CN101519193B - Acid preparing method by coal gas wet oxidation and desulfurization - Google Patents
Acid preparing method by coal gas wet oxidation and desulfurization Download PDFInfo
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- CN101519193B CN101519193B CN2008100338597A CN200810033859A CN101519193B CN 101519193 B CN101519193 B CN 101519193B CN 2008100338597 A CN2008100338597 A CN 2008100338597A CN 200810033859 A CN200810033859 A CN 200810033859A CN 101519193 B CN101519193 B CN 101519193B
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Abstract
The invention provides an acid preparing method by coal gas wet oxidation and desulfurization, which comprises the following steps of: introducing sulfur-containing coal gas into an absorption sectionof a desulfurization regeneration tower from the bottom, and then introducing desulfurization barren solution into the absorption section from the upper part to contact the coal gas countercurrent; d elivering desulfurization rich liquid from the bottom of the absorption section at the lower part of the desulfurization regeneration tower into a regeneration section at the top of the desulfurization regeneration tower; introducing regeneration air into the regeneration section to obtain the mixture of the desulfurization barren solution and sulfur foam; concentrating the sulfur foam into sulfurpulp to be delivered in a combustion furnace after being atomized by adopting compressed air through a nozzle and then delivered into a converter provided with vanadium catalyst to be converted to su lfur trioxide after the furnace gas is cooled, washed and dried; and delivering the sulfur trioxide into an absorption tower to be converted into product sulfuric acid with weight concentration of 94 percent to 98 percent. The method reduces exhaust emissions, does not emit liquid waste outwards, and has conversion rate of sulfur dioxide over 99.6 percent and good economic and social benefits.
Description
Technical field
The present invention relates to the method for coal gas desulfurization relieving haperacidity, specifically a kind of coal gas wet oxidation and desulfurization sulphur slurry that utilizes is raw material system vitriolic method.
Background technology
It is alkali source that traditional coal gas wet oxidation and desulfurization technology is used ammoniacal liquor and diluted alkaline (yellow soda ash) more, absorbs hydrogen sulfide and prussic acid in the coal gas in thionizer, and regenerator column is oxidized to the sulphur foam by air with hydrogen sulfide then, and generates corresponding salt.
At present, domestic sulphur foam adopts the molten sulphur of steam heating, makes wherein that sulphur content reaches 50～90%, and desulfurization waste liquor is allocated in the coking coal.The catalyzer that desulfurization is used is Resorcinol and phthalocyanine cobalt sulfonate organometallics, or adopts 1,4-naphthoquinones-2-sodium sulfonate, and in doctor solution, add an amount of Seignette salt and 0.12～0.28% sodium metavanadate.Described method desulfurization waste liquor corrodibility is big, and toxicity is big, and is very big to environmental influence.Be unfavorable for suitability for industrialized production, need improve.
Summary of the invention
The object of the present invention is to provide a kind of acid preparation method by coal gas wet oxidation and desulfurization, to overcome the above-mentioned defective that prior art exists.
Method of the present invention comprises the steps:
With the absorber portion of sulfur-containing coal gas from bottom feeding desulfurization regeneration tower, the desulfurization lean solution is fed desulfurization regeneration tower absorber portion from top, with the coal gas counter current contact, absorb hydrogen sulfide and prussic acid in the coal gas;
Said desulfurization lean solution refers to, and does not have the doctor solution of absorbing hydrogen sulphide and prussic acid;
Said desulfurization lean solution is that the ammoniacal liquor or the equivalent concentration that contain ammonia 7 grams per liters～18 grams per liters are the aqueous sodium carbonate of 0.4～0.6N, the pH value is 8.5～9.5, and contain catalyzer, said catalyzer is Resorcinol and phthalocyanine cobalt sulfonate organometallics or 1,4-naphthoquinones-2-sodium sulfonate, this catalyzer is sulfur-containing coal gas desulfurization catalyzer commonly used, catalyzer as 2006 " Henan metallurgy " " some problems of wet oxidation process COG sulfur removal technology " bibliographical information, in the desulfurization lean solution, the weight content of catalyzer is 3 grams per liters～5 grams per liters;
In the said sulfur-containing coal gas, each components contents is as follows:
The ratio of sulfur-containing coal gas and desulfurization lean solution is:
40～50 mark rice
3Sulfur-containing coal gas/rise desulfurization lean solution.
The desulfurization rich solution that has absorbed hydrogen sulfide and prussic acid is sent into the RS Regenerator Section at top, absorption tower from the absorber portion bottom of bottom, absorption tower, simultaneously, regeneration air is fed RS Regenerator Section, hydrogen sulfide in the desulfurization rich solution and prussic acid are oxidized to the sulphur foam, obtain desulfurization lean solution and sulphur foamy mixture, after the desulfurization lean solution was converged with the ammonia, yellow soda ash and the water that replenish, circulation entered the absorber portion of bottom, absorption tower;
The weight percent of said mixture consists of:
Said sulfosalt comprises more than one in sodium sulfocynanate, thiocyanation ammonia, Sulfothiorine, ammonia thiosulfate, sodium sulfate, sulfate of ammoniac, S-WAT, sulfurous acid ammonia, sodium sulphite or the sodium sulphite etc.;
The sulphur foam by whizzer or under 60～70 ℃, is starched by the concentrated sulphur that becomes of concentration kettle, as system sulfuric acid raw material, the weight content 10～30% of sulphur wherein, the weight content 20～40% of sulfosalt, the weight content of water are 35～65%, separate the clear liquid that obtains, return desulfurization regeneration tower 1;
The volume ratio of regeneration air and desulfurization rich solution is:
2～3 mark rice
3Regeneration air/rise desulfurization rich solution;
Sulphur slurry by nozzle and after adopting the pressurized air atomizing, is sent in the roasting kiln, be fuel with coal gas, be that oxygenant burns with the air that sulphur and sulfosalt perfect combustion also are converted into the furnace gas that contains sulfurous gas;
Compressed-air actuated pressure is 0.4～0.7Mpa, and the particle diameter of the sulphur slurry atomizing particle of delivery nozzle is 50～500 μ m, and the roasting kiln furnace temperature is 1000～1300 ℃, and the sulphur slurry with compressed-air actuated volume ratio is:
0.1～0.2 kilogram of sulphur slurry/rice
3Pressurized air;
In the furnace gas that obtains, the volume content of sulfurous gas is 4～7%, and the volume content of oxygen is 4～7%, and the content of oxygen can be regulated by the feeding amount of air;
The furnace gas that will go out roasting kiln is cooled to 350～420 ℃, washes and further be cooled to 65～90 ℃ then with water;
Above-mentioned refrigerative furnace gas is sent into drying tower, is 95～98% sulfuric acid absorption with weight concentration, removes the moisture in the furnace gas, and the weight content that makes moisture in the furnace gas is 0.02～0.08%;
The vitriolic weight consumption is: 5000～ten thousand metres
3Refrigerative furnace gas/kilogram sulfuric acid;
The dried furnace gas that will go out drying tower is sent into by gas blower and is provided with the vanadium catalyst convertor, enters the furnace gas of convertor, in the presence of vanadium catalyst, is sulphur trioxide with Sulphur Dioxide;
Said vanadium catalyst is a prior art, catalyzer as 2007 " chemistry and biotechnology " " research of preparing sulfuric acid by oxidizing sulfur dioxide support of the catalyst and application " bibliographical information, can adopt commercially available product, as the catalyzer of Xiangfan Jingxin Catalyst Co., Ltd.'s production;
Invert point is 420～540 ℃;
To go out the furnace gas that contains sulphur trioxide after convertor transforms and send into the absorption tower, be that 95% sulfuric acid contact with weight concentration, and the absorption sulphur trioxide changes into weight concentration and be 94～98% product sulfuric acid.
Above-mentioned " mark rice
3" refer to: the volume under 1 normal atmosphere, 0 ℃ of condition.
The present invention also can adopt coal gas wet oxidation and desulfurization production to contain the more sulphur of impurity such as sulfosalt be raw material system sulfuric acid, wherein sulphur and sulfosalt weight content all can be used to make sulfuric acid at sulphur impure more than 40%.The desulfurization waste liquor of sulfur melting kettle also can be blended into the sulphur slurry as raw material system sulfuric acid, and desulfurization waste liquor and sulphur slurry are allocated into by 1: 1～5: 1 part by weight.
Unusual effect of the present invention is: 1, a tower desulfurization occupation of land is little, exhaust gas emission minimizing or zero release, and the desulfurization acid-making process is complete; 2, be raw material system sulfuric acid with coal gas wet oxidation method desulfurization sulphur slurry, no waste liquid effluxes, and the Sulphur Dioxide rate has thoroughly solved the influence that sulphur slurry and waste liquid bring environment more than 99.6%; 3, the present domestic coal gas desulfurization overwhelming majority adopts wet oxidation process, is raw material with coal gas wet-type desulfurization sulphur slurry, has very strong suitability and promotional value; 4, be raw material with coke-oven gas wet type desulfurizing sulphur slurry, can cancel in the existing coal gas wet-type desulfurizer facilities such as sulfur melting kettle, improve environment, improve coal gas desulfurization efficient; 5, form of nozzle is adopted in the roasting kiln charging, atomizes with pressurized air, and sulphur and sulfosalt can fully burn sulphur transformation efficiency height in the raw material, sulfuric acid yield height in desulfurization sulphur slurry and the waste liquid; 6, can produce impure more sulphur and desulfurization waste liquor is a raw material production sulfuric acid with existing coal gas wet-type desulfurizer, wherein sulphur and sulfosalt content all can be used to make sulfuric acid more than 40%, solve the outlet of coal gas desulfurization sulphur and waste liquid.
The economic benefit that the present invention produced is: be raw material with coal gas wet oxidation and desulfurization sulphur slurry 1,, 1 ton of sulphur slurry can be produced 1 ton of 94～98% sulfuric acid, and 2 tons of about 2.5～3Mpa steam have good economic benefit; 2, do not efflux owing to desulfurization sulphur slurry system sulfuric acid has waste liquid, environmental benefit is very remarkable; 3, can be raw material system sulfuric acid with existing coal gas desulfurization sulphur and waste liquid, wherein sulphur and sulfosalt content all can be used to make sulfuric acid more than 40%, improved the utility value of impure sulphur greatly, impure sulphur per ton is worth and can increases more than 50%, meets the energy-saving and environmental protection requirement.
Description of drawings
Fig. 1 is a schema of the present invention.
Fig. 2 is a desulfurization regeneration tower structure synoptic diagram.
Fig. 3 is the nozzle arrangements synoptic diagram.
Fig. 4 is the converter structure synoptic diagram.
Concrete embodiment
Referring to Fig. 1, method of the present invention comprises the steps:
With the absorber portion 101 of sulfur-containing coal gas,,, absorb hydrogen sulfide and prussic acid in the coal gas with the coal gas counter current contact with the absorber portion 101 of desulfurization lean solution from top feeding desulfurization regeneration tower 1 from bottom feeding desulfurization regeneration tower 1;
The structure of said desulfurization regeneration tower 1 such as Fig. 2, this desulfurization regeneration tower 1 comprises tower body, be arranged on the RS Regenerator Section 102 on tower body top and be arranged on the absorber portion 101 of RS Regenerator Section 102 bottoms, and said RS Regenerator Section 102 comprises: be arranged on Wen's injector 103 at RS Regenerator Section 102 tops, the sulphur foam separation baffle plate 104 that is arranged on RS Regenerator Section 102 tops, the sulphur that is arranged on sulphur foam separation baffle plate 104 tops and bubble out mouthfuls 105 and be arranged on the desulfurization lean solution outlet 106 of sulphur foam separation baffle plate 104 belows;
The desulfurization rich solution that has absorbed hydrogen sulfide and prussic acid is sent into the RS Regenerator Section 102 at desulfurization regeneration tower 1 top from absorber portion 101 bottoms of desulfurization regeneration tower 1 bottom, desulfurization rich solution and regeneration air are fed RS Regenerator Section 102 by Wen's injector 103, hydrogen sulfide in the desulfurization rich solution and prussic acid are oxidized to the sulphur foam, obtain desulfurization lean solution and sulphur foamy mixture, after the desulfurization lean solution is converged with the ammonia, yellow soda ash and the water that replenish, circulation enters the absorber portion 101 of desulfurization regeneration tower 1 bottom, purifies coal gas and discharges from the top of absorber portion 101;
The sulphur foam by whizzer 3 or under 60～70 ℃, is starched by the concentration kettle 4 concentrated sulphur that become, as system sulfuric acid raw material, the weight content 10～30% of sulphur wherein, the weight content 20～40% of sulfosalt, the weight content of water are 35～65%, separate the clear liquid that obtains, return desulfurization regeneration tower 1;
Preferably, will send into upgrading tower 5 and condensing still 6 successively by the sulphur slurry that whizzer 3 obtains, the sulphur slurry is concentrated the weight content 10～30% that becomes sulphur, the weight content 20～40% of sulfosalt, the weight content of water are 35～65% system sulfuric acid raw material.In upgrading tower 5 and condensing still 6, the concentrated of sulphur slurry realized by the partition heating.
Sulphur slurry by nozzle 701 and after adopting the pressurized air atomizing, is sent in the roasting kiln 7, be fuel with coal gas, be that oxygenant burns with the air that sulphur and sulfosalt perfect combustion also are converted into the furnace gas that contains sulfurous gas;
As shown in Figure 3, said nozzle comprises co-axial pipe core 20 and outer tube 30, and the sulphur slurry enters roasting kiln 7 by pipe core, and pressurized air enters roasting kiln 7 from outer tube 30;
The temperature that will go out roasting kiln 7 is that 1000～1300 ℃ furnace gas is cooled to 350～420 ℃, washes and further be cooled to 65～90 ℃ then with water;
Preferably, the temperature that will go out roasting kiln 7 is that 1000～1300 ℃ furnace gas passes through waste heat boiler 8, reclaims heat, and produces 2.5～3.0Mpa steam, and furnace gas is cooled to 350～420 ℃;
Preferably, the furnace gas that is cooled to 350～420 ℃ enters 9 washings of Wen's sluicing pipe, and furnace gas further is cooled to 70～95 ℃, enter again to clean tower 10, and dust and particle in the washing furnace gas, furnace gas is cooled to 65～90 ℃, adopts electrostatic precipitator 11 to remove acid mist then;
Above-mentioned refrigerative furnace gas is sent into drying tower 12, use sulfuric acid absorption, remove the moisture in the furnace gas;
The dried furnace gas that will go out drying tower 12 is sent into by gas blower 13 and is provided with the vanadium catalyst convertor, enters in the furnace gas of convertor, and in the presence of vanadium catalyst, be sulphur trioxide with Sulphur Dioxide;
To go out the furnace gas that contains sulphur trioxide after the conversion of convertor and send into the absorption tower, contact, absorb sulphur trioxide, change into product sulfuric acid with sulfuric acid;
Preferably, as Fig. 4, said convertor 14 comprises that eclipsed transforms one section 141 successively, transforms two section 142, transforms three section 143 and transform four section 144;
Said absorption tower comprises first absorption tower 151 and second absorption tower 152;
The dried furnace gas that goes out drying tower 12 is sent into successively by gas blower 13 and is provided with vanadium catalyst convertor 14 and transforms three section 143 and transform one section 141, cooling then, reduce temperature, enter first absorption tower 151 again, sulphur trioxide changes into the vitriol oil after adopting sulfuric acid absorption, the tail gas that contains sulfurous gas on a small quantity enters successively and transforms two section 142 and transform four section 144, enters second absorption tower 152 after changing into sulphur trioxide, uses sulfuric acid absorption.
SO in the tail gas
2Content≤300PPM, tail gas is up to standard after smoke stack emission.
Transform 420～460 ℃ of three sections inlet temperatures, transform 540～580 ℃ of three sections temperature outs;
Transform 420～460 ℃ of one section inlet temperatures, temperature out is 460～500 ℃;
Transform 420～450 ℃ of four sections inlet temperatures, transform 430～460 ℃ of four sections temperature outs.
Transform 420～450 ℃ of two sections inlet temperatures, temperature out is 420～440 ℃.
Adopt flow process, the desulfurization regeneration tower of Fig. 2, the nozzle of Fig. 3 and the convertor of Fig. 4 of Fig. 1.The basic technology condition is as follows:
The component of sulfur-containing coal gas and content:
Hydrogen sulfide 8g/m
3, prussic acid 2g/m
3, hydrogen 35g/m
3, carbon monoxide 5g/m
3, methane 30g/m
3, carbonic acid gas 1g/m
3
The component and the concentration of desulfurization lean solution are as follows:
Ammoniacal liquor contains ammonia 18 grams per liters, and the pH value is 9.5, and catalyzer is Resorcinol and phthalocyanine cobalt sulfonate organometallics, and the weight content of catalyzer is 5 grams per liters;
Absorption temperature is 40 ℃, and absorption pressure is 15Kpa;
The ratio of sulfur-containing coal gas and desulfurization lean solution is: 50 mark rice
3Sulfur-containing coal gas/rise desulfurization lean solution;
As Fig. 1, sulfur-containing coal gas is fed desulfurization regeneration tower 1 from the bottom, the desulfurization lean solution is fed desulfurization regeneration tower 1 from top, with the coal gas counter current contact, absorb hydrogen sulfide and prussic acid in the coal gas;
The desulfurization rich solution that has absorbed hydrogen sulfide and prussic acid is sent into the RS Regenerator Section 102 at desulfurization regeneration tower 1 top from absorber portion 101 bottoms of desulfurization regeneration tower 1 bottom, desulfurization rich solution and regeneration air are fed RS Regenerator Section 102 by Wen's injector 103, hydrogen sulfide in the desulfurization rich solution is oxidized to the sulphur foam, obtain desulfurization lean solution and sulphur foamy mixture, after the desulfurization lean solution was converged with the ammonia, yellow soda ash and the water that replenish, circulation entered the absorber portion 101 of desulfurization regeneration tower 1 bottom;
The ratio of desulfurization rich solution and regeneration air is:
3 mark rice
3Regeneration air/rise desulfurization rich solution;
Under 65 ℃, concentrating by concentration kettle 4 becomes the sulphur slurry with the sulphur foam, as system sulfuric acid raw material, and the weight content 30% of sulphur wherein, the weight content 35% of sulfosalt, the weight content of water are 35%, separate the clear liquid that obtains, and return desulfurization regeneration tower 1;
With sulphur slurry by nozzle and after adopting the pressurized air atomizing, send in the roasting kiln 7, be fuel with coal gas, be that oxygenant burns with the air, sulphur and sulfosalt perfect combustion also are converted into the furnace gas that contains sulfurous gas, the sulfurous gas volume content is 7% in the furnace gas, the feeding amount of control air, the volume content that makes the oxygen in the furnace gas is 7%;
Compressed-air actuated pressure is 0.7Mpa, and the median size of the sulphur slurry atomizing particle of delivery nozzle is 50 μ m, and the roasting kiln furnace temperature is 1300 ℃, and the envelope-bulk to weight ratio of pressurized air and sulphur slurry is:
5 meters
3Pressurized air/kilogram sulphur slurry;
The temperature that will go out roasting kiln 7 is that 1300 ℃ furnace gas passes through waste heat boiler 8, reclaims heat, and produces 3.0Mpa steam, and furnace gas is cooled to 420 ℃; The furnace gas that is cooled to 420 ℃ is entered 9 washings of Wen's sluicing pipe, and furnace gas further is cooled to 95 ℃, and enter again and clean tower 10, dust and particle in the washing furnace gas, furnace gas is cooled to 90 ℃, adopts electrostatic precipitator 11 to remove acid mist then;
Above-mentioned refrigerative furnace gas is sent into drying tower 12, is 95% sulfuric acid absorption with weight concentration, removes the moisture in the furnace gas, and the weight content that makes moisture in the furnace gas is 0.02%;
The dried furnace gas that goes out drying tower 12 is sent into three section 143 of the conversion that is provided with vanadium catalyst successively and is transformed one section 141 by gas blower 13, cooling then, reduce temperature, enter first absorption tower 151 again, the employing weight concentration is 98% sulfuric acid absorption, it is 98% product sulfuric acid that sulphur trioxide changes into weight concentration, the tail gas that contains sulfurous gas on a small quantity enters successively and transforms two section 142 and transform four section 144, after changing into sulphur trioxide, enter second absorption tower 152, with weight concentration is 98% sulfuric acid absorption, obtains weight concentration and be 98% product sulfuric acid.
SO in the tail gas
2Content≤300PPM, tail gas is up to standard after smoke stack emission.
Transform 460 ℃ of three sections inlet temperatures, transform 580 ℃ of three sections temperature outs;
Transform 460 ℃ of one section inlet temperatures, temperature out is 500 ℃;
Transform 450 ℃ of four sections inlet temperatures, transform 460 ℃ of four sections temperature outs.
Transform 450 ℃ of two sections inlet temperatures, temperature out is 440 ℃;
The catalyzer that said vanadium catalyst adopts Xiangfan Jingxin Catalyst Co., Ltd. to produce.
The Sulphur Dioxide rate is that 99.8%, 1 ton of sulphur slurry can be produced 1 ton of 98% sulfuric acid, 2 tons of 3Mpa steam.
Embodiment 2
Adopt flow process, the desulfurization regeneration tower of Fig. 2, the nozzle of Fig. 3 and the convertor of Fig. 4 of Fig. 1.The basic technology condition is as follows:
The component of sulfur-containing coal gas and content:
Hydrogen sulfide 1g/m
3, prussic acid 1g/m
3, hydrogen 60g/m
3, carbon monoxide 60g/m
3, methane 1g/m
3, carbonic acid gas 20g/m
3
The component and the concentration of desulfurization lean solution are as follows:
Yellow soda ash 0.5N, (equivalent concentration), pH value are 8.5, and catalyzer is 1, and 4-naphthoquinones-2-sodium sulfonate, the weight content of catalyzer are 3%;
Absorption temperature is 25 ℃, and absorption pressure is 10Kpa;
The ratio of sulfur-containing coal gas and desulfurization lean solution is: 40 mark rice
3Sulfur-containing coal gas/rise desulfurization lean solution;
As Fig. 1, sulfur-containing coal gas is fed desulfurization regeneration tower 1 from the bottom, the desulfurization lean solution is fed desulfurization regeneration tower 1 from top, with the coal gas counter current contact, absorb hydrogen sulfide and prussic acid in the coal gas;
The desulfurization rich solution that has absorbed hydrogen sulfide and prussic acid is sent into the RS Regenerator Section 102 at desulfurization regeneration tower 1 top from absorber portion 101 bottoms of desulfurization regeneration tower 1 bottom, desulfurization rich solution and regeneration air are fed RS Regenerator Section 102 by Wen's injector 103; Hydrogen sulfide in the desulfurization rich solution is oxidized to the sulphur foam, obtains desulfurization lean solution and sulphur foamy mixture, after the desulfurization lean solution was converged with the ammonia, yellow soda ash and the water that replenish, circulation entered the absorber portion 101 of desulfurization regeneration tower 1 bottom;
The ratio of desulfurization rich solution and regeneration air is:
2 mark rice
3Regeneration air/rise desulfurization rich solution;
The sulphur foam is concentrated by whizzer 3, send into upgrading tower 5 and condensing still 6 then successively, with the partition heating concentrated weight content 10% that become sulphur of sulphur slurry by steam, the weight content 25% of sulfosalt, the weight content of water is 65% system sulfuric acid raw material, separate the clear liquid that obtains, return desulfurization regeneration tower 1;
Sulphur slurry by nozzle and after adopting the pressurized air atomizing, is sent in the roasting kiln 7, be fuel with coal gas, be that oxygenant burns with the air that sulphur and sulfosalt perfect combustion also are converted into the furnace gas that contains sulfurous gas, the sulfurous gas volume content is 4% in the furnace gas; The volume content of oxygen is 6% in the control furnace gas;
Compressed-air actuated pressure is 0.4Mpa, and the median size of the sulphur slurry atomizing particle of delivery nozzle is 500 μ m, and the roasting kiln furnace temperature is 1000 ℃;
The envelope-bulk to weight ratio of pressurized air and sulphur slurry is:
10 meters
3Pressurized air/kilogram sulphur slurry;
The temperature that will go out roasting kiln 7 is that 1000 ℃ furnace gas passes through waste heat boiler 8, reclaims heat, and produces 2.5Mpa steam, and furnace gas is cooled to 350 ℃; The furnace gas that is cooled to 350 ℃ is entered 9 washings of Wen's sluicing pipe, and furnace gas further is cooled to 70 ℃, and enter again and clean tower 19, dust and particle in the washing furnace gas, furnace gas is cooled to 65 ℃, adopts electrostatic precipitator 11 to remove acid mist then;
Above-mentioned refrigerative furnace gas is sent into drying tower 12, is 95% sulfuric acid absorption with weight concentration, removes the moisture in the furnace gas, and the weight content that makes moisture in the furnace gas is 0.08%;
The dried furnace gas that goes out drying tower 12 is sent into successively by gas blower 13 and is provided with vanadium catalyst convertor 14 and transforms three section 143 and transform one section 141, cooling then, reduce temperature, enter first absorption tower 151 again, adopt weight concentration be after 95% the sulfuric acid absorption sulphur trioxide to change into weight concentration be 94% product sulfuric acid, the tail gas that contains sulfurous gas on a small quantity enters successively and transforms two section 142 and transform four section 144, cooling then, reduce temperature, enter second absorption tower 152 again, adopting concentration is 95% sulfuric acid absorption, and it is 94% product sulfuric acid that sulphur trioxide changes into concentration, obtains weight concentration and be 94% product sulfuric acid.
SO2 content≤300PPM in the tail gas, tail gas is up to standard after smoke stack emission.
Transform 420 ℃ of three sections inlet temperatures, transform 540 ℃ of three sections temperature outs;
Transform 420 ℃ of one section inlet temperatures, temperature out is 460 ℃;
Transform 420 ℃ of four sections inlet temperatures, transform 430 ℃ of four sections temperature outs.
Transform 420 ℃ of two sections inlet temperatures, temperature out is 420 ℃;
The catalyzer that said vanadium catalyst adopts Xiangfan Jingxin Catalyst Co., Ltd. to produce.
The Sulphur Dioxide rate is that 99.6%, 1 ton of sulphur slurry can be produced 1.04 ton of 94% sulfuric acid, 2 tons of 2.5Mpa steam.
Claims (5)
1. an acid preparation method by coal gas wet oxidation and desulfurization is characterized in that, comprises the steps:
With the absorber portion (101) of sulfur-containing coal gas, with the absorber portion (101) of desulfurization lean solution, with the coal gas counter current contact from top feeding desulfurization regeneration tower (1) from bottom feeding desulfurization regeneration tower (1);
The desulfurization rich solution that has absorbed hydrogen sulfide and prussic acid is sent into the RS Regenerator Section (102) at desulfurization regeneration tower (1) top from absorber portion (101) bottom of desulfurization regeneration tower (1) bottom, simultaneously, regeneration air is fed RS Regenerator Section (102), obtain desulfurization lean solution and sulphur foamy mixture, after the desulfurization lean solution was converged with the ammonia, yellow soda ash and the water that replenish, circulation entered the absorber portion (101) of bottom, absorption tower;
With the concentrated sulphur slurry that becomes of sulphur foam, isolating clear liquid returns desulfurization regeneration tower (1);
The sulphur slurry by nozzle and after adopting the pressurized air atomizing, is sent into roasting kiln (7) internal combustion;
The furnace gas that will go out roasting kiln (7) is cooled to 350～420 ℃, washes and further be cooled to 65～90 ℃ then with water;
Above-mentioned refrigerative furnace gas is sent into drying tower (12), remove moisture;
The dried furnace gas that will go out drying tower (12) is sent into and is provided with vanadium catalyst convertor (14), in the presence of vanadium catalyst, is sulphur trioxide with Sulphur Dioxide;
Said convertor (14) is provided with and transforms one section (141), transforms two sections (142), transforms three sections (143) and transforms four sections (144), and said absorption tower (15) comprise first absorption tower (151) and second absorption tower (152);
The dried furnace gas that goes out drying tower (12) is sent into the conversion three sections (603) that is provided with vanadium catalyst convertor (14) successively and is transformed one section (601) by gas blower (13), cooling then, enter first absorption tower (151) again, sulphur trioxide changes into the vitriol oil after adopting sulfuric acid absorption, the tail gas that contains sulfurous gas enters and transforms two sections (142) more successively and transforms four sections (144), enter second absorption tower (152) after changing into sulphur trioxide, with weight concentration is that 95% sulfuric acid contacts, absorb sulphur trioxide, change into weight concentration and be 94～98% product sulfuric acid;
Transform 420～460 ℃ of one section inlet temperatures, temperature out is 460～500 ℃; Transform 420～450 ℃ of two sections inlet temperatures, temperature out is 420～440 ℃; Transform 420～460 ℃ of three sections inlet temperatures, transform 540～580 ℃ of three sections temperature outs; Transform 420～450 ℃ of four sections inlet temperatures, transform 430～460 ℃ of four sections temperature outs.
2. method according to claim 1 is characterized in that, the temperature that will go out roasting kiln (7) is that 1000～1300 ℃ furnace gas passes through waste heat boiler (8), reclaims heat, and produces 2.5～3.0MPa steam.
3. method according to claim 2 is characterized in that, furnace gas is entered Wen's sluicing pipe (9) washing, furnace gas is cooled to 70～95 ℃, enters clean tower again, dust and particle in the washing furnace gas, furnace gas is cooled to 65～90 ℃, adopts electrostatic precipitator to remove acid mist then.
4. method according to claim 1, it is characterized in that, said desulfurization lean solution is that weight content is that ammoniacal liquor or the equivalent concentration that contains ammonia 7 grams per liters～18 grams per liters is the aqueous sodium carbonate of 0.4～0.6N, the pH value is 8.5～9.5, and containing catalyzer, said catalyzer is Resorcinol and phthalocyanine cobalt sulfonate organometallics or 1,4-naphthoquinones-2-sodium sulfonate, in the desulfurization lean solution, the weight content of catalyzer is 3～5 grams per liters.
5. according to each described method of claim 1～4, it is characterized in that in the said sulfur-containing coal gas, each components contents is as follows:
Hydrogen sulfide 1～8g/m
3, prussic acid 1～2g/m
3, hydrogen 35～60g/m
3, carbon monoxide 5～60g/m
3, methane 1～30g/m
3, carbonic acid gas 1～20g/m
3
Absorption temperature is 25～40 ℃, and absorption pressure is 10～15KPa;
The ratio of sulfur-containing coal gas and desulfurization lean solution is:
40～50 mark rice
3Sulfur-containing coal gas/rise desulfurization lean solution;
The ratio of desulfurization rich solution and regeneration air is:
2～3 mark rice
3Regeneration air/rise desulfurization rich solution;
The roasting kiln furnace temperature is 1000～1300 ℃;
The sulphur slurry with compressed-air actuated volume ratio is:
0.1～0.2 kilogram of sulphur slurry/rice
3Pressurized air;
Above-mentioned " mark rice
3" refer to: the volume under 1 normal atmosphere, 0 ℃ of condition.
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Cited By (1)
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| CN106430116A (en) * | 2016-08-24 | 2017-02-22 | 金能科技股份有限公司 | Method for preparing sulfuric acid by utilizing sulfur-containing waste liquid generated during gas wet type oxidation process |
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| CN101966984A (en) * | 2010-11-12 | 2011-02-09 | 姜辉 | Method for producing sulfuric acid by utilizing sulfur foam generated by ferric oxide powder suspension desulfurization |
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