺
陈登福
谢兰
罗新蕾
罗捷
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Chongqing University
CPI Yuanda Environmental Protection Engineering Co Ltd
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Chongqing University
CPI Yuanda Environmental Protection Engineering Co Ltd
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Abstract

The invention discloses a limestone activity testing method and the analysis system thereof, making limestone pulp directly react with SO2 fume, simulating actual desulfation course, and reflecting limestone activity by measuring SO2 removal ratio, where the higher the SO2 removal ratio is, the better the limestone activity is and vice versa. And the analysis system mainly comprises limestone pulptank, pulp pump, absorption tower, gas steel cylinder, gas flow controller, limestone pump recover tank and pulp flow controller. And the invention can truly reflect limestone activity and reduce investment and operating cost. And the method is simple, effective and easy to implement, and able to accurately evaluate limestone activity and provides theoretical basis for fume desulfation engineering.

Description

Investigating method for lime activity and analytic system thereof
Technical field
The present invention relates to be applied to the detection technique of flue gas desulfurization course, be used to instruct flue gas desulphurization system design and optimization.Belong to the flue gas desulfurization technique field.
Background technology
Along with economy development constantly rapidly, atmosphere is by SO 2The severe contamination situation is day by day remarkable.As Chinese SO 2Discharge capacity reaches more than 2,000 ten thousand tons, becomes world SO 2First big country of discharging.Coal burning flue gas desulfurization (FGD) is uniquely now can reduce SO on a large scale 2The approach of discharging, in this technology, limestone/gypsum wet process of FGD (WFGD) occupies leading position.In WFGD, lime stone slurry is as SO 2Absorbing agent, work as SO 2When concentration was identical, its absorption rate was decided by the dissolution characteristics of lime stone.The active combined reaction of lime stone lime stone absorb the ability of sulphuric dioxide, thereby the activity of lime stone is significant to desulfuration efficiency, desulphurization system design.
In flue-gas desulfurizing engineering design, often design according to the activity of lime stone slurrying capacity to pulping system, if designed capacity is excessive, can cause the waste of resource; Designed capacity is too small, does not reach the requirement of desulfurization again.And at present domestic each power plant when carrying out the pulping system design since to the activity of lime stone do not know much have less understanding into, and test is inaccurate, often designs slurrying capacity very greatly to be on the safe side, thereby has caused unnecessary input.
The activity of lime stone is an important parameter of desulfuration efficiency in the evaluation of flue gas sweetening process.At present, at present both at home and abroad at the test of limestone activity almost all based on acidometric titration, and all be a spot of lime stone sample to be carried out express-analysis in the laboratory, do not have the proving installation of system; What development was ripe is the autotitrator that AEE company is produced, and is set up based on acidometric titration.But because the reaction mechanism of acidometric titration is different with the practical sulphur removal process, so its test result can not provide reference for the problem that is occurred in the engineering operation process.
At present, domestic still do not have complete, a unified limestone activity testing standard, and each producer all is according to concrete sweetener, sets up testing standard and experimental technique with reference to external method, do not have versatility, and standard is inconsistent.Domestic existing a kind of method of testing limestone activity is that power industry was in enforcement on June 1 " People's Republic of China's power industry standard " DL/T943 (the smoke-gas wet desulfurization mensuration of agstone reaction rate) in 2005.The method must accurately be analyzed the composition of lime stone, and thinks the reactive identical of lime carbonate and magnesium carbonate and hydrochloric acid in the lime stone, if the lime stone constituent analysis has error, then measurement result has little significance, and the historical facts or anecdotes border is used less.What use both at home and abroad was more at present is the AEE method of testing.Take a broad view of present investigating method for lime activity both at home and abroad, its common point be adopt mostly acidometric titration method, the advantage of acidometric titration method be simple to operate, detect rapid; Shortcoming then is that reaction mechanism is different with the practical sulphur removal process, often can not correctly reflect the activity of lime stone.Investigating method for lime activity and device are to estimate the gordian technique of the activity of lime stone to desulfuration efficiency, desulphurization system design.Therefore, seek a kind of simple, safety and be very important to the comparatively similar analogue means of actual engineering.
Summary of the invention
At the deficiency of existing limestone activity titration experiments device, the purpose of this invention is to provide a kind of can simulated flue gas desulfurization real process, and method that can more accurate evaluation limestone activity.
Another object of the present invention provides a kind of analytic system that realizes said method.
The object of the present invention is achieved like this: investigating method for lime activity is characterized in that: with the same SO of lime stone slurry 2Flue gas directly reacts, and simulation practical sulphur removal process is by measuring SO 2Removal efficiency reflect the activity of lime stone, SO 2Removal efficiency is high more, illustrates that limestone activity is good more; SO 2Removal efficiency is low more, illustrates that limestone activity is poor more.
Concrete steps are as follows:
A, test are prepared
(1) lime stone to be analyzed is ground into 250 purpose powder;
(2) preparation lime stone slurry, grout coordinate ratio is 5% (w/v);
B, testing procedure
(1) simulated flue gas and flow control are regulated N by reduction valve 2, CO 2, O 2And SO 2Gas flow;
(2) open temperature controller, setting flue-gas temperature is about 135 ℃;
(3) lime stone slurry of preparation is put into the slurries pond, keep its temperature about 50 ℃, and keep stirring, make limestone particle wherein be unlikely to sedimentation;
(4) open slush pump, Control Flow is 20L/h, opens the pH controller, regulates the pH value in the stock tank; When not carrying out pH regulator, can save; And record absorbs SO in the tail gas 2Content, ultimate analysis.
Realize the limestone activity detecting and analysing system of said method, comprise limestone slurry liquid pool, slush pump, absorption tower, gas bomb, gas flow controller, lime stone slurry recovery pond, slurry flow controller; The slurries pond is communicated with total tube inlet at top, absorption tower by pipeline, slush pump, slurry flow controller, and house steward is provided with the slurry flow controller and is communicated with the absorption tower, and the bottom, absorption tower sets out a mouthful feeding lime stone slurry recovery pond; The absorption tower following current absorbs the end and connects the flue-gas temperature controller; Counter-current absorption end, absorption tower connects gas analyzer through the DATA REASONING mouth; The gas bomb simulated flue gas feeds the flue-gas temperature controller by gas flow controller; Be provided with stirring apparatus and thermostat in limestone slurry liquid pool and the lime stone slurry recovery pond.
Further, be provided with the PH controller between described limestone slurry liquid pool, the lime stone slurry recovery pond.
The advantage of the inventive method is mainly reflected in the following aspects:
(1) taken all factors into consideration the each side character such as composition, impurity, structure of lime stone to SO 2The influence that absorbs;
(2) absorption reaction condition and actual industrial process are very approaching, actual response the activity of lime stone;
(3) adopt the inventive method that limestone activity is analyzed, not only help selecting suitable absorbing agent, and can determine the optimized operation operating parameter, and then reduce investment and operation in the operation phase at the WFGD system design stage;
(4) this test macro can be simulated actual industrial process, and the research lime stone slurry is to the absorbing state of sulphuric dioxide;
(5) assay method is simple, effective, is easy to realize, can correctly estimate the activity of lime stone, for flue-gas desulfurizing engineering design provides theoretical foundation;
(6) simulation system of the present invention is actual near industry, and is simple in structure, and is easy to control.
Description of drawings
Fig. 1 is a detecting and analysing system principle flow chart of the present invention.
Embodiment
Investigating method for lime activity is with the same SO of lime stone slurry 2Flue gas directly reacts, and simulation practical sulphur removal process is by measuring SO 2Removal efficiency reflect the activity of lime stone, SO 2Removal efficiency is high more, illustrates that limestone activity is good more; SO 2Removal efficiency is low more, illustrates that limestone activity is poor more.Concrete steps are as follows:
A, test are prepared
(1) lime stone to be analyzed is ground into 250 purpose powder;
(2) preparation lime stone slurry, grout coordinate ratio is 5% (as lime stone: water=50g: 1L);
B, testing procedure
(1) simulated flue gas and flow control are regulated N by reduction valve 2, CO 2, O 2And SO 2Gas flow; Be respectively as four kinds of gas flows: N 2=1.64m 3/ h, CO 2=0.24m 3/ h, O 2=0.12m 3/ h, SO 2=120mL/min;
(2) open temperature controller, setting flue-gas temperature is 135 ℃;
(3) lime stone slurry of preparation is put into the slurries pond, keep its temperature about 50 ℃, and keep stirring, make limestone particle wherein be unlikely to sedimentation;
(4) open slush pump, Control Flow is 20L/h, opens the pH controller, regulates the pH value in the stock tank; When not carrying out pH regulator, can save; And record absorbs SO in the tail gas 2Content, ultimate analysis.
As shown in Figure 1, the limestone activity detecting and analysing system comprises limestone slurry liquid pool 11, slush pump 12, absorption tower 13, gas bomb 14, gas flow controller J-N, lime stone slurry recovery pond 15, slurry flow controller A-I; Slurries pond 11 is communicated with house steward's 16 inlets at 13 tops, absorption tower by pipeline, slush pump 12, slurry flow controller I, and house steward 16 is provided with slurry flow controller A-F and is communicated with absorption tower 13, and 13 bottoms, absorption tower set out a mouthful feeding lime stone slurry recovery pond 15; Absorption tower 13 following currents absorb the end and connect flue-gas temperature controller R; 13 counter-current absorption ends, absorption tower connect gas analyzer through DATA REASONING mouth 1-5; Gas bomb 14 simulated flue gas feed flue-gas temperature controller R by gas flow controller J-N; Be provided with stirring apparatus P, O and thermostat in limestone slurry liquid pool 11 and the lime stone slurry recovery pond 15; Gas analyzer adopts existing matured product to get final product.
Referring to Fig. 1, be provided with PH controller Q between limestone slurry liquid pool 11, the lime stone slurry recovery pond 15, determine the flow direction of lime stone slurry by the selection of switch valve G, H.
Test result of the present invention:
This measuring technology and engineering reality comparatively meet, and can accurately measure limestone activity, and the method can simulated flue gas desulfurization real process, the accuracy height.By the limestone activity parameter that this method obtains, can be used for the flue gas desulfurization design, this limestone activity measuring technology belongs to advanced level at home and abroad.
Activity rating
Actual industrial process can be simulated by the inventive method and system, and the research lime stone slurry is to the absorbing state of sulphuric dioxide.The technological parameter and the actual conditions of absorption process are approaching, and the activity of lime stone adopts SO 2The mean speed of dissolving is measured.The key reaction that contains sulfur dioxide flue gas and lime stone slurry is:
SO 2+CaCO 3→CaSO 3+CO 2↑
Lime stone in the momentary rate of moment t is:
A 2 , i ′ = c i - 1 - c i Δ t i , i = 1,2,3 . . . . . . n
A 2 ′ = Σ 1 n A 2 , i ′ n
In the formula, c i-i outlet SO constantly 2Concentration, ppm;
c I-1-i-1 outlet SO constantly 2Concentration, ppm;
Δ t i-i the moment and the i-1 time interval constantly, s;
A 2i'-SO 2At Δ t iAverage dissolution rate in time;
A ' 2-SO 2Average dissolution rate, be limestone activity.
N-SO 2Reading times, n 〉=100
Adopt SO 2The mean speed of dissolving is estimated the activity of lime stone.SO 2The mean speed of dissolving is big more, and limestone activity is big more; SO 2The mean speed of dissolving is more little, and limestone activity is more little.
The present invention is directed to the practical operation situation exploitation analogue means comparatively similar,, obtain limestone activity value more accurately by simulation to the practical sulphur removal process to actual engineering, for engineering design provides foundation, thus the input expense of reduction flue gas desulfurization.
The present invention as source of the gas, uses flowmeter adjustments of gas composition and flow, the flue gas that obtains simulating industrial actual conditions after the electrical heating with steel cylinder.The temperature of reaction tank, stirring intensity, oxygenation intensity are set in determined value, and the adding with pH meter control lime stone slurry remains unchanged the pH value.The activity of lime stone adopts SO 2The mean speed of dissolving is measured.
Simulated flue gas part: the principal ingredient N in the flue gas 2, O 2And CO 2, SO 2The controlling object of attaching most importance to, the bottled pure gas of all gases.
Absorption tower part: adopt liquid curtain absorption tower to simulate.Necessary long enough of the residence time of simulated flue gas in tower is to guarantee the abundant absorption of sulphuric dioxide.
Working specification of the present invention: in actual engineering, all can carry out strict pH control to the slurries that enter the absorption tower, but in the limestone activity test of this project, owing to only need to consider the smoke absorption of the absorption tower first half, oxidizing process for Lower Half need not considered, and consider the operation more complicated of carrying out the control of pH value, so most of simulated flue gas can not carry out pH regulator among the present invention.In fact, whether the pH value of sprayed slurry is not regulated and can be exerted an influence to the active order of several lime stones,,, the activity of several lime stones is increased simultaneously because the pH value is higher when not carrying out pH regulator when directly spraying the lime stone virgin pulp liquid; And when carrying out pH regulator, the pH value of the loop slurry of spray is reduced, thereby the activity of several lime stones is descended simultaneously, but its variation tendency should be identical, and active size order should not change, and has verified this conclusion from testing observable result yet.
And the AEE assay method adopts acid that lime stone is carried out titration, because amount of lime is less when analyzing, because of the lime stone sampling causes component segregation, finally causes active result inaccurate easily, and the reaction mechanism of acidometric titration and the existence of practical sulphur removal technology are than big-difference.

Claims (1)

1. the limestone activity detecting and analysing system is characterized in that comprising limestone slurry liquid pool (11), slush pump (12), spray absorber (13), gas bomb (14), gas flow controller (J-N), lime stone slurry recovery pond (15), slurry flow controller (A-I); Slurries pond (11) is communicated with house steward (16) inlet at spray absorber (13) top by pipeline, slush pump (12), a slurry flow controller (I), house steward (16) is provided with another group slurry flow controller (A-F) and is communicated with spray absorber (13), and spray absorber (13) bottom sets out a mouthful feeding lime stone slurry recovery pond (15); Spray absorber (13) following current absorbs the end and connects flue-gas temperature controller (R); Spray absorber (13) counter-current absorption end connects gas analyzer through DATA REASONING mouth (1-5); Gas bomb (14) simulated flue gas feeds flue-gas temperature controller (R) by gas flow controller (J-N); Be provided with stirring apparatus (P, O) and thermostat in limestone slurry liquid pool (11) and the lime stone slurry recovery pond (15); Be provided with PH controller (Q) between described limestone slurry liquid pool (11), the lime stone slurry recovery pond (15).
CN200610054309A 2006-05-18 2006-05-18 Investigating method for lime activity and its analysing system Expired - Fee Related CN1869685B (en)

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Families Citing this family (7)

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Publication number Priority date Publication date Assignee Title
CN100493679C (en) * 2007-06-07 2009-06-03 中电投远达环保工程有限公司 Method of controlling fume speed inside desulfurizing absorption tower
CN101122590B (en) * 2007-08-17 2010-06-02 东南大学 Limestone activity test method and test device for wet process of FGD
CN102819274B (en) * 2012-07-31 2014-07-16 浙江省电力公司电力科学研究院 Blind zone detection method in process of controlling pH value of desulfurization system
CN103055687B (en) * 2013-01-08 2015-02-11 浙江天蓝环保技术股份有限公司 Calcium sulfite oxidation reaction stimulation apparatus and method thereof
CN103336087B (en) * 2013-06-07 2015-04-22 中电投远达环保工程有限公司 Testing device of desulphurization efficiency and testing method thereof
CN106290707A (en) * 2015-05-12 2017-01-04 中国石油天然气股份有限公司 The Performance Test System of desulfurization solvent
CN107376629B (en) * 2017-07-03 2020-01-24 清华大学 Method for determining limestone desulfurization reaction activity index and optimal particle size

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CN1327871A (en) * 2000-06-14 2001-12-26 王宇 Wet dusting and desulfurizing process
CN1493391A (en) * 2002-07-16 2004-05-05 巴布考克及威尔考克斯公司 Method of transforming upflow/downflow type wet flue gas desulfur system as single circuit upflow type wet flue gas desulfur system
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