CN105032154A - Ammonia desulphurization absorbent product S<4+> oxidation system and optimal regulation and control method - Google Patents

Ammonia desulphurization absorbent product S<4+> oxidation system and optimal regulation and control method Download PDF

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CN105032154A
CN105032154A CN201510464978.8A CN201510464978A CN105032154A CN 105032154 A CN105032154 A CN 105032154A CN 201510464978 A CN201510464978 A CN 201510464978A CN 105032154 A CN105032154 A CN 105032154A
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formula
slurry pool
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valency
slurries
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CN105032154B (en
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贾勇
陈�光
戴波
吴胜华
盛广宏
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安徽工业大学
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Abstract

The invention discloses an ammonia desulphurization absorbent product S<4+> oxidation system and an optimal regulation and control method, and belongs to the technical field of air pollution control. Model parameters in an ammonia desulphurization system are determined at first; the model parameters are input, an initial pH value, an oxidation air capacity Q and initial concentrations (shown in the description) of S<4+> and S<6+> are set, and the oxidation ratio r(IV)V/MSO2 of S<4+> in a slurry pond is calculated by use of an oxidation ratio model of S<4+>; the oxidation ratio r(IV)V/MSO2 of S<4+> is substituted into |r(IV)V/MSO2-CS<6+>/Cs|<=0.001 for inspection, if the formula is not valid, the values of CS<4+> and CS<6+> are re-calculated till |r(IV)V/MSO2-CS<6+>/Cs|<=0.001 is valid, the obtained oxidation ratio and the set value in the project are compared, the pH value, the oxidation air capacity Q, CS<4+> and CS<6+> in the model are adjusted to ensure that the oxidation ratio of S<4+> can meet the project demand. The oxidation ratio model can provide theoretical reference for the design and the operation of the ammonia desulphurization absorbent product S<4+> oxidation system, and further, the stability and the economical efficiency of the ammonia desulphurization technology are improved.

Description

Ammonia process of desulfurization absorption product+4 valency sulphur oxidative system and optimization regulating method thereof

Technical field

The invention belongs to technical field of atmospheric pollution control, more particularly, relate to a kind of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system and optimization regulating method thereof.

Background technology

Sulfur dioxide (SO 2) be the Air Pollutants being only second to particle at present in China's harm, but it is also a kind of resource simultaneously.Along with the appearance of national new standard, Sulfur Dioxide Emission Allowances is 400mg/Nm 3, this is for selecting a kind of economy much old use coal-burning boiler producer, the tail gas treatment process that treatment effect is good, is the most urgent task of manufacturer.

Desulfurization method of limestone-gypsum technique leading at present, because desulfurizer investment is larger, medium or small hot power station is difficult to bear, and operating cost is higher, desulfurizing byproduct gypsum adopts and abandons method or landfill method process, easily cause secondary pollution, the great amount of carbon dioxide simultaneously produced in sweetening process is a kind of greenhouse gases, thus limits the application of this method.Compared with calcium method sulfur removal technology, the ammonia process of desulfurization is with the higher ammonia (NH of chemical reactivity 3) be the SO in desulfurizing agent absorption flue gas 2, system dynamic consumes low, at efficient removal SO 2while, can also realize the recovery of Sulphur ressource, and without the discharge of waste water and waste residue, meet China and to develop a circular economy, create the Policy Demand of conservation-minded society, therefore it becomes and solves SO 2direct discharge causes the effective way of Air seriously polluted, and the ammonia process of desulfurization is progressively widely applied in the big-and-middle-sized coal-fired flue gas desulfurization project of China, and development prospect is good.But the byproduct of the ammonia process of desulfurization is (NH 4) 2sO 3and NH 4hSO 3, be heated in atmosphere and easily decompose, direct value is little, need be oxidized to ammonium sulfate further and recycle.Ammonia process of desulfurization spray column is the core of ammonia method desulfurizing system, usually adopts and pass into air directly in spray column, to make (NH in prior art 4) 2sO 3and NH 4hSO 3stable+6 valency sulphur (NH can be oxidized to 4) 2sO 4, at right+4 valency sulphur (NH 4) 2sO 3and NH 4hSO 3when carrying out oxidation processes, the key reaction related to is as follows:

Therefore, how efficiently, low energy consumption+4 valency sulphur are oxidized into+6 valency sulphur is realize that the ammonia process of desulfurization is stablized, the basis of economical operation, thus has attracted the concern of numerous researcher and engineers and technicians.

The oxidation of ammonia process of desulfurization absorption product+4 valency sulphur is mainly by the impact of all many condition such as slurry pH value ,+4 valency sulphur concentrations ,+6 valency sulphur concentrations, oxidation air amount and temperature.Up to now, sulfite oxidation dynamics aspect is mainly concentrated on to the thio-oxidizing research of ammonia process of desulfurization absorption product+4 valency, more typically mainly contain: (the ChemicalEngineeringScience such as ZhouJH, 2000,55 (23): 5637-5641) certain density O is passed into the top of solution in stirred reactor 2, O 2diffuse into solution and ammonium sulfite generation oxidation reaction, result of study shows that the oxidation rate of ammonium sulfite is 1 grade to oxygen concentration, inferior sulfate radical concentration lower than during critical concentration to it in-1 grade, in inferior sulfate radical concentration higher than being 0.2 grade to it during critical concentration.(the ChemicalEngineeringScience such as ZhaoB, 2005,60 (3): 863-868) set up Single bubble reaction unit and experimental study has been carried out to the oxidizing process of ammonium sulfite, result shows, the oxidation rate of ammonium sulfite in inferior sulfate radical concentration lower than being 1 grade to it during critical concentration, in inferior sulfate radical concentration higher than being 0 grade to it during critical concentration, the oxidation rate of ammonium sulfite increases with the increase of solution ph, when pH value is 6 ~ 9 time, pH value is on the impact of oxidation rate linearly rule.Although scholars achieve some useful results in sulfite oxidation research, due to with oxidation rate can not individually record, not to occupy the majority in ammonia process of desulfurization absorption product+4 valency sulphur in research in the past oxidation distinguish, and in experiment pH value control with differ in actual ammonia process of desulfurization engineering comparatively greatly, have ignored the impact that acid/adjusting PH with base value causes ionic strength to change, the oxidizing process mechanism of ammonia process of desulfurization absorption product+4 valency sulphur is not reasonably annotated.

In Practical Project, ammonia process of desulfurization absorption product+4 valency sulphur is often become stable ammonium sulfate by the air oxidation blasted in the slurry pool of spray-absorption tower bottom, its slurry pool can be similar to regards Continuous Flow continuous stir reactor bubbling reactor as, in spray column bottom slurry pond, the temperature of slurries is generally at about 323.15K, and the oxidation of+4 valency sulphur is relevant with factors such as total sulfur concentration, oxidation air amount and the time of staying of slurries in slurry pool in slurry pH value, slurries.Oxygenation efficiency weighs the leading indicator of+4 valency sulphur oxidation effectivenesses, the experience that depends in current engineering controls the thio-oxidizing process conditions of ammonia process of desulfurization absorption product+4 valency, easily cause energy waste or+4 valency sulfur oxidation rates on the low side, and the stable of+4 valency sulfur oxidation rates in slurry tank can not be maintained, and then cause the problems such as system cloud gray model is unstable, ammonium sulfate byproduct recovery rate is low.

Therefore, work out one and can realize ammonia process of desulfurization absorption product+4 valency sulfur highly effective, stable oxidation, and can be used in the system of true engineering practice, and can be used in directly instructing the model of the design and running optimizing this oxidative system just to have important theory significance and engineer applied value.

Summary of the invention

1. invent the technical problem that will solve

The object of the invention is to overcome the ammonia process of desulfurization spray column used in current engineering and can not realize that desulfurization absorption product+4 valency sulphur is stable, efficient oxidation, and the control of its oxidation process conditions depends on experience, easily cause the deficiency that energy waste, system cloud gray model instability and ammonium sulfate byproduct yield are low, provide a kind of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system and optimization regulating method thereof.The oxygenation efficiency model of+4 valency sulphur in the application of the invention, can be used in directly instructing optimal design and the operation of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system in the present invention, thus the oxygenation efficiency of ammonia process of desulfurization absorption product+4 valency sulphur can be made to meet industrial requirements.

2. technical scheme

For achieving the above object, technical scheme provided by the invention is:

One, a kind of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present invention, comprise spray column body, this spray column body interior comprises except fog-zone, spray district and slurry pool from top to bottom successively, wherein, be provided with neat stress outlet at the top of described spray column body, be provided with demister in the fog-zone of removing of neat stress outlet below, this demister is connected with the technique water tank of spray column outside; Be provided with shower on the top in described spray district, and be provided with gas approach in the tower body side that spray bottom, district is corresponding; Be provided with air sparger in the bottom of described slurry pool, the air inlet duct of this air sparger is connected with oxidation fan; The tower body side corresponding at slurry pool is connected with slurries extraction pump by extraction pipeline, and this slurry pool is connected with the water inlet of shower by circulating line, circulating line is also provided with circulating pump, is also connected with ammoniacal liquor inlet tube with the circulating line of the inlet communication of circulating pump.

Further, smoke on-line monitoring system is respectively equipped with exporting on the pipeline that is connected with gas approach and neat stress.

Further, the circulating line be connected in described slurry pool and with circulating-pump outlet is equipped with pH meter.

Its two, the optimization regulating method of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present invention, the steps include:

Step one, determine following model parameter: the D of ammonia method desulfurizing system spray column r, G, F, q, and pH, C of slurries in spray column bottom slurry pond s, V, t r, μ land σ l;

Wherein, D rfor the diameter of ammonia method desulfurizing system spray column, by measuring direct acquisition, unit is m; G is the flue gas flow rate being entered the pending flue gas in spray column by gas approach, is recorded by smoke on-line monitoring system, and unit is m 3s -1; with be respectively SO in spray column gas approach and neat stress exiting flue gas 2concentration, recorded by smoke on-line monitoring system, unit is mgm -3; F is the liquid-gas ratio in spray column, and be the setting value of system cloud gray model, unit is Lm -3; Q is the oxidation air amount in spray column slurry pool, and its value is theoretical air requirement Q 01 ~ 4 times, unit is m 3s -1; PH is the pH value of slurries in slurry pool; C sfor the total sulfur concentration of slurries in slurry pool, be+4 valency sulphur concentrations with+6 valency sulphur concentrations sum, its unit is molL -1; V is the volume of slurries in slurry pool, by the time of staying t of slurries in adjustment slurry pool rcontrol, V=60t rl in, unit is m 3, the L in this formula infor being flow to the slurry flow rate of slurry pool by shower, unit is m 3s -1, pass through L in=F × G/1000m 3s -1calculate; The viscosity, mu of slurries lwith surface tension σ lutilize viscosimeter and surface tension instrument to record respectively, its unit is respectively Pas and Nm -1;

Model parameter in step 2, input step one, and set an initial pH value, oxidation air amount Q and C sin the initial concentration of+4 valency sulphur and+6 valency sulphur and meet the oxygenation efficiency model of+4 valency sulphur is utilized to calculate the oxygenation efficiency of+4 valency sulphur in slurry pool

Step 3, the oxygenation efficiency of+4 valency sulphur will calculated in step 2 bring following formula into test:

| r ( I V ) V M SO 2 - C S 6 + C s | &le; 0.001

If the oxygenation efficiency of+4 valency sulphur calculated do not meet above formula, be back in step 2 and adjust with value, if r ( I V ) V / M SO 2 < C S 6 + / C S , Then increase and reduce if r ( I V ) V / M SO 2 > C S 6 + / C S , Then reduce and increase recalculate r (IV)v, until above formula is set up, finally exports with the oxygenation efficiency of+4 valency sulphur

Step 4 ,+4 valency sulfur oxidation rates will exported in step 3 compare with the target set point in Practical Project, if model calculation value lower than target set point, be then back in step 2 and adjust parameter p H, Q and C as follows sin one or more, and re-start calculating, until+4 valency sulfur oxidation rates exported in step 3 engineering demands:

Reduce the pH of slurries in slurry pool, step-length is 0.1; Increase oxidation air amount Q, step-length is 0.5; Reduce the total sulfur concentration C of slurries in slurry pool s, step-length is 0.1, C sbe decreased through and increase by the slurry flow rate L of slurries extraction pump extraction outrealize.

Further, in step 2, in slurry pool, the oxygenation efficiency of+4 valency sulphur calculates by with drag:

&eta; = r ( I V ) V / M SO 2 - - - ( 1 ) ,

In formula (1) for the SO that spray column spray district absorbs 2molar flow rate, unit is mols -1, its through type (2) calculates:

M SO 2 = G &times; ( C SO 2 , i n - C SO 2 , o u t ) / ( 1000 &times; 64 ) - - - ( 2 ) ,

R in formula (1) (IV)for the oxidation rate of+4 valency sulphur in slurry pool, unit is molL -1min -1, it calculates by formula (3):

r ( I V ) = C O 2 * / ( 1 k L a + 1 k 0 exp ( - 2.8 &times; 10 4 R T ) &CenterDot; 1 10 - 0.39 p H - 1.14 &CenterDot; 1 C SO 3 2 - - 0.5 &CenterDot; 1 - 4 C S 6 + + 9 ) - - - ( 3 ) ,

In formula (3), k 0for frequency factor, its value is 1.44 × 10 4; R is ideal gas constant, is 8.31Jmol -1k -1; T is temperature in spray column, and unit is K; for the equilibrium concentration of gas-liquid interface place oxygen in slurry pool, unit is molL -1, its through type (4) calculates:

C O 2 * = Hp O 2 * - - - ( 4 ) ,

In formula (4), for gas-liquid interface place O in slurry pool 2equilibrium partial pressure, unit is Pa; H is O 2solubility coefficient in slurry pool in slurries, unit is molm -3pa -1, H calculates by formula (5):

l o g ( H 0 H ) = h 1 I 1 + h 2 I 2 + ... + h i I i + ... - - - ( 5 ) ,

In formula (5), H 0for O 2solubility coefficient in water; h ifor the O that slurry pool Inner electrolysis matter causes 2solubility reduces coefficient, and unit is m 3kion -1; I ithe ionic strength of each ion in liquid pool Inner electrolysis matter, unit is kionm -3, h iand I icalculate respectively by formula (6) and formula (7):

h i=h ++h -+h G(6),

I i = 1 2 &Sigma;C i Z i 2 - - - ( 7 ) ,

In formula (6), h +, h -, h gthe numerical value being respectively this electrolyte positive and negative ion and being caused by the oxygen dissolved; C in formula (7) ifor the concentration of each ion of slurry pool Inner electrolysis matter, Z ifor the valence mumber of each ion; In the pH value range controlled in ammonia desulfurizing process, H in slurries 2sO 3and NH 3h 2the concentration of O is low, negligible, and the electrolyte in slurries refers to NH 4hSO 3, (NH 4) 2sO 3(NH 4) 2sO 4;

In formula (3), k lfor oxygen mass tranfer coefficient in the liquid phase, unit is ms -1, it calculates by formula (8):

k L = 0.5 g 5 / 8 D O 2 1 / 2 &rho; L 3 / 8 &sigma; L - 3 / 8 d v s 1 / 2 - - - ( 8 ) ,

In formula (8), ρ lfor the density of slurries in slurry pool, unit is kgm -3, its through type (9) calculates:

&rho; L = ( 99 &delta; 1 C S 4 + + 116 &delta; 2 C S 4 + + 132 C S 6 + ) / 1000 - - - ( 9 ) ,

In formula (9), δ 1and δ 2be respectively with breadth coefficient, wherein:

&delta; 1 = K a 1 &lsqb; H + &rsqb; &lsqb; H + &rsqb; 2 + K a 1 &lsqb; H + &rsqb; + K a 1 K a 2 - - - ( 10 ) ,

&delta; 2 = K a 1 K a 2 &lsqb; H + &rsqb; 2 + K a 1 &lsqb; H + &rsqb; + K a 1 K a 2 - - - ( 11 ) ,

In formula (10) and (11), K a1and K a2be respectively balanced reaction with reaction equilibrium constant; [H +] be hydrionic active concentration in slurry pool (501) interior slurries, calculated by pH value;

In formula (8) and d vsbe respectively the average diameter of bubble in the diffusion coefficient of oxygen in slurry pool liquid phase and slurry pool liquid phase, its unit is respectively m 2s -1and m, and d vscalculate by formula (12), (13) respectively:

D O 2 = 7.4 &times; 10 - 12 ( &alpha;M B ) 0.5 T &mu; L V A 0.6 - - - ( 12 ) ,

d v s = 26 D R ( gD R 2 &sigma; L ) - 0.5 ( gD R 3 &rho; L 2 &mu; L 2 ) - 0.12 ( u O G gD R ) - 0.12 - - - ( 13 ) ,

In formula (12), α is the associated factors of solvent in slurries in slurry pool, and value is 2.6; M bfor the molal weight of solvent in slurries in slurry pool, unit is gmol -1; V afor the diffuse volumetric of oxygen molecule, unit is cm 3mol -1;

In formula (13), u oGfor the superficial gas velocity of slurry pool internal oxidition air, unit is ms -1, it calculates by formula (14):

u O G = Q / ( &pi;D R 2 / 4 ) - - - ( 14 ) ,

In formula (3), a is gas-liquid contact interfacial area, and unit is m 2m -3, calculate by formula (15):

a = 6 &epsiv; G d V S - - - ( 15 ) ,

In formula (15), the gas holdup ε in slurry pool in liquid phase gcalculate by following formula:

&epsiv; G ( 1 - &epsiv; G ) 4 = 0.25 &times; ( u O G &mu; L &sigma; L ) ( &rho; L &sigma; L 3 g&mu; L 4 ) 7 / 24 - - - ( 16 ) ,

In formula (3), concentration calculate by following formula:

C SO 3 2 - = &delta; 2 C S 4 + - - - ( 17 ) ,

Simultaneous formula (1) ~ (17) namely calculate the oxygenation efficiency of+4 valency sulphur in slurry pool

Further, parameter p H, Q, C is adjusted in step 4 sparameter area require as follows: in slurry pool, the pH of slurries is 5.0 ~ 6.0, C sbe 1.9 ~ 2.3mol/L, actual oxidation air capacity Q and theoretical oxidation air capacity Q 0the scope of ratio m be 1 ~ 4.

The oxidation of ammonia process of desulfurization absorption product+4 valency sulphur is carried out in spray column bottom slurry pond, under stable operation condition, slurry pool can be similar to and regard Continuous Flow mixed bubbling reactor entirely as, in addition, the oxygenation efficiency of+4 valency sulphur is mainly relevant with the factor such as pH value, total sulfur concentration, oxidation air amount and the time of staying of slurries in slurry pool.Based on These characteristics, the present invention combines+4 valency sulphur oxidation rate equations, sets up the thio-oxidizing Mathematical Modeling of+4 valency in slurry pool.

The oxygenation efficiency formula of interior+4 valency sulphur of slurry pool in the present invention derivation as follows:

Under limit, the slurry pool in the ammonia process of desulfurization spray column in Fig. 1 can be reduced to model as shown in Figure 2, flow to and the slurries that flow out slurry pool exist following equilibrium relation:

L in=L out+L re(18),

In formula (1), L infor being entered the slurry flow rate of slurry pool by shower, L outfor being discharged the slurry flow rate of slurry pool by slurries extraction pump, L refor the slurry flow rate of being extracted out by slurry pool by circulating pump, its unit is m 3s -1; Wherein, L in=F × G/1000m 3s -1, in order to maintain the constant of concentration of slurry in slurry pool, make fraction slurries discharge slurry pool and carry out later crystallization process, the flow rate of discharging this part slurries of slurry pool can calculate by formula (19):

L o u t ( C S 4 + + C S 6 + ) = M SO 2 - - - ( 19 ) ,

In slurry pool each ion concentration over time speed can be expressed as:

dC i d t = ( N i + r r e a c t ) / V - - - ( 20 ) ,

In formula (20), N ifor the molar flow rate of slurry pool import and export slurries intermediate ion, unit is molmin -1, it calculates by formula (21):

N i=L inC i,in-L reC i,re-L outC i,out(21),

C in formula (21) i, in, C i, reand C i, outbe respectively by shower enter slurry pool, extracted out by slurry pool by circulating pump, by slurries extraction pump discharge slurry pool slurries in ion concentration; Convolution (20), (21), interior+4 valency sulphur of slurry pool and+6 valency sulphion concentration over time speed are respectively:

d ( C SO 3 2 - + C HSO 3 - + C H 2 SO 3 ) d t = ( N SO 3 2 - + N HSO 3 - + N H 2 SO 3 - r r e a c t ) / V - - - ( 22 ) ,

dC SO 4 2 - d t = ( N SO 4 2 - + r r e a c t ) / V - - - ( 23 ) ,

In spray district, SO 2be rapidly absorbed into liquid phase and form+4 valency sulphur (H 2sO 3, with ), SO 2uptake is + 4 valency sulphur that spray district is formed enter in slurry pool and are also partly oxidized into+6 valency sulphur.In the ammonia process of desulfurization+4 valency sulphur oxidizing process, the speed that+4 valency sulphur concentrations reduce equals the speed that+6 valency sulphur concentrations increase, and under limit in slurry pool slurries ion concentration keep constant, therefore, in formula (22), (23)+4 valency sulphur and+6 valency sulphion concentration over time speed be 0, that is: then have:

If the oxygenation efficiency of+4 valency sulphur is η, then:

In formula (22) ~ (24), r reactfor the generating rate of+6 valency sulphur in slurry pool, unit is molmin -1, it can calculate according to following formula:

r react=r (IV)V(26);

Formula (25), (26) are substituted into formula (24), the oxygenation efficiency of+4 valency sulphur:

The density calculation formula of slurries in slurry pool in the present invention derive as follows:

In ammonia process of desulfurization process, SO 2dissolving enters liquid phase and following ionic equilibrium occurs:

+ 4 valency sulphur in slurries middle H 2sO 3, with breadth coefficient δ 0, δ 1and δ 2can be expressed as respectively:

&delta; 0 = &lsqb; H 2 SO 3 &rsqb; &lsqb; H 2 SO 3 &rsqb; + &lsqb; HSO 3 - &rsqb; + &lsqb; SO 3 2 - &rsqb; - - - ( 30 ) ,

&delta; 1 = &lsqb; HSO 3 - &rsqb; &lsqb; H 2 SO 3 &rsqb; + &lsqb; HSO 3 - &rsqb; + &lsqb; SO 3 2 - &rsqb; - - - ( 31 ) ,

&delta; 2 = &lsqb; SO 3 2 - &rsqb; &lsqb; H 2 SO 3 &rsqb; + &lsqb; HSO 3 - &rsqb; + &lsqb; SO 3 2 - &rsqb; - - - ( 32 ) ,

Convolution (27) ~ (29), with concentration can be expressed as respectively:

&lsqb; H + &rsqb; &lsqb; HSO 3 - &rsqb; &lsqb; H 2 SO 3 &rsqb; = K a 1 &DoubleRightArrow; &lsqb; HSO 3 - &rsqb; = K a 1 &lsqb; H 2 SO 3 &rsqb; &lsqb; H + &rsqb; - - - ( 33 ) ,

&lsqb; H + &rsqb; &lsqb; SO 3 2 - &rsqb; &lsqb; HSO 3 2 - &rsqb; = K a 2 &DoubleRightArrow; &lsqb; SO 3 2 - &rsqb; = K a 2 &lsqb; HSO 3 - &rsqb; &lsqb; H + &rsqb; - - - ( 34 ) ,

Convolution (30) ~ (34), H 2sO 3, with breadth coefficient δ 0, δ 1and δ 2can turn to respectively:

&delta; 0 = &lsqb; H + &rsqb; 2 &lsqb; H + &rsqb; 2 + K a 1 &lsqb; H + &rsqb; + K a 1 K a 2 - - - ( 35 ) ,

&delta; 1 = K a 1 &lsqb; H + &rsqb; &lsqb; H + &rsqb; 2 + K a 1 &lsqb; H + &rsqb; + K a 1 K a 2 - - - ( 36 ) ,

&delta; 2 = K a 1 K a 2 &lsqb; H + &rsqb; 2 + K a 1 &lsqb; H + &rsqb; + K a 1 K a 2 - - - ( 37 ) ,

As can be seen from formula (35) ~ (37), H 2sO 3, with breadth coefficient δ 0, δ 1and δ 2for the function of pH value.And from formula (35), in the scope that pH is 5.0 ~ 6.0, H 2sO 3breadth coefficient δ 0numerical value is very little, can ignore.Slurries in concentration be δ 1 concentration be δ 2 mainly NH in solution 4hSO 3, (NH 4) 2sO 3(NH 4) 2sO 4, therefore, the density p of slurries lcan be similar to and calculate by following formula:

&rho; L = ( 99 &delta; 1 C S 4 + + 116 &delta; 2 C S 4 + + 132 C S 6 + ) / 1000.

Each model parameter in the present invention as shown in Table 1.

Table 1 model parameter explanation of the present invention

3. beneficial effect

Adopt technical scheme provided by the invention, compared with prior art, there is following remarkable result:

(1) ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present invention, after pending flue gas enters spray column, spray district with to be sprayed by shower and under spray liquid counter current contacting after fall in slurry pool, the air sparger arranged bottom slurry pool can make slurries fully contact with oxygen, promotes the oxidation of+4 valency sulphur.Pass through extraction pipeline in the tower body side that slurry pool is corresponding in the present invention to be connected with slurries extraction pump, thus slurries can be made constantly to discharge from slurry pool, be conducive to maintaining the ion concentration in slurry pool, ensure that interior+4 valencys of slurry pool are thio-oxidizing and stablize and efficiently carry out; Slurry pool in the present invention is connected with the water inlet of shower by circulating line, circulating line is also provided with circulating pump, also be connected with ammoniacal liquor inlet tube with the circulating line of the inlet communication of circulating pump, thus serum recycle can be made to use, be conducive to economizing on resources, and constantly inject fresh ammoniacal liquor by ammoniacal liquor inlet tube, be conducive to regulating the pH entering spray liquid in shower, ensure that spray liquid absorbs SO 2ability.

(2) optimization regulating method of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present invention, it is the feature based on ammonia process of desulfurization absorption product+4 valency sulphur oxidation technology, founding mathematical models carries out numerical simulation to the oxidizing process of+4 valencys in spray column slurry pool in engineering practice, adopt this model can calculate the oxygenation efficiency of+4 valency sulphur under different technology conditions, by the inspection formula between model calculation value and setting value, comparison test is carried out to result of calculation, and incorporation engineering is actual regulates the thio-oxidizing Cs of+4 valency in oxidation trough, the technological parameters such as pH and Q, enable the oxygenation efficiency engineering demands of+4 valency sulphur, thus the design and running of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system can be instructed, be conducive to the optimization of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system.

(3) optimization regulating method of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present invention, error between its model calculation value and engineering survey value is less than 5%, model can simulate the oxidizing process of ammonia process of desulfurization absorption product+4 valency sulphur comparatively accurately, thus make the design and running of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system more reliable, improve stability and the economy of ammonia method desulfurizing system operation.

Accompanying drawing explanation

Fig. 1 is the structural representation of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present invention;

Fig. 2 is the schematic diagram of slurry pool model in spray column in the present invention;

Fig. 3 is the model computing block diagram in the present invention;

Fig. 4 is the comparison diagram of the model calculation value in the measured value of+4 valency sulfur oxidation rates and the present invention.

Label declaration in figure:

1, oxidation fan; 2, air sparger; 3, slurries extraction pump; 4, circulating pump; 5, spray column body; 501, slurry pool; 502, district is sprayed; 503, gas approach; 504, shower; 505, demister; 506, neat stress outlet; 6, ammoniacal liquor inlet tube; 7, sample tap.

Detailed description of the invention

For understanding content of the present invention further, existing the present invention is described in detail in conjunction with the accompanying drawings and embodiments.

Embodiment 1

As shown in Figure 1, a kind of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment, comprise spray column body 5, this spray column body 5 inside comprises except fog-zone, spray district 502 and slurry pool 501 from top to bottom successively, wherein, be provided with neat stress outlet 506 at the top of spray column body 5, the fog-zone of removing below neat stress outlet 506 is provided with demister 505, and this demister 505 is connected with the technique water tank of spray column outside.Be provided with shower 504 on the top in spray district 502, and be provided with gas approach 503 in tower body side corresponding to spray bottom, district 502, be equipped with smoke on-line monitoring system exporting on 506 pipelines be connected with gas approach 503 and neat stress.Be provided with air sparger 2 in the bottom of slurry pool 501, the air inlet duct of this air sparger 2 is connected with oxidation fan 1; Be connected with slurries extraction pump 3 by extraction pipeline in the tower body side of slurry pool 501 correspondence, and this slurry pool 501 is connected by the water inlet of circulating line with shower 504.Circulating line is also provided with circulating pump 4, this circulating line is provided with sample tap 7 near one end of loop slurry outlet, and is also connected with ammoniacal liquor inlet tube 6 with the circulating line of the inlet communication of circulating pump 4.In slurry pool 501 and with the circulating line of this circulating pump 4 outlet on be equipped with pH meter, thus slurries in slurry pool can be measured in real time and pass into the pH value entering the spray liquid of shower after ammoniacal liquor regulates.

In the present embodiment, pending flue gas is turned back upwards after entering spray column by the gas approach 503 on spray column body 5, spray district 502 with sprayed by shower 504 and under slurries counter current contacting, substantially increase SO in flue gas 2removal effect.At spray district SO 2dissolving enters liquid phase and reacts with absorbent in spray liquid and generates+4 valency sulphur (NH 4) 2sO 3and NH 4hSO 3, be stripped of SO 2flue gas continue upwards to carry out washing process and the demist process of demister 505, the neat stress finally obtained by neat stress outlet 506 discharges of tower top, and absorbs SO 2slurries then fall in the slurry pool 501 bottom spray column.In slurry pool 501, oxygen is passed into continuously, with by+4 valency sulphur (NH by the air sparger 2 bottom slurry pool 501 4) 2sO 3and NH 4hSO 3be oxidized to stable+6 valency sulphur (NH 4) 2sO 4.In running, the fraction slurries in slurry pool 501 is constantly made to be discharged by serum outlet by slurries extraction pump 3 on the one hand, carry out follow-up crystallization treatment, thus the constant of ion concentration in slurry pool 501 can be maintained, make+4 valency sulphur (NH in slurry pool 501 4) 2sO 3and NH 4hSO 3oxygenation efficiency can remain constant.Deliver to shower 504 by circulating pump 4 slurries extracted in slurry pool 501 on the other hand to recycle, thus can economize on resources.Also be connected with ammoniacal liquor inlet tube 6 with the circulation line of circulating pump 4 inlet communication, thus constantly can supplementing ammoniacal liquor to keep spray liquid to SO in spray liquid 2absorbability, the magnitude of recruitment of ammoniacal liquor in ammoniacal liquor inlet tube 6 can be regulated by the pH of slurries in the slurry pool 501 measured, meet the demands with the pH of spray liquid after making supplementary ammoniacal liquor.

As shown in Figure 3, the optimization regulating method of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment, its concrete steps are:

Step one, determine following model parameter: the D of ammonia method desulfurizing system spray column r, G, F, q, and pH, C of slurries in spray column bottom slurry pond 501 s, V, t r, μ land σ l.

Wherein, D rfor the diameter of ammonia method desulfurizing system spray column, by measuring direct acquisition, unit is m; G is the flue gas flow rate being entered the pending flue gas in spray column by gas approach 503, is recorded by smoke on-line monitoring system, and unit is m 3s -1; with be respectively spray column gas approach 503 and neat stress exports SO in 506 flue gases 2concentration, recorded by smoke on-line monitoring system, unit is mgm -3; F is the liquid-gas ratio in spray column, and be the setting value of system cloud gray model, unit is Lm -3; Q is the oxidation air amount in spray column slurry pool 501, and its value is theoretical air requirement Q 01 ~ 4 times, wherein, theoretical oxidation air capacity unit is m 3s -1; PH is the pH value of slurries in slurry pool 501; C sfor the total sulfur concentration of slurries in slurry pool 501, be+4 valency sulphur concentrations with+6 valency sulphur concentrations sum, its unit is molL -1; V is the volume of slurries in slurry pool 501, by the time of staying t of slurries in adjustment slurry pool 501 rcontrol, V=60t rl in, unit is m 3, the L in this formula infor being flow to the slurry flow rate of slurry pool 501 by shower 504, unit is m 3s -1, pass through L in=F × G/1000m 3s -1calculate; The viscosity, mu of slurries lwith surface tension σ lutilize viscosimeter and surface tension instrument to record respectively, its unit is respectively Pas and Nm -1;

In the present embodiment, D rfor 8.6m, t rfor 17.62min, G are 116.9m 3s -1, for 1556mgm -3, for 37mgm -3, F is 3.5Lm -3, C sfor 2.2molL -1, pH is 5.2, Q is 0.16m 3s -1, μ lfor 0.5494Pas, surface tension σ lfor 67.77Nm -1, according to V=60t rl incan calculate slurry volume V in slurry pool 501 is 432.55m 3.

Model parameter in step 2, input step one, and set C sin the initial concentration of+4 valency sulphur and+6 valency sulphur and meet in the present embodiment the oxygenation efficiency model of+4 valency sulphur is utilized to calculate the oxygenation efficiency of+4 valency sulphur in slurry pool 501 the oxygenation efficiency model being somebody's turn to do+4 valency sulphur is specific as follows:

&eta; = r ( I V ) V / M SO 2 - - - ( 1 ) ,

In formula (1) for the SO that spray column spray district 502 absorbs 2molar flow rate, unit is mols -1, its through type (2) calculates:

M SO 2 = G &times; ( C SO 2 , i n - C SO 2 , o u t ) / ( 1000 &times; 64 ) - - - ( 2 ) ,

R in formula (1) (IV)for the oxidation rate of+4 valency sulphur in slurry pool 501, unit is molL -1min -1, it calculates by formula (3):

r ( I V ) = C O 2 * / ( 1 k L a + 1 k 0 exp ( - 2.8 &times; 10 4 R T ) &CenterDot; 1 10 - 0.39 p H - 1.14 &CenterDot; 1 C SO 3 2 - - 0.5 &CenterDot; 1 - 4 C S 6 + + 9 ) - - - ( 3 ) ,

In formula (3), k 0for frequency factor, its value is 1.44 × 10 4; R is ideal gas constant, is 8.31Jmol -1k -1; T is temperature in spray column, is 323.15K; for the equilibrium concentration of gas-liquid interface place oxygen in slurry pool 501, unit is molL -1, its through type (4) calculates:

C O 2 * = Hp O 2 * - - - ( 4 ) ,

In formula (4), for gas-liquid interface place O in slurry pool 501 2equilibrium partial pressure, unit is Pa, in the present embodiment be 2.13 × 10 4pa; H is O 2solubility coefficient in slurry pool 501 in slurries, unit is molm -3pa -1, H calculates by formula (5):

l o g ( H 0 H ) = h 1 I 1 + h 2 I 2 + ... + h i I i + ... - - - ( 5 ) ,

In formula (5), H 0for O 2solubility coefficient in water, its value is 9.45 × 10 -6molm -3pa -1; h ifor the O that slurry pool 501 Inner electrolysis matter causes 2solubility reduces coefficient, and unit is m 3kion -1; I ifor the ionic strength of each ion in slurry pool 501 Inner electrolysis matter, unit is kionm -3.In the pH value range controlled in ammonia desulfurizing process, H in slurries 2sO 3and NH 3h 2the concentration of O is low, negligible, and the electrolyte in slurries refers to NH 4hSO 3, (NH 4) 2sO 3(NH 4) 2sO 4; h iand I icalculate respectively by formula (6) and formula (7):

h i=h ++h -+h G(6),

I i = 1 2 &Sigma;C i Z i 2 - - - ( 7 ) ,

In formula (6), slurry pool 501 Inner electrolysis matter NH 4hSO 3, (NH 4) 2sO 3(NH 4) 2sO 4middle positive and negative ion and the numerical value h caused by the oxygen dissolved +, h -and h gas shown in table 2, C in formula (7) ifor the concentration of each ion in slurry pool 501 Inner electrolysis matter, Z ifor the valence mumber of each ion.

Proportionality constant (the h of each ion in table 2 embodiment 1 formula (6) +, h -andh g)

In formula (3), k lfor oxygen mass tranfer coefficient in the liquid phase, unit is ms -1, it calculates by formula (8):

k L = 0.5 g 5 / 8 D O 2 1 / 2 &rho; L 3 / 8 &sigma; L - 3 / 8 d v s 1 / 2 - - - ( 8 ) ,

In formula (8), ρ lfor the density of slurries in slurry pool, unit is kgm -3, its through type (9) calculates:

&rho; L = ( 99 &delta; 1 C S 4 + + 116 &delta; 2 C S 4 + + 132 C S 6 + ) / 1000 - - - ( 9 ) ,

In formula (9), δ 1and δ 2be respectively with breadth coefficient, wherein,

&delta; 1 = K a 1 &lsqb; H + &rsqb; &lsqb; H + &rsqb; 2 + K a 1 &lsqb; H + &rsqb; + K a 1 K a 2 - - - ( 10 ) ,

&delta; 2 = K a 1 K a 2 &lsqb; H + &rsqb; 2 + K a 1 &lsqb; H + &rsqb; + K a 1 K a 2 - - - ( 11 ) ,

In formula (10) and (11), K a1and K a2be respectively balanced reaction with reaction equilibrium constant, wherein, lgK a1=853/T-4.74, lgK a2=621.9/T-9.278; [H +] be hydrionic active concentration in slurry pool (501) interior slurries, calculated by pH value.

In formula (8) and d vsbe respectively the average diameter of bubble in the diffusion coefficient of oxygen in slurry pool liquid phase and slurry pool liquid phase, its unit is respectively m 2s -1and m, and d vscalculate by formula (12), (13) respectively:

D O 2 = 7.4 &times; 10 - 12 ( &alpha;M B ) 0.5 T &mu; L V A 0.6 - - - ( 12 ) ,

d v s = 26 D R ( gD R 2 &sigma; L ) - 0.5 ( gD R 3 &rho; L 2 &mu; L 2 ) - 0.12 ( u O G gD R ) - 0.12 - - - ( 13 ) ,

In formula (12), α is the associated factors of solvent in slurries in slurry pool, and value is 2.6; M bfor the molal weight of solvent in slurries in slurry pool, unit is gmol -1, M in the present embodiment bfor 18gmol -1; V afor the diffuse volumetric of oxygen molecule, unit is cm 3mol -1, be 16.6cm in the present embodiment 3mol -1.

In formula (13), u oGfor the superficial gas velocity of slurry pool internal oxidition air, unit is ms -1, it calculates by formula (14):

u O G = Q / ( &pi;D R 2 / 4 ) - - - ( 14 ) ,

In formula (3), a is gas-liquid contact interfacial area, and unit is m 2m -3, calculate by formula (15):

a = 6 &epsiv; G d V S - - - ( 15 ) ,

In formula (15), the gas holdup ε in slurry pool in liquid phase gcalculate by following formula:

&epsiv; G ( 1 - &epsiv; G ) 4 = 0.25 &times; ( u O G &mu; L &sigma; L ) ( &rho; L &sigma; L 3 g&mu; L 4 ) 7 / 24 - - - ( 16 ) ,

In formula (3), concentration calculate by following formula:

C SO 3 2 - = &delta; 2 C S 4 + - - - ( 17 ) ,

Each parameter is substituted into formula (1) ~ (17), and simultaneous formula (1) ~ (17) calculate the oxygenation efficiency of+4 valency sulphur in slurry pool 501 be 1.1597.

Step 3, the oxygenation efficiency of+4 valency sulphur will calculated in step 2 with bring following discriminate into test, discriminate is false:

| r ( I V ) V M SO 2 - C S 6 + C s | &le; 0.001 ,

Be back in step 2 and adjust with value, if then increase and reduce if then reduce and increase recalculate r (IV)v, until above formula is set up, finally exports the oxygenation efficiency of+4 valency sulphur be 96%.

Step 4 ,+4 valency sulfur oxidation rates will exported in step 3 compare with the target set point in Practical Project, if model calculation value lower than target set point, be then back in step 2 and adjust parameter p H, Q and C as follows sin one or more, and re-start calculating, until+4 valency sulfur oxidation rates exported in step 3 engineering demands: the pH reducing slurries in slurry pool 501, step-length is 0.1; Increase oxidation air amount Q, step-length is 0.5; Reduce the total sulfur concentration C of slurries in slurry pool 501 s, step-length is 0.1, C sbe decreased through and increase by the slurry flow rate L of slurries extraction pump 3 extraction outrealize.Wherein, more than adjusting during each technological parameter, should adjust in following adjusting range: in slurry pool 501, the pH of slurries is 5.0 ~ 6.0, C sbe 1.9 ~ 2.3mol/L, actual oxidation air capacity Q and theoretical oxidation air capacity Q 0the scope of ratio m be 1 ~ 4.In the present embodiment, require in engineering that the oxygenation efficiency of+4 valency sulphur is not less than 98%, keeps other parameter constant of the first step, regulate pH to be 5.0, continue to perform second step and the 3rd step, the oxygenation efficiency calculating+4 valency sulphur is 98.16%.

When using the oxygenation efficiency model in the present invention to instruct the design and running of oxidative system in Practical Project, first according to the build-in attribute of spray column desulphurization system in Practical Project, as spray column diameter D r, SO in the flue gas flow rate G of the pending flue gas entered in spray column and spray column gas approach 503 flue gas 2concentration deng, and to the target set point of ammonia process of desulfurization absorption product+4 valency sulfur oxidation rate in incorporation engineering, a first given initial pH value, oxidation air amount Q and C sin the initial concentration of+4 valency sulphur and+6 valency sulphur above initial value is substituted into oxygenation efficiency model in the present invention to calculate oxygenation efficiency numerical value, and the oxygenation efficiency that will calculate numerical value and setting initial value substitutes into in test, if this discriminate is false, then returns in step 2 and adjust C sin with value, until above-mentioned discriminate is set up, export oxygenation efficiency numerical value now / C s, and the target set point in itself and engineering is compared, if its discontented foot-eye setting value, then by pH value, the oxidation air amount Q and C of slurries in slurry pool sin one or more, and to recalculate, until the oxygenation efficiency exported meets the target set point in engineering.

What deserves to be explained is, inventor (Jia Yong, ACTA Scientiae Circumstantiae, 2014, 34 (8): 1 ~ 7) one section of document about the scale-model investigation of ammonia desulfurizing process S (IV) oxidation kinetics was disclosed in 2010, inventor is based on the feature of ammonia flue gas desulfurization technique in the above documents, in batch (-type) blistering reaction device, experimental study is carried out to the oxidation kinetics process of accessory substance+4 valency sulphur, in conjunction with the gas holdup under different condition in research, Oxygen in Liquid equation for mass transfer coefficient, only be deduced the expression formula of+4 valency sulphur oxidations rate theoretically, but the expression formula of being somebody's turn to do+4 valency sulphur oxidations rate can not be used to guide the operation of true engineering practice, namely do not instruct by the expression formula of this oxidation rate the design and running optimizing ammonia process of desulfurization absorption product+4 valency sulphur oxidative system, this also result in the difficult problem of puzzlement inventor's long period.And the oxygenation efficiency model of ammonia process of desulfurization absorption product+4 valency sulphur in the present invention is that inventor continues through a large amount of practical studies, find out in conjunction with the truth of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system in Practical Project, the oxygenation efficiency model of+4 valency sulphur in the present invention, the design and running instructing ammonia process of desulfurization absorption product+4 valency sulphur oxidative system in true engineering can be directly used in, enable the oxygenation efficiency engineering demands of+4 valency sulphur in ammonia process of desulfurization spray column slurry pool (Continuous Flow bubbling oxidation reaction device).

Embodiment 2:

A kind of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment is with embodiment 1.

The optimization regulating method of above-mentioned ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment, its concrete steps are:

Step one, determine following model parameter: the D of ammonia method desulfurizing system spray column r, G, F, q, and pH, C of slurries in spray column bottom slurry pond 501 s, V, t r, μ land σ l.

Wherein, D in above-mentioned parameter rfor 8.6m, t rfor 17.62min, G are 116.9m 3s -1, for 1556mgm -3, for 37mgm -3, F is 3.5, C sfor 2.2molL -1, pH is 5.4, Q is 0.16m 3s -1, μ lfor 0.5494Pas, surface tension σ lfor 67.77Nm -1, according to V=60t rl in, calculating slurry pool body slurry volume V is 432.55m 3.

Model parameter in step 2, input step one, and set C sin the initial concentration of+4 valency sulphur and+6 valency sulphur and meet in the present embodiment the oxygenation efficiency model of+4 valency sulphur is utilized to calculate the oxygenation efficiency of+4 valency sulphur in slurry pool 501 the oxygenation efficiency model being somebody's turn to do+4 valency sulphur is specific as follows:

&eta; = r ( I V ) V / M SO 2 - - - ( 1 ) ,

In formula (1) for the SO that spray column spray district 502 absorbs 2molar flow rate, unit is mols -1, its through type (2) calculates:

M SO 2 = G &times; ( C SO 2 , i n - C SO 2 , o u t ) / ( 1000 &times; 64 ) - - - ( 2 ) ,

R in formula (1) (IV)for the oxidation rate of+4 valency sulphur in slurry pool 501, unit is molL -1min -1, it calculates by formula (3):

r ( I V ) = C O 2 * / ( 1 k L a + 1 k 0 exp ( - 2.8 &times; 10 4 R T ) &CenterDot; 1 10 - 0.39 p H - 1.14 &CenterDot; 1 C SO 3 2 - - 0.5 &CenterDot; 1 - 4 C S 6 + + 9 ) - - - ( 3 ) ,

In formula (3), k 0for frequency factor, its value is 1.44 × 10 4; R is ideal gas constant, is 8.31Jmol -1k -1; T is temperature in spray column, is 323.15K; for the equilibrium concentration of gas-liquid interface place oxygen in slurry pool 501, unit is molL -1, its through type (4) calculates:

C O 2 * = Hp O 2 * - - - ( 4 ) ,

In formula (4), for gas-liquid interface place O in slurry pool 501 2equilibrium partial pressure, unit is Pa, in the present embodiment be 2.13 × 10 4pa; H is O 2solubility coefficient in slurry pool 501 in slurries, unit is molm -3pa -1, H calculates by formula (5):

l o g ( H 0 H ) = h 1 I 1 + h 2 I 2 + ... + h i I i + ... - - - ( 5 ) ,

In formula (5), H 0for O 2solubility coefficient in water, its value is 9.45 × 10 -6molm -3pa -1; h ifor the O that slurry pool 501 Inner electrolysis matter causes 2solubility reduces coefficient, and unit is m 3kion -1; I ifor the ionic strength of each ion in slurry pool 501 Inner electrolysis matter, unit is kionm -3.In the pH value range controlled in ammonia desulfurizing process, H in slurries 2sO 3and NH 3h 2the concentration of O is low, negligible, and the electrolyte in slurries refers to NH 4hSO 3, (NH 4) 2sO 3(NH 4) 2sO 4; h iand I icalculate respectively by formula (6) and formula (7):

h i=h ++h -+h G(6),

I i = 1 2 &Sigma;C i Z i 2 - - - ( 7 ) ,

In formula (6), slurry pool 501 Inner electrolysis matter NH 4hSO 3, (NH 4) 2sO 3(NH 4) 2sO 4the O caused 2solubility reduces coefficient h iwith embodiment 1, C in formula (7) ifor the concentration of each ion in slurry pool 501 Inner electrolysis matter, Z ifor the valence mumber of each ion.

In formula (3), k lfor oxygen mass tranfer coefficient in the liquid phase, unit is ms -1, it calculates by formula (8):

k L = 0.5 g 5 / 8 D O 2 1 / 2 &rho; L 3 / 8 &sigma; L - 3 / 8 d v s 1 / 2 - - - ( 8 ) ,

In formula (8), ρ lfor the density of slurries in slurry pool, unit is kgm -3, its through type (9) calculates:

&rho; L = ( 99 &delta; 1 C S 4 + + 116 &delta; 2 C S 4 + + 132 C S 6 + ) / 1000 - - - ( 9 ) ,

In formula (9), δ 1and δ 2be respectively with breadth coefficient, wherein,

&delta; 1 = K a 1 &lsqb; H + &rsqb; &lsqb; H + &rsqb; 2 + K a 1 &lsqb; H + &rsqb; + K a 1 K a 2 - - - ( 10 ) ,

&delta; 2 = K a 1 K a 2 &lsqb; H + &rsqb; 2 + K a 1 &lsqb; H + &rsqb; + K a 1 K a 2 - - - ( 11 ) ,

In formula (10) and (11), K a1and K a2be respectively balanced reaction with reaction equilibrium constant, wherein, lgK a1=853/T-4.74, lgK a2=621.9/T-9.278; [H +] be hydrionic active concentration in slurry pool (501) interior slurries, calculated by pH value.

D in formula (8) o2and d vsbe respectively the average diameter of bubble in the diffusion coefficient of oxygen in slurry pool liquid phase and slurry pool liquid phase, its unit is respectively m 2s -1and m, and d vscalculate by formula (12), (13) respectively:

D O 2 = 7.4 &times; 10 - 12 ( &alpha;M B ) 0.5 T &mu; L V A 0.6 - - - ( 12 ) ,

d v s = 26 D R ( gD R 2 &sigma; L ) - 0.5 ( gD R 3 &rho; L 2 &mu; L 2 ) - 0.12 ( u O G gD R ) - 0.12 - - - ( 13 ) ,

In formula (12), α is the associated factors of solvent in slurries in slurry pool, and value is 2.6; M bfor the molal weight of solvent in slurries in slurry pool, unit is gmol -1, M in the present embodiment bfor 18gmol -1; V afor the diffuse volumetric of oxygen molecule, unit is cm 3mol -1, be 16.6cm in the present embodiment 3mol -1.

In formula (13), u oGfor the superficial gas velocity of slurry pool internal oxidition air, unit is ms -1, it calculates by formula (14):

u O G = Q / ( &pi;D R 2 / 4 ) - - - ( 14 ) ,

In formula (3), a is gas-liquid contact interfacial area, and unit is m 2m -3, calculate by formula (15):

a = 6 &epsiv; G d V S - - - ( 15 ) ,

In formula (15), the gas holdup ε in slurry pool in liquid phase gcalculate by following formula:

&epsiv; G ( 1 - &epsiv; G ) 4 = 0.25 &times; ( u O G &mu; L &sigma; L ) ( &rho; L &sigma; L 3 g&mu; L 4 ) 7 / 24 - - - ( 16 ) ,

In formula (3), concentration calculate by following formula:

C SO 3 2 - = &delta; 2 C S 4 + - - - ( 17 ) ,

Each parameter is substituted into formula (1) ~ (17), and simultaneous formula (1) ~ (17) calculate the oxygenation efficiency of+4 valency sulphur in slurry pool 501 be 0.9234.

Step 3, the oxygenation efficiency of+4 valency sulphur will calculated in step 2 with bring following discriminate into test, discriminate is false:

| r ( I V ) V M SO 2 - C S 6 + C s | &le; 0.001 ,

Be back in step 2 and adjust with value, if then increase and reduce if then reduce and increase recalculate r (IV)v, until above formula is set up, finally exports the oxygenation efficiency of+4 valency sulphur be 91.35%.

Step 4 ,+4 valency sulfur oxidation rates will exported in step 3 compare with the target set point in Practical Project, if+4 valency sulfur oxidation rates calculated in step 3 the oxygenation efficiency comparing engine request is low, then return second step and adjust parameter p H, Q and C sin one or more, re-start calculating, until+4 valency sulfur oxidation rates exported in step 3 engineering demands, in the present embodiment, the method for adjustment of parameter is with embodiment 1.

Embodiment 3:

A kind of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment is with embodiment 1.

The optimization regulating method of above-mentioned ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment, its concrete steps are close with embodiment 1, and its difference is: the C in step one sfor 2.0molL -1, pH is 5.4, and other parameters are with embodiment 1; Calculate in step 2 be 1.4643, last+4 valency sulfur oxidation rates exported after adjustment in step 3 be 99.80%.

If+4 valency sulfur oxidation rates calculated in the 3rd step the oxygenation efficiency comparing engine request is low, then return second step and adjust parameter p H, Q and C as follows sin one or more, re-start calculating, until the 3rd step export+4 valency sulfur oxidation rates engineering demands, method is with embodiment 1.

Embodiment 4:

A kind of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment is with embodiment 1.

The optimization regulating method of above-mentioned ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment, its concrete steps are close with embodiment 1, and its difference is: the C in step one sfor 2.3molL -1, pH is 5.4, and other parameters are with embodiment 1; Calculate in step 2 be 0.5521, last+4 valency sulfur oxidation rates exported after adjustment in step 3 be 87.51%.

If+4 valency sulfur oxidation rates calculated in the 3rd step the oxygenation efficiency comparing engine request is low, then return second step and adjust parameter p H, Q and C as follows sin one or more, re-start calculating, until the 3rd step export+4 valency sulfur oxidation rates engineering demands, method is with embodiment 1.

Embodiment 5:

A kind of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment is with embodiment 1.

The optimization regulating method of above-mentioned ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment, its concrete steps are close with embodiment 1, and its difference is: the pH in step one is 5.4, Q is 0.32m 3s -1, other parameters are with embodiment 1; Calculate in step 2 be 0.9382, last+4 valency sulfur oxidation rates exported after adjustment in step 3 be 91.74%%.

If+4 valency sulfur oxidation rates calculated in the 3rd step the oxygenation efficiency comparing engine request is low, then return second step and adjust parameter p H, Q and C as follows sin one or more, re-start calculating, until the 3rd step export+4 valency sulfur oxidation rates engineering demands, method is with embodiment 1.

Embodiment 6:

A kind of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment is with embodiment 1.

The optimization regulating method of above-mentioned ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment, its concrete steps are close with embodiment 1, and its difference is: the pH in step one is 5.4, Q is 0.48m 3s -1, other parameters are with embodiment 1; Calculate in step 2 be 0.9501, last+4 valency sulfur oxidation rates exported after adjustment in step 3 be 91.83%.

If+4 valency sulfur oxidation rates calculated in the 3rd step the oxygenation efficiency comparing engine request is low, then return second step and adjust parameter p H, Q and C as follows sin one or more, re-start calculating, until the 3rd step export+4 valency sulfur oxidation rates engineering demands, method is with embodiment 1.

Embodiment 7:

A kind of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment is with embodiment 1.

The optimization regulating method of above-mentioned ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment, its concrete steps are close with embodiment 1, and its difference is: the t in step one rfor 14min, pH are 5.4, according to V=G × F × t r/ (1000 × 60), calculating slurry pool body slurry volume V is 343.68m 3; Calculate in step 2 be 0.6755, last+4 valency sulfur oxidation rates exported after adjustment in step 3 be 88.85%.

If+4 valency sulfur oxidation rates calculated in the 3rd step the oxygenation efficiency comparing engine request is low, then return second step and adjust parameter p H, Q and C as follows sin one or more, re-start calculating, until the 3rd step export+4 valency sulfur oxidation rates engineering demands, method is with embodiment 1.

Embodiment 8:

A kind of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment is with embodiment 1.

The optimization regulating method of above-mentioned ammonia process of desulfurization absorption product+4 valency sulphur oxidative system of the present embodiment, its concrete steps are close with embodiment 1, and its difference is: the t in step one rfor 20min, pH are 5.4, according to V=G × F × t r/ (1000 × 60), calculating slurry pool body slurry volume V is 343.68m 3; Calculate in step 2 be 0.9419, last+4 valency sulfur oxidation rates exported after adjustment in step 3 be 92.22%.

If+4 valency sulfur oxidation rates calculated in the 3rd step the oxygenation efficiency comparing engine request is low, then return second step and adjust parameter p H, Q and C as follows sin one or more, re-start calculating, until the 3rd step export+4 valency sulfur oxidation rates engineering demands, method is with embodiment 1.

Embodiment 9:

In order to the reasonability of verification model, sampling and testing 2 × 150MW boiler matching build ammonia method desulfurizing system slurry pool in slurries pH, with pH adopts Hana HI98128 type pH meter to measure, adopt iodometric determination, adopt ion chromatography, in slurries, the oxygenation efficiency of+4 valency sulphur can by formula calculate.Experiment records slurry pool slurries pH about 5.3 ~ 5.4, C sbe about 1.95 ~ 2.16molL -1, the oxygenation efficiency about 96.2% ~ 99% of+4 valency sulphur.

Confirming model parameter D rfor 8.6m, t rfor 17.62min, G are 420833m 3h -1, for 1556mgm -3, for 37mgm -3, F is 3.5, Q is 0.32m 3s -1, above-mentioned parameter is brought into+4 valency sulfur oxidation rate models of the present invention simultaneously and calculate, model calculation process as shown in Figure 3.Contrasted by the model calculation value of above-mentioned measured value of experiment and the present embodiment, as shown in Figure 4, in Fig. 4, A, B line is the error line of ± 10% to result.As can be seen from Figure 4, the model calculation value of+4 valency sulphur and the error of measured value of experiment are less than 10%, and model can meet the required precision of engineer applied.

Schematically above be described the present invention and embodiment thereof, this description does not have restricted, and also just one of the embodiments of the present invention shown in accompanying drawing, actual structure is not limited thereto.So, if those of ordinary skill in the art enlightens by it, when not departing from the invention aim, designing the frame mode similar to this technical scheme and embodiment without creationary, all should protection scope of the present invention be belonged to.

Claims (6)

1. ammonia process of desulfurization absorption product+4 valency sulphur oxidative system, comprise spray column body (5), it is characterized in that: this spray column body (5) inside comprises except fog-zone, spray district (502) and slurry pool (501) from top to bottom successively, wherein, neat stress outlet (506) is provided with at the top of described spray column body (5), be provided with demister (505) in the fog-zone of removing of neat stress outlet (506) below, this demister (505) is connected with the technique water tank of spray column outside; Be provided with shower (504) on the top in described spray district (502), and be provided with gas approach (503) in the tower body side that spray district (502) bottom is corresponding; Be provided with air sparger (2) in the bottom of described slurry pool (501), the air inlet duct of this air sparger (2) is connected with oxidation fan (1); The tower body side corresponding at slurry pool (501) is connected with slurries extraction pump (3) by extraction pipeline, and this slurry pool (501) is connected by the water inlet of circulating line with shower (504), circulating line is also provided with circulating pump (4), is also connected with ammoniacal liquor inlet tube (6) with the circulating line of the inlet communication of circulating pump (4).
2. a kind of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system according to claim 1, is characterized in that: be respectively equipped with smoke on-line monitoring system exporting with neat stress on pipeline that (506) be connected with gas approach (503).
3. a kind of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system according to claim 1 and 2, is characterized in that: the circulating line be connected in described slurry pool (501) and with the outlet of circulating pump (4) is equipped with pH meter.
4. an optimization regulating method for ammonia process of desulfurization absorption product+4 valency sulphur oxidative system, the steps include:
Step one, determine following model parameter: the D of ammonia method desulfurizing system spray column r, G, F, q, and pH, C of spray column bottom slurry pond (501) interior slurries s, V, t r, μ land σ l;
Wherein, D rfor the diameter of ammonia method desulfurizing system spray column, by measuring direct acquisition, unit is m; G is for being entered the flue gas flow rate of the pending flue gas in spray column by gas approach (503), recorded by smoke on-line monitoring system, unit is m 3s -1; with be respectively SO in spray column gas approach (503) and neat stress outlet (506) flue gas 2concentration, recorded by smoke on-line monitoring system, unit is mgm -3; F is the liquid-gas ratio in spray column, and be the setting value of system cloud gray model, unit is Lm -3; Q is the oxidation air amount in spray column slurry pool (501), and its value is theoretical air requirement Q 01 ~ 4 times, unit is m 3s -1; PH is the pH value of slurry pool (501) interior slurries; C sfor the total sulfur concentration of slurry pool (501) interior slurries, be+4 valency sulphur concentrations with+6 valency sulphur concentrations sum, its unit is molL -1; V is the volume of slurry pool (501) interior slurries, by adjusting the time of staying t of slurry pool (501) interior slurries rcontrol, V=60t rl in, unit is m 3, the L in this formula infor being flow to the slurry flow rate of slurry pool (501) by shower (504), unit is m 3s -1, pass through L in=F × G/1000m 3s -1calculate; The viscosity, mu of slurries lwith surface tension σ lutilize viscosimeter and surface tension instrument to record respectively, its unit is respectively Pas and Nm -1;
Model parameter in step 2, input step one, and set an initial pH value, oxidation air amount Q and C sin the initial concentration C of+4 valency sulphur and+6 valency sulphur s4+, C s6+, and meet the oxygenation efficiency model of+4 valency sulphur is utilized to calculate the oxygenation efficiency of+4 valency sulphur in slurry pool (501)
Step 3, the oxygenation efficiency of+4 valency sulphur will calculated in step 2 bring following formula into test:
| r ( I V ) V M SO 2 - C S 6 + C s | &le; 0.001
If the oxygenation efficiency of+4 valency sulphur calculated do not meet above formula, be back in step 2 and adjust with value, if r ( I V ) V / M SO 2 < C S 6 + / C S , Then increase and reduce if r ( I V ) V / M SO 2 > C S 6 + / C S , Then reduce and increase recalculate r (IV)v, until above formula is set up, finally exports now with the oxygenation efficiency of+4 valency sulphur
Step 4 ,+4 valency sulfur oxidation rates will exported in step 3 compare with the target set point in Practical Project, if model calculation value lower than target set point, be then back in step 2 and adjust parameter p H, Q and C as follows sin one or more, and re-start calculating, until+4 valency sulfur oxidation rates exported in step 3 engineering demands:
Reduce the pH of slurry pool (501) interior slurries, step-length is 0.1; Increase oxidation air amount Q, step-length is 0.5; Reduce the total sulfur concentration C of slurry pool (501) interior slurries s, step-length is 0.1, C sbe decreased through and increase by the slurry flow rate L of slurries extraction pump (3) extraction outrealize.
5. the optimization regulating method of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system according to claim 4, is characterized in that: in step 2, in slurry pool (501), the oxygenation efficiency of+4 valency sulphur calculates by with drag:
&eta; = r ( I V ) V / M SO 2 - - - ( 1 ) ,
In formula (1) for the SO that spray column spray district (502) absorbs 2molar flow rate, unit is mols -1, its through type (2) calculates:
M SO 2 = G &times; ( C SO 2 , i n - C SO 2 , o u t ) / ( 1000 &times; 64 ) - - - ( 2 ) ,
R in formula (1) (IV)for the oxidation rate of+4 valency sulphur in slurry pool (501), unit is molL -1min -1, it calculates by formula (3):
r ( I V ) = C O 2 * / ( 1 k L a + 1 k 0 exp ( - 2.8 &times; 10 4 R T ) &CenterDot; 1 10 - 0.39 p H - 1.14 &CenterDot; 1 C SO 3 2 - - 0.5 &CenterDot; 1 - 4 C S 6 + + 9 ) - - - ( 3 ) ,
In formula (3), k 0for frequency factor, its value is 1.44 × 10 4; R is ideal gas constant, is 8.31Jmol -1k -1; T is temperature in spray column, and unit is K; for the equilibrium concentration of slurry pool (501) interior gas-liquid interface place oxygen, unit is molL -1, its through type (4) calculates:
C O 2 * = Hp O 2 * - - - ( 4 ) ,
In formula (4), for slurry pool (501) interior gas-liquid interface place O 2equilibrium partial pressure, unit is Pa; H is O 2solubility coefficient in slurry pool (501) in slurries, unit is molm -3pa -1, H calculates by formula (5):
l o g ( H 0 H ) = h 1 I 1 + h 2 I 2 + ... + h i I i + ... - - - ( 5 ) ,
In formula (5), H 0for O 2solubility coefficient in water; h ifor the O that slurry pool (501) Inner electrolysis matter causes 2solubility reduces coefficient, and unit is m 3kion -1; I ifor the ionic strength of each ion in slurry pool (501) Inner electrolysis matter, unit is kionm -3, h iand I icalculate respectively by formula (6) and formula (7):
h i=h ++h -+h G(6),
I i = 1 2 &Sigma;C i Z i 2 - - - ( 7 ) ,
In formula (6), h +, h -, h gthe numerical value being respectively electrolyte positive and negative ion and being caused by the oxygen dissolved; C in formula (7) ifor the concentration of each ion in slurry pool (501) Inner electrolysis matter, Z ifor the valence mumber of each ion; In the pH value range controlled in ammonia desulfurizing process, H in slurries 2sO 3and NH 3h 2the concentration of O is low, negligible, and the electrolyte in slurries refers to NH 4hSO 3, (NH 4) 2sO 3(NH 4) 2sO 4;
In formula (3), k lfor oxygen mass tranfer coefficient in the liquid phase, unit is ms -1, it calculates by formula (8):
k L = 0.5 g 5 / 8 D O 2 1 / 2 &rho; L 3 / 8 &sigma; L - 3 / 8 d v s 1 / 2 - - - ( 8 ) ,
In formula (8), ρ lfor the density of slurry pool (501) interior slurries, unit is kgm -3, its through type (9) calculates:
&rho; L = ( 99 &delta; 1 C S 4 + + 116 &delta; 2 C S 4 + + 132 C S 6 + ) / 1000 - - - ( 9 ) ,
In formula (9), δ 1and δ 2be respectively with breadth coefficient, wherein:
&delta; 1 = K a 1 &lsqb; H + &rsqb; &lsqb; H + &rsqb; 2 + K a 1 &lsqb; H + &rsqb; + K a 1 K a 2 - - - ( 10 ) ,
&delta; 2 = K a 1 K a 2 &lsqb; H + &rsqb; 2 + K a 1 &lsqb; H + &rsqb; + K a 1 K a 2 - - - ( 11 ) ,
In formula (10) and (11), K a1and K a2be respectively balanced reaction with reaction equilibrium constant; [H +] be hydrionic active concentration in slurry pool (501) interior slurries, calculated by pH value;
In formula (8) and d vsbe respectively the average diameter of bubble in the diffusion coefficient of oxygen in slurry pool (501) liquid phase and slurry pool (501) liquid phase, its unit is respectively m 2s -1and m, and d vscalculate by formula (12), (13) respectively:
D O 2 = 7.4 &times; 10 - 12 ( &alpha;M B ) 0.5 T &mu; L V A 0.6 - - - ( 12 ) ,
d v s = 26 D R ( gD R 2 &sigma; L ) - 0.5 ( gD R 3 &rho; L 2 &mu; L 2 ) - 0.12 ( u O G gD R ) - 0.12 - - - ( 13 ) ,
In formula (12), α is the associated factors of solvent in slurry pool (501) interior slurries, and value is 2.6; M bfor the molal weight of solvent in slurry pool (501) interior slurries, unit is gmol -1; V afor the diffuse volumetric of oxygen molecule, unit is cm 3mol -1;
In formula (13), u oGfor the superficial gas velocity of slurry pool (501) internal oxidition air, unit is ms -1, it calculates by formula (14):
u O G = Q / ( &pi;D R 2 / 4 ) - - - ( 14 ) ,
In formula (3), a is gas-liquid contact interfacial area, and unit is m 2m -3, calculate by formula (15):
a = 6 &epsiv; G d V S - - - ( 15 ) ,
In formula (15), the gas holdup ε in slurry pool (501) interior liquid phase gcalculate by following formula:
&epsiv; G ( 1 - &epsiv; G ) 4 = 0.25 &times; ( u O G &mu; L &sigma; L ) ( &rho; L &sigma; L 3 g&mu; L 4 ) 7 / 24 - - - ( 16 ) ,
In formula (3), concentration calculate by following formula:
C SO 3 2 - = &delta; 2 C S 4 + - - - ( 17 ) ,
Simultaneous formula (1) ~ (17) namely calculate the oxygenation efficiency of+4 valency sulphur in slurry pool (501)
6. the optimization regulating method of ammonia process of desulfurization absorption product+4 valency sulphur oxidative system according to claim 4 or 5, is characterized in that: adjust parameter p H, Q, C in step 4 sparameter area require as follows: the pH of slurry pool (501) interior slurries is 5.0 ~ 6.0, C sbe 1.9 ~ 2.3mol/L, actual oxidation air capacity Q and theoretical oxidation air capacity Q 0the scope of ratio m be 1 ~ 4.
CN201510464978.8A 2015-07-29 2015-07-29 Ammonia desulphurization absorbent product S4+ oxidation system and optimal regulation and control method CN105032154B (en)

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