CN1301584A - Complex utilization method for boiler fume - Google Patents

Abstract

By adding ardealite flux and other matter into fuel coal for boiler, SO2 is produced at combustion temperature. Then, through combined denitration, desulfurization and defluorination process, SO2 is converted into SO3 and further H2SO4 is produced. Finally H2SO4 and phosphate rock power react to produce phosphoric acid and ardealite which is reused as flux. By means of the "sulfur" circulation including SO2, H2SO4 and ardealite in gas liquid and solid phase states, the exhausted dust and laughing gas from boiler are reduced to zero, the exhausted NOx and SO2 are reduced by about 97% and 90% separately, and there result in clean combustion of boiler, no sulfur resource loss and pollutionless production of H2SO4 and phosphoric acid.

Description

Comprehensive utilization method of boiler flue gas

The invention belongs to the technology of industrial waste gas prevention and control, and particularly relates to a comprehensive utilization method of coal-fired boiler flue gas.

At present, about 50 hundred million tons of coal are burned every year in the world, most of the coal is used by a power generation boiler, and a large amount of dust and laughing gas (N) are discharged to the atmosphere₂O), oxides of Nitrogen (NO) of two or more valences)、SO₂、CO₂The air is turbid, the ozone layer of the earth atmosphere is damaged, the air is acidified, and the greenhouse effect is achieved; a large amount of ash slag discharged to the ground forms a stacked land and pollutes the underground water. Only China is piled with 1.5 million tons of fly ash discharged by a power generation boiler every year, and the land occupation is up to 15 ten thousand mu. In addition, the phosphate fertilizer for increasing the yield of grains and avoiding hunger of human beings also brings great pollution to the ecological environment, and about 90 percent of the phosphate fertilizer is generated by the reaction of about 2.5 to 3.1 tons of sulfuric acid and phosphate rock powder by a wet-process phosphoric acid technology to generate 1 ton of phosphoric acid (P)₂O₅) And 3.5 kilograms of SO is discharged to the atmosphere on average when 1 ton of sulfuric acid is produced₂0.1 kg of acid mist, 16 tons of sewage containing arsenic, cadmium, lead and mercury, and 500 kg of pyrite cinder (calculated by pyrite used for 83 percent of sulfuric acid in China) so that each ton of P₂O₅The production of phosphoric acid discharges 10kg of SO₂0.3kg of acid mist, 50 tons of sewage, 1.5 tons of pyrite cinder and 4.5 tons of phosphogypsum (published by Ministry of chemistry and industry, 1991, Von Ministry of Qi, handbook of chemical fertilizers, P)_{152、153、223}Page). The United states is the country which produces the most phosphate fertilizers in the world nowadays, and the annual production of the phosphate fertilizers is about 1600 ten thousand tons of P₂O₅Zhongren 60kgP₂O₅Almost ten times of the average amount of people in China, and because the high-grade phosphate ores in China are concentrated at the upstream of rivers in the Yunnan Guiyuansi plateau, a disaster is inevitably formed if the pollution of phosphate fertilizer production to the environment is not solved obviously after the consumption of the phosphate fertilizer in China reaches the United states.

The human beings have gone through a lot of curved roads in the treatment of boiler coal burning and phosphate fertilizer pollution, and after the second war, Federal Germany adopts a liquid slag-discharging boiler and uses limestone as cosolventThe ash slag is liquefied to convert the ash slag into the active material with cement, and the utilization rate of the ash slag reaches 69 percent in 1970, but at the moment, people find that the atmosphere is seriously polluted by nitrogen oxide and sulfur dioxide, and a slagging boiler is just the boiler with the largest discharge amount of the nitrogen oxide. After the 1979 Japanese inner tile signed by International Agreement for preventing remote air pollution across national boundaries, various countries have legislation for limiting NO_X、SO₂Emission, so that the liquid boiler must adopt flue gas denitration (NO)₂) Desulfurization (SO)₂) The purification technology makes the pollution of the flue gas to the atmosphere meet the legal requirements. However, the cost of the technology reduces the power generation profit by about 30% to 50%, and even in the SNOX flue gas purification method with low cost, the power generation profit per KWh is reduced by 0.87 Fenni (European economic Committee of N-oxide emission control technology experience summary, department of electric Power, 1994 publication, pages P1, 14 and 187). since the slag tapping boiler is only ash liquefaction, only the ash has low use value and cannot create profit to offset the cost of flue gas denitration and desulfurization, then mankind starts to turn to the circulating fluidized bed boiler which is NO although NO is used for denitration and desulfurization_X、SO₂The emission is low, but the ash residue has no utilization value, people walk on the utilization of boiler ash residue for more than 100 years and return to the original starting point, after a hole appears in the Antarctic ozone layer in 1980, three gases of chlorofluorocarbon, salon and laughing gas which destroy the ozone layer are noticed, and meanwhile, a plan for canceling chlorofluorocarbon and salon is made, after 1991, the environmental protection agency of the European economic Committee finds that the popularized 'environmental protection' type circulating fluidized bed boiler is the boiler with the most serious laughing gas emission, and no technology for eliminating laughing gas is invented so far by people, because the laughing gas emitted after the comprehensive popularization of the circulating fluidized bed boiler is probably multiple times of the existing salon and chlorofluorocarbon, so that people can prevent and treat the laughing gas after the comprehensive popularization of the circulating fluidized bed boilerThe pollution of the boiler is trapped in a dilemma.

On the aspect of how to treat the pollution of the phosphate fertilizer industry, the discovery that the establishment of sulfur cycle by-product phosphoric acid by-product of the by-product sulfuric acid generated by the burning of phosphogypsum in a cement kiln and the preparation of cement from CaO in the phosphogypsum is a good method, but because the amount of burning coal is less than that of burnt phosphogypsum, the sulfur in the coal is difficult to make up for the sulfur cycle of cementIn SO₂And H₂SO₄The loss of sulfur element formed by loss and the need of supplementing natural pyrite lead to low economic benefit, which makes the technology difficult to popularize all the time. So far, only a plurality of cement plants in thousands of cement plants in China use sulfur to produce cement circularly, which fully explains that the elimination of pollution in the phosphate fertilizer industry is difficult and serious.

The invention aims to provide a clean technology for co-producing phosphoric acid and sulfuric acid by using a power boiler, which has low energy consumption and high benefit.

The technical scheme of the invention is to combine the prior conventional technologies, namely a slag tapping boiler, a combined denitration and desulfurization technology of SNOX flue gas and a defluorination technology of a DESONOX technology, a semi-hydrated or dihydrate-semi-hydrated process wet-process phosphoric acid and the like, to form a sulfur cycle which can automatically maintain balance without supplementing natural sulfur resources and ensures that phosphoric acid and sulfuric acid are 'by-produced' by the cycle, wherein the amount of coal burning is larger than that of phosphorus gypsum.

The method comprises the following steps:

(1) coal, ardealite fluxing agent and other additives enter a boiler to be combusted simultaneously to generate SO₂Smoke and liquid glass slurry, wherein the glass slurry is discharged out of the boiler for additional utilization;

(2) inputting the flue gas obtained in the step (1) into a SNOX flue gas purification technology bag type dust remover, maintaining the inlet temperature of the dust remover at 190 +/-5 ℃, and reducing the dust in the flue gas to 5mg/Nm³The following;

(3) heating the dedusted flue gas at 390-410 ℃, then feeding the heated flue gas into a denitrator, simultaneously adding ammonia, and removing NO and NO under the action of a catalyst₂In the presence of NO_XA compound;

(4) removing NO by step (3)_XThe compound flue gas enters a desulfurizer, and SO is made under the action of a catalyst at the temperature of 41-500 DEG C₂Conversion to SO₃；

(5) Step (4) contains SO₃The flue gas of the gas passes through a sulfuric acid catcher and an electric acid mist remover with the function of a low-temperature air preheater to ensure that SO is removed₃Generating H with the concentration meeting the requirement of wet-process phosphoric acid production₂SO₄；

(6) The flue gas desulfurized in the step (5) enters a defluorination device, so that more than 90% of fluoride in the flue gas is absorbed, and then the flue gas is discharged into the atmosphere through a chimney;

(7) h obtained by the step (5)₂SO₄Mixing with ground phosphate rock to prepare phosphoric acid, and returning the discharged phosphogypsum to the step (1)to be used as a fluxing agent.

The other additives in the step (1) are selected from two or more than two ores of serpentine or forsterite, limestone, quartz sand or silica, dolomite or magnesite, and ores containing zinc, copper, magnesium, manganese and molybdenum elements can be added when the functional glass microelement fertilizer is prepared by melting liquid glass slurry according to requirements.

The addition of the cosolvent phosphogypsum and other additives including serpentine, limestone, quartz sand and dolomite meets the condition of vitrifying the coal ash, and the specific requirements are as follows:

the addition amount of the phosphogypsum fluxing agent and other additives meets the condition of vitrifying the coal ash (the following percentages all take the glass slurry as a reference):

(1)Al₂O₃≤25％,(2)SiO₂35-50％,(3)CaO 20-40％,(4)MgO 3.5-20％,

(5) CaO + MgO more than 35%, viscosity at 1500 deg.C η less than 50 poise, and (7) n_o/n_si≤4.5，

In the formula, n_o、n_siIs the number of oxygen and silicon atoms in the glass slurry, $\left(8\right)3\≤\frac{n_0}{n_{\mathrm{si}}+n_p+1/2n_{\mathrm{Al}}}\≤4,$ in the formula, n_p、n_AlThe number of atoms of phosphorus and aluminum in the glass slurry, and (9) FeO₃≤15％，

In the formula, X^JIs X¹、X²、X³、X⁴、X⁵Respectively representing the addition amount (Kg/T coal) of phosphogypsum, serpentine, limestone, quartz sand, dolomite or substitute ore thereof which meets the above conditions; q_DW、Q_{Allow for}Respectively representing the low-level calorific value (KJ/Kg coal) of the base coal received by the slagging boiler, the lowest calorific value (KJ/Kg coal) allowed by the mixed powder of the coal powder carried into the boiler by primary air, the additive powder and the remelted coal ash, and determining by a combustion test; epsilon is a combustion safety coefficient, is determined by boiler thermotechnical calculation or combustion tests and is generally 1.05-1.3; phi, G_PLRespectively representing the rate of the meltback fly ash of the slagging boiler (determined by tests) and the quantity of the glass slurry (Kg/T coal) converted from ash vitrification per ton of fuel coal, $G_{\mathrm{PL}}=1000\mathrm{Aar}(1-a_z)+\underset{J=1}{\overset{5}{\mathrm{\Σ}}}{X}^J(1-{a^J}_z),$ in the formula: aar, a_zRespectively representing the base ash content (%) of the coal and the ash burning loss (%) of the ash at 1600 ℃ and determined by an assay; a is^J _zRepresents the loss on ignition (%) of the additive of the J th type at 1600 ℃ and is determined by an experiment.

In order to meet the vitrification requirement of the coal ash, the method can be achieved by adopting the following steps:

(1) according to SiO in coal ash₂、Al₂O₃Four kinds of SiO with contents of 35%, 40%, 45% and 50%₂Quaternary viscosity phase diagram of contents, selecting a SiO₂Graph (if not equal to integral multiple of 5 and 10, two graphs are selected for averaging), and the graph is based on Al₂O₃To determine the quaternary system SiO that meets the viscosity requirements₂-Al₂O₃CaO-MgO composition, the quaternary phase-viscosity diagram being accessible to known data (Wang Shi, slag atlas, P276, Metallurgical Press, 1958);

(2) according to the components determined by the quaternary viscosity phase diagram, the amount of the vitrification additive is calculated by the following simultaneous equations by adopting a trial algorithm and an interpolation method: $1000A_{\mathrm{ai}}{a}_I,+\underset{J=1}{\overset{5}{\mathrm{\Σ}}}{X}^J\·X_i,={\left(\mathrm{PL}\right)}_i,$

in the formula: j =1, 2, 3, 4,5, i' =4,5,6,7 are CaO, MgO, Al in each ore J, respectively₂O₃、SiO₂A chemical component of_i' represents CaO, MgO, Al in coal ash₂O₃、SiO₂Content (%), X^JIs X¹、X²、X³、X⁴、X⁵Respectively representing the addition amounts (Kg/T coal) of phosphogypsum, serpentine, limestone, quartz stone and dolomite, and X^J _IRespectively represents CaO, MgO and SiO in phosphogypsum, serpentine, limestone, quartz sand and dolomite (J =1, 2, 3, 4 and 5)₂、Al₂O₃(i' =4,5,6,7) content (%), determined by assay, (PL)_i(i' =4,5,6,7) respectively represent the components CaO, MgO, SiO of the glass slurry which meet the viscosity condition and are selected in a quaternary viscosity phase diagram₂、Al₂O₃Data (%).

The above are different in four (PL)_iThe following system of equations has four equations, but the unknown number X^JThere are 5, should try the algorithm to solve with the following principle, its principle is:

(a) adding the phosphogypsum and the limestone in the amount of X¹The larger the limestone, the better the limestone addition X³Smaller is better, equal to zero is best;

(b) the addition amount of serpentine, quartz sand and dolomite is X²The more the better, the more the addition X of the quartz sand and the dolomite⁴、X⁵Smaller is better, equal to zero is best;

(c) total weight of additivesX^JAnd the smaller the viscosity, the better.

(3) The quantity X of the ash vitrification additive determined according to the step (2)^JTo n is paired_o/n_si≤4.5 $3\≤\frac{-\mathrm{no}}{n_{\mathrm{si}}+n_p+1/2n_{\mathrm{Al}}}\≤4$

And (4) checking and calculating, and if the product is not qualified, repeating the steps (1) and (2) until the product is qualified.

The phosphogypsum fluxing agent in the step (1) is a by-product of the preparation of the phosphoric acid in the step (7) of the invention, and contains a small amount of H₂SO₄And trace amounts of HF and H₂SiF₆And trace phosphoric acid and a large amount of water, so the raw materials are neutralized before entering the boiler, air-dried at normal temperature, and dried by a conventional drying method such as a rotary drum dryer after being pelletized and crushed if necessary to reduce the water content to below 3 percent without influencing combustion.

The phosphogypsum is decomposed into H in turn at the high temperature of boiler combustion₂O,SO₂,O₂And generating CaO&SiO₂And the like, thereby not only realizing the sulfur circulation solid-gas phase conversion, but also achieving the fluxing action of reducing the melting temperature of the ash slag. During the combustion in step (1), SO is also generated from the sulfur in the coal₂. The bag filter in the step (2) is a bag filter used in the SNOX method and mainly has the function of ensuring that the dust in the flue gas is changed from 10000m/Nm³The above is reduced to 5mg/Nm³The denitration and desulfurization catalyst in the downstream step is protected from poisoning by pollution and the by-product H is produced₂SO₄The quality is qualified.

The denitration and desulfurization byproduct sulfuric acid method in the steps (3) to (5) adopts a SNOX combined denitration and desulfurization method (the European economic Committee of the United nations 'experience summary of nitrogen oxide emission control technology', 1994 version 160 of the institute of thermal engineering of Western-style safety of environmental protection offices of the department of Electrical Power, hereinafter referred to as "experience summary"). In the denitration, after ammonia is added into the flue gas, NO and NO are eliminated under the action of a catalyst₂Etc. NOx compounds, which react as follows:

the adding amount of ammonia in the denitration process is calculated according to 1.0-1.1 times of theoretical consumption, so that NO is eliminated_XThe efficiency reaches more than 97%, the amount of ammonia added in different coals and combustion methods is different, and the denitrated flue gas enters a desulfurization device and reacts as follows under the action of a catalyst:

conversion to SO₃The flue gas is cooled to below the dew point of the flue gas, and then the following reactions occur: i.e. sulphuric acid having a concentration that meets the requirements for wet-process phosphoric acid manufacture, said desulphurisation catalyst also being known.

The defluorination method described in step (6) is performed by the dessonox technique (summary of experience, page 163). When phosphogypsum is used as fluxing agent, HF and SiF need to be carried into flue gas₄Therefore, the gas is required to pass through a defluorination device, so that the fluoride gas is absorbed by more than 90 percent.

The method for preparing phosphoric acid in the step (7) adopts the known semi-water or dihydrate-semi-water flow wet-process phosphoric acid technology (Von Mingchen, China fertilizer handbook, page 154), and the sulfuric acid obtained in the step (6) reacts with the powdered rock phosphate to obtain phosphoric acid and phosphogypsum, namely, the sulfur in the flue gas is converted into solid-phase sulfide phosphogypsum through the sulfuric acid which is a byproduct of desulfurization, and the solid-phase sulfide phosphogypsum is reused. The addition amount of the phosphate rock powder can be calculated according to the grade of the phosphate rock.

The method of the present invention is specifically described below with reference to the flowchart.

FIG. 1 is a schematic flow chart of the present invention (schematic process of the sulfur cycle of a slagging boiler).

As shown in figure 1, coal and glass additives, i.e. phosphogypsum and other additives are added into a slag boiler 2 in proportion, flue gas generated after high-temperature combustion enters a dust remover 5 after passing through an air preheater 3 and a fine adjustment cooler 4, the flue gas after dust removal is led out by an induced draft fan 6 and is sent into an SNOX (selective non-oxidation) denitration device 8 through a heat exchanger 7 to eliminate NO_XThen enters a desulfurizing device 9 to ensure that SO is generated₂To SO₃Then the waste gas enters a sulfuric acid catcher 10, the trapped sulfuric acid enters a storage tank 14, then enters a wet-process phosphoric acid device 16, meanwhile, phosphate mineral powder 15 is added, the generated phosphoric acid enters a phosphoric acid storage tank 18, the phosphogypsum enters a phosphogypsum treatment device 17 for treatment and then returns to a fuel system 1 for recycling, the fly ash separated by a dust remover 5 is remelted or discharged, the denitrated and desulfurized flue gas enters a defluorinator 13 after acid mist is removed by an electric acid mist remover 12, and the defluorinated flue gas is discharged into the atmosphere. In the figure, 11 is a blower, 19 is an ammonia storage tank, and 20 is a water quenching granulation box.

The apparatus of the present invention is a known product.

The invention has the main advantages and effects that:

the invention is suitable for liquid slag discharging boilers and cyclone furnaces. By utilizing the function of the furnace, phosphogypsum is added to decompose with sulfur in coal at high temperature to generate SO₂,SO₂And by known denitration (NO)_X) Conversion of desulfurization techniques to SO₃Further to produce H₂SO₄,H2_SO₄Reacting with powdered rock phosphate to generate phosphoric acid and phosphogypsum, and reusing the phosphogypsum to form a gas-liquid-solid three-phase state, namely SO₂、H₂SO₄The three sulfur-containing chemical substances of the phosphogypsum form sulfur circulation, so that the flue gas of the boiler is purified, the cost is reduced to zero, and the boiler has profit, thereby realizing clean production of the boiler, producing phosphate fertilizer, glass fertilizer and no ash discharge, and supplying heat and power by clean smoke exhaust; the adopted technologies of denitration, desulfurization, defluorination and phosphoric acid preparation are mature methods, so that industrialization is easy to realize, and the method has strong practicability; the method of the invention recycles the sulfur in the flue gas, and the flue gasThe dust and laughing gas (nitrous oxide) in the smoke are almost equal to fog, so that the smoke NO can be generated_X、SO₂The pollution to the environment is respectively reduced by about 97 percent and 90 percent; in addition, the invention can approximately consider that the phosphoric acid is produced under the condition of no sulfur resource consumption due to the circulation of the sulfur, which is the same as the conventional method for producing 1 ton of sulfuric acid by 0.97 ton of pyrite and 1 ton of P by 2.5-3.10 ton of sulfuric acid₂O₅Compared with the wet-process phosphoric acid technology of phosphoric acid, the method can save 2.4 to 3 tons of pyrite/ton of P₂O, thereby also reducing the cost of producing phosphoric acid. In conclusion, the invention has great economic benefit and social benefit, and is a technology with practical significance and practical value.

The features of the present invention are further illustrated by the following specific examples.

Examples

The fuel is Xishan lean coal, the calorific value is 25600kJ/kg, the sulfur content is 1.5%, the powder coal meltback rate phi is 11.765%, the additives serpentine, limestone and dolomite are high-quality ores, the production places are Shaanxi black woods, Hebei Changning camping gyuan and Yingkou Chenjiabao respectively, and the adding amount is shown in Table 1:

tests show that the addition amount of the phosphogypsum of 211.53kg/T coal can enable the calorific value of the mixed powder to be equal to Q_{Allow for}The maximum amount of the added phosphogypsum is reached, and the balance cannot be achieved due to the fact that CaO in the glass is still insufficient, which indicates that the limestone cannot be completely replaced by the phosphogypsum, and 43.94kg/T of coal limestone still needs to be added.

The loss on ignition and the weight of the glass formed for the coal and the additives are shown in Table 2, the chemical composition and the addition amount of the additives are shown in Table 3, the chemical composition of the Liuyang phosphate ore is shown in Table 4, and the ash is vitrified at a viscosity of η₁₅₀₀Less than 5.4 poise, CaO, MgO, SiO as chemical component₂、Al₂O₃、Fe₂O₃23.8%, 14.37%, 37.65%, 17.8%, 5.08%, P₂O₅The component is O.52%; in glass n_o、n_si、n_p、n_Al13078, 3121, 17.94, 2579, respectively, n_o/n_si≌4.3,n_o/n_si+n_p+1/2n_Al≌3.285。Q_{Allow for}15900-16750kJ/kg, ε =1.05.

Adding the coal and the additive into a horizontal cyclone furnace with slag capturing rate of 85 percent at 75-130 tons/hour, and according to the combined flow: SNOX device denitration (NO)_X) And desulfurization with an efficiency of 97% to contain P₂O₅30.4 percent of Liuyang phosphate rock powder is used as a raw material, a semi-water or two-water and semi-water process wet-process phosphoric acid device is adopted, and the conversion rate is 97 percent. This allows 45.63 tons (P) of phosphoric acid to be produced in the sulfur cycle for every 1000 tons of coal fired by the boiler₂O₅Calculated) 48.00 tons of 72% strength sulfuric acid (34.56 tons of 100% strength sulfuric acid). The phosphoric acid and the sulfuric acid can be sold as commodities, and can also be used for producing ammonium phosphate fertilizers and ammonium sulfate fertilizers, and 79 tons of monoammonium phosphate and 46.08 tons of ammonium sulfate can be produced by burning 1000 tons of coal in Xishan.

TABLE 1 West mountain coal Properties

Name (R)	Coal composition								Chemical composition of ash
														Low positionHeating value		Ash content	Sulfur content	Selenium	Germanium (Ge)	Arsenic (As)	Cadmium (Cd)	P2O5		K2O+Na2O
	Unit of	KJ/kg		％	％	PPM	PPM	PPM	PPM	％		％
Number of															25600		21.48	1.5	1	3	9	0.1	0.10		0.964
	Name (R)	Chemical composition of ash slag
CaO															MgO	SiO2	Al2O3	Fe2O3	MnO		ZnO		CuO		MoO3
		Unit of	％	％	％	％	％	％		％		％		％
Number of	4.02															0.18	49.19	37.63	5.95	6.45×10-3		6×10-3		7.5×10-3		3×10-3
		Name (R)	Chemical composition of ash slag
CoO																Cr2O3		SnO		NiO		V2O5		B2O3		Loss of heat (SO3)
			Unit of	％		％		％		％		％		％													％
Number of	5.075×10-3															4.4×10-3		1.27×lO-3		8.9×10-3		0.0375		0.0129		0.43

TABLE 2 loss on ignition of coal ash and additives and amount of glass formed per ton of coal and additives

Name (R)	Coal ash slag	Phosphogypsum	Serpentine stone	Limestone	Dolomite
						Addition amount of coal	214.8	211.53	140.8l	43.94	63.57
Loss on ignition,%	0.43	52.58	14.1	41.48	46.50
						Amount of glass, kg/T coal	210.7	100.03	121.77	25.71	34.33

TABLE 3 additive addition and chemical composition

Mine Stone (stone)	Producing area	Adding amount of kg/T coal	Chemical composition (%)
											CaO	MgO	SiO2	Al2O3	Fe2O3	SeO2	GeO	Loss of heat
			Phosphorus stone Ointment	Hunan Liuyang phosphate ore Generating	211.53	31.28	0.23	9.09	1.87	1.45									7.09×10-7	6.10×10-6	52.58
Snake lines Stone (stone)	Ling Xili wood forest	140.94									0.30	39.53	40.11	0.65	5.14	1.26×10-5	6.10×10-4	14.11
			Lime Stone (stone)	Hebei funinghuo exercise Camp	43.93	53	0.66	3.00	0.63	0.44									5.7×10-5	8.9×10-4	41.48
White cloud Stone (stone)	Liaoning Yingkou Chenjia Fort shape	63.57									29.50	21.10	1	0.50	1.10	5.7×10-5	8.9×10-4	46.5

TABLE 4 Liuyang phosphate rock chemical composition

Mine species	P2O5	CaO	MgO	Fe2O3	Al2O3	CO2	SiO2	F
									Raw ore	30.46	42.61	0.669	2.65	3.43	2.47	13.74	2.88

Claims (4)

1. A comprehensive utilization method of boiler flue gas is characterized by comprising the following steps:

(1) coal, the dried phosphogypsum fluxing agent and other additives enter a boiler to be combusted at the same time to generate SO₂The flue gas and the liquid glass slurry are discharged from the boiler for additional utilization,

(2) inputting the flue gas obtained in the step (1) into a bag type dust collector, keeping the dust removal temperature at 190 +/-5 ℃, and reducing the dust in the flue gas to 5mg/Nm³In the following, the following description is given,

(3) heating the dedusted flue gas to 390-410 ℃, then feeding the flue gas into a denitrator, simultaneously adding ammonia, and removing NO and NO under the action of a catalyst₂In the presence of NO_xA compound which is a mixture of a compound having a structure,

(4) removing NO by step (3)_xThe flue gas after the compound enters a desulfurizer, and SO is enabled to be generated at the temperature of 410-500 ℃ under the action of a catalyst₂Conversion to SO₃，

(5) Step (3) contains SO₃The flue gas passes through a sulfuric acid catcher and an electric acid mist removing device with the function of a low-temperature air preheater to ensure that SO is generated₃The generated sulfuric acid with the concentration meeting the requirement of wet-process phosphoric acid production enters a sulfuric acid storage tank,

(6) the flue gas desulfurized in the step (5) enters a defluorinating device for defluorination and then is discharged into the atmosphere through a chimney,

(7) obtaining H with the concentration meeting the wet-process phosphoric acid requirement by the step (5)₂SO₄Reacting with phosphate rock powder in a semi-hydrated or dihydrate-semi-hydrated wet-process phosphoric acid device to obtain phosphoric acid and phosphogypsum, feeding the phosphoric acid into a phosphoric acid storage tank, and returning the phosphogypsum to the step (1) for reuse.

2. A process according to claim 1, wherein the other additive is selected from the group consisting of two or more of serpentine or forsterite, limestone, quartz sand or silica, dolomite or magnesite.

3. A method according to claim 1 or 2, characterised in that the phosphogypsum flux and other additives are added in amounts which satisfy the conditions for vitrifying the soot (the following percentages are based on the glass slurry):

(1)Al₂O₃≤25％,(2)SiO₂35-50％,(3)CaO₂0-40％,(4)MgO 3.5-20％,

(5) CaO + MgO more than 35%, viscosity at 1500 deg.C η less than 50 poise, and (7) n_o/n_si≤4.5，

In the formula, n_o、n_siIs the number of oxygen and silicon atoms in the glass slurry,

$\left(8\right)3\≤\frac{n_o}{n_{\mathrm{si}}+n_p+\frac{1}{2}{n}_{\mathrm{Al}}}\≤4,$ in the formula, n_p、n_AlFor phosphorus and aluminium in glass slurry

The number of atoms,

(9)Fe₂O₃≤15％，

in the formula, X^JIs X¹、X²、X³、X⁴、X⁵Respectively representing the addition amounts (Kg/Kg coal) of the phosphogypsum, the serpentine, the limestone, the quartz sand and the dolomite which meet the conditions; q_DW、Q_{Allow for}Respectively representing the low calorific value (KJ/T coal) of the base coal received by the slag tapping boiler, the coal powder carried into the boiler by primary air, the additive powder and the mixed powder of the remelted coal ashThe lowest permissible calorific value (KJ/Kg coal), determined by combustion tests; epsilon is combustion safety coefficient and is determined by boiler thermodynamic calculation or combustion test, generally1.05-1.3；φ、G_PLRespectively represents the rate of the meltback fly ash of the slagging tap boiler (determined by tests), the amount of the glass slurry (Kg/T coal) converted from ash vitrification per ton of fuel coal, and G_pL=1000Aar(1-a_z) $+\underset{J=1}{\overset{5}{\mathrm{\Σ}}}{X}^J(1-a_z^J)$ In the formula: aar, a^J _zRespectively representing the base ash content (%) of the coal and the ash burning loss (%) of the ash at 1600 ℃ and determined by an assay; a is^J _zRepresents the loss on ignition (%) of the J additive at 1600 ℃ and is determined by an assay.

4. The process according to claim 1, characterized in that the ammonia is added in step (3) in an amount of 1.0 to 1.1 times the theoretical consumption.

Images