CN103405998A - Equipment and method for preparing sulfuric acid - Google Patents
Equipment and method for preparing sulfuric acid Download PDFInfo
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- CN103405998A CN103405998A CN2013103229018A CN201310322901A CN103405998A CN 103405998 A CN103405998 A CN 103405998A CN 2013103229018 A CN2013103229018 A CN 2013103229018A CN 201310322901 A CN201310322901 A CN 201310322901A CN 103405998 A CN103405998 A CN 103405998A
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Abstract
The invention provides equipment and a method for preparing sulfuric acid. The equipment comprises a high-concentration flue gas supply device, a sulfur dioxide transformation device, a sulfur trioxide absorbing device, an absorbing device, a desorbing device and a sulfur dioxide liquefying device, connected in sequence, wherein a sulfur dioxide absorbing agent is arranged in the absorbing device to absorb sulfur dioxide in high-concentration flue gas; the desorbing device is used for releasing sulfur dioxide through rising the temperature; the sulfur dioxide transformation device is used for transforming sulfur dioxide into sulfur trioxide; the sulfur trioxide absorbing device is used for absorbing sulfur trioxide with sulfuric acid to obtain sulfuric acid and acid making exhaust gas containing sulfur dioxide; the sulfur dioxide liquefying device is used for liquefying gaseous sulfur dioxide. The flue gas purification equipment can provide sulfur dioxide enriched or recovered from flue gas, and finally obtain sulfuric acid or liquid sulfur dioxide.
Description
Technical field
The present invention relates to chemical field, particularly, the present invention relates to a kind of equipment for the preparation of sulfuric acid and sulfuric acid preparation method.
Background technology
Flue gas is the mixture of gas and flue dust, is the main cause of polluting the residential block atmosphere.The composition of flue gas is very complicated, and gas comprises sulfur dioxide, carbon monoxide, carbon dioxide etc.Flue gas is the combined pollution of multiple poisonous substance to the pollution of environment.Can be that sulfur trioxide carries out preparing sulfuric acid by sulfuric acid absorption by the Sulphur Dioxide in flue gas.Yet, due to the sulfur dioxide concentration in flue gas lower (fluctuating larger), thereby can't meet the needs that contact method prepares sulfuric acid.
Thereby the current means for the preparation of sulfuric acid still remain to be improved.
Summary of the invention
The present invention is intended to solve at least one of above-mentioned defect in prior art.
One aspect of the invention is to provide a kind of equipment for the preparation of sulfuric acid, utilizes this equipment the flue gas that contains sulfur dioxide can be prepared to sulfuric acid.
For this reason, the invention provides a kind of equipment for the preparation of sulfuric acid, it comprises: high-concentration fume feedway, Sulphur Dioxide device, described Sulphur Dioxide device is connected with described high-concentration fume feedway, for by Sulphur Dioxide, being sulfur trioxide; The sulfur trioxide absorption plant, described sulfur trioxide absorption plant is connected with described Sulphur Dioxide device, for the relieving haperacidity tail gas that obtains sulfuric acid and contain sulfur dioxide by the sulfuric acid absorption sulfur trioxide; Absorption plant, be provided with the sulfur dioxide absorbent for absorbing the sulfur dioxide to described relieving haperacidity tail gas in described absorption plant; Desorption apparatus, described desorption apparatus is connected with described absorption plant, for the sulfur dioxide to absorbing, regenerates, in order to obtain high concentration sulfur dioxide; The sulfur dioxide liquefaction device, described sulfur dioxide liquefaction device is connected with described desorption apparatus, for described high concentration sulfur dioxide gas is liquefied, in order to obtain sulfur dioxide liquid.Thus, utilize this equipment effectively from the flue gas that contains sulfur dioxide, to prepare sulfuric acid.
In addition, the equipment for preparing sulfuric acid according to the above embodiment of the present invention can also have following additional technical feature:
According to embodiments of the invention, in described high-concentration fume, the content of sulfur dioxide is 3%-11%.
According to embodiments of the invention, the above-mentioned equipment for preparing sulfuric acid further comprises the low-concentration flue gas feedway, described low-concentration flue gas feedway is connected with described absorption plant, and to described absorption plant, supply with low-concentration flue gas, in order in described absorption plant, described low-concentration flue gas is carried out to the desulfurization processing.
According to embodiments of the invention, in described low-concentration flue gas, the content of sulfur dioxide is lower than 1%.
According to embodiments of the invention, the above-mentioned equipment for preparing sulfuric acid further comprises: dedusting and purifying device, described dedusting and purifying device is connected with described Sulphur Dioxide device, for described high-concentration fume was carried out to the purifying and dedusting processing before input Sulphur Dioxide device.
According to embodiments of the invention, described sulfur dioxide liquefaction device be selected from being connected by valve one of at least of described high-concentration fume feedway, described Sulphur Dioxide device and described dedusting and purifying device.
According to embodiments of the invention, the above-mentioned equipment for preparing sulfuric acid further comprises the sulfur dioxide concentration supervising device, being connected one of at least of described sulfur dioxide concentration supervising device and described sulfur dioxide liquefaction device, described high-concentration fume feedway, described Sulphur Dioxide device and described dedusting and purifying device.
According to embodiments of the invention, the above-mentioned equipment for preparing sulfuric acid further comprises valve control device, described valve control device is connected with described sulfur dioxide concentration supervising device with described valve respectively, for the monitored results based on described sulfur dioxide concentration supervising device, described valve is controlled.
According to embodiments of the invention, described sulfur dioxide absorbent is the Diamines absorbent.
According to embodiments of the invention, described sulfur dioxide absorbent is hexamethylene diamine.
In still another aspect of the invention, the present invention proposes a kind of method for preparing sulfuric acid from flue gas, it comprises:
Sulfur dioxide in high-concentration fume is carried out to conversion processing, in order to obtain sulfur trioxide; And utilize sulfuric acid to absorb processing to the sulfur trioxide obtained, in order to obtain sulfuric acid and relieving haperacidity tail gas; Utilize the sulfur dioxide absorbent to absorb described relieving haperacidity tail gas, in order to be absorbed product; Described absorption product is carried out to desorb, in order to obtain the high concentration sulfur dioxide gas; Described high concentration sulfur dioxide gas is liquefied, in order to obtain sulfur dioxide liquid.Thus, utilize the method, can effectively from flue gas, prepare sulfuric acid.
According to embodiments of the invention, above-mentioned method for the preparation of sulfuric acid can also have following additional technical feature:
According to embodiments of the invention, in described high-concentration fume, the content of sulfur dioxide is 3%-11%.
According to embodiments of the invention, before described relieving haperacidity tail gas is absorbed, described relieving haperacidity tail gas is mixed with low-concentration flue gas.
According to embodiments of the invention, in described low-concentration flue gas, content of sulfur dioxide is lower than 1%.
According to embodiments of the invention, before described high-concentration fume is carried out to conversion processing, described high-concentration fume is carried out to the udst separation processing, and will carry out described conversion processing through the flue gas that udst separation is processed.
According to embodiments of the invention, before the described flue gas of processing through udst separation was carried out to described conversion processing, the flue gas that described udst separation is processed mixed with described high concentration sulfur dioxide.
According to embodiments of the invention, described flue gas through the udst separation processing and the sulfur dioxide concentration in high concentration sulfur dioxide are monitored, in order to control the startup that the flue gas of described udst separation processing is mixed with described high concentration sulfur dioxide and close.
According to embodiments of the invention, described sulfur dioxide absorbent is the Diamines absorbent.According to embodiments of the invention, described sulfur dioxide absorbent is hexamethylene diamine.Can further improve absorption rate of sulfur dioxide thus.
According to the equipment for preparing sulfuric acid of the embodiment of the present invention, can realize that following advantages is one of at least:
1, can be from flue gas, reclaiming and enrichment sulfur dioxide;
2, the sulfur dioxide concentration obtained meets the requirement that industry prepares sulfuric acid;
3, can obtain continuous high concentration sulfur dioxide;
4, can control the recovery of sulfur dioxide;
5, can recycle absorbent;
6, cost is low;
7, can prepare sulfuric acid from flue gas;
8, can obtain the sulfur dioxide liquid product.
The aspect that the present invention adds and advantage part in the following description provide, and part will become obviously from the following description, or recognize by practice of the present invention.
The accompanying drawing explanation
Above-mentioned and/or the additional aspect of the present invention and advantage will become from the following description of the accompanying drawings of embodiments and obviously and easily understand, wherein:
Fig. 1 is for preparing according to an embodiment of the invention the structural representation of the equipment of sulfuric acid.
Fig. 2 is for preparing according to an embodiment of the invention the structural representation of the equipment of sulfuric acid.
Fig. 3 is for preparing according to an embodiment of the invention the process chart of sulfuric acid.
Fig. 4 is for preparing according to an embodiment of the invention the process chart of sulfuric acid.
The specific embodiment
Below describe embodiments of the invention in detail, the example of described embodiment is shown in the drawings, and wherein same or similar label means same or similar element or the element with identical or similar functions from start to finish.Below by the embodiment be described with reference to the drawings, be exemplary, only be used to explaining the present invention, and can not be interpreted as limitation of the present invention.In addition, the position of shown element and size are also exemplary in the accompanying drawings, can not be interpreted as limitation of the present invention.
Disclosing hereinafter provides many different embodiment or example to be used for realizing different structure of the present invention.Of the present invention open in order to simplify, hereinafter parts and the setting of specific examples are described.Certainly, they are only example, and purpose does not lie in restriction the present invention.In addition, the present invention can be in different examples repeat reference numerals and/or letter.This repetition is in order to simplify and purpose clearly, itself do not indicate the relation between the various embodiment of discuss and/or setting.In addition, the various specific technique the invention provides and the example of material, but those of ordinary skills can recognize the property of can be applicable to of other techniques and/or the use of other materials.In addition, First Characteristic described below Second Characteristic it " on " structure can comprise that the first and second Characteristics creations are the direct embodiment of contact, also can comprise the embodiment of other Characteristics creation between the first and second features, such the first and second features may not be direct contacts.
With reference to Fig. 1-2, the present invention mainly is to provide a kind of equipment for preparing sulfuric acid.According to embodiments of the invention, along technological process direction (being the indicated direction of arrow in Fig. 1), this equipment comprises high-concentration fume feedway 100, Sulphur Dioxide device 200 and sulfur trioxide absorption equipment 300, absorption plant 400, desorption apparatus 500 and sulfur dioxide liquefaction device 600 successively.
High-concentration fume feedway 100 is for supplying with the flue gas of high concentration to the Sulphur Dioxide device, according to a particular embodiment of the invention, the concentration of the sulfur dioxide in flue gas of high concentration also is not particularly limited, according to concrete example of the present invention, the content of sulfur dioxide can, higher than 3%, can significantly improve relieving haperacidity stability thus.
What adopt in the present invention is one to turn a suction-contact method and prepare sulfuric acid.Concrete, according to embodiments of the invention, the sulfuric acid preparation system comprises Sulphur Dioxide device 200 and sulfur trioxide absorption plant 300 with reference to figure 1.Wherein, Sulphur Dioxide device 200 is for being sulfur trioxide by Sulphur Dioxide, described Sulphur Dioxide device 200 is provided with reforming unit sulfur dioxide charging aperture 201 and reforming unit sulfur trioxide discharging opening 202, reforming unit sulfur dioxide charging aperture 201 is connected with high-concentration fume feedway 100 fluids, for from high-concentration fume feedway 100, receiving sulfur dioxide.The method that is sulfur trioxide by Sulphur Dioxide is not particularly limited, and can be undertaken by catalytic oxidation.For example adopt catalyst such as vanadic anhydride, sulfur dioxide is contacted with oxygen, thereby be sulfur trioxide by oxidizing sulfur dioxide, and discharge from sulfur trioxide discharging opening 202, enter sulfur trioxide absorption plant 300.Sulfur trioxide absorption plant 300 obtains sulfuric acid be used to absorbing sulfur trioxide, wherein sulfur trioxide absorption plant 300 is provided with sulfur trioxide charging aperture 301, this sulfur trioxide charging aperture 301 is connected with reforming unit sulfur trioxide discharging opening 202 fluids, for from Sulphur Dioxide device 200, receiving sulfur trioxide.Thus, utilize flue gas purifying equipment of the present invention, can be by the sulfur dioxide removal in flue gas for the preparation of sulfuric acid, thereby greatly reduce the discharge capacity of sulfur dioxide, especially the policy that meets the current national saving energy, lowering energy consumption and reducing pollutants discharge, enterprise discontinuous for producing, fluctuate large or low concentration sulphur dioxide flue gas solves the difficult problem of environmental protection provides good approach.
According to one embodiment of present invention, flue gas carries out high-concentration fume after a series of processing become sulfur trioxide by the Sulphur Dioxide in flue gas to be prepared into sulfuric acid through above-mentioned acid-producing apparatus.According to a particular embodiment of the invention, above-mentioned high-concentration fume after treatment also can more remaining relieving haperacidity tail gas, also contain a small amount of sulfur dioxide in this relieving haperacidity tail gas.Therefore according to a particular embodiment of the invention, this equipment for preparing sulfuric acid also further comprises absorption plant 400, desorption apparatus 500 and sulfur dioxide liquefaction device 600, the charging aperture 401 of absorption plant 400 is connected with the tail gas outlet 302 of sulfur trioxide absorption plant 300, for receiving the relieving haperacidity tail gas of discharging from sulfur trioxide absorption plant 300.In absorption plant 400, be provided with sulfur dioxide absorbent (for illustrating) for absorbing the sulfur dioxide of relieving haperacidity tail gas; The charging aperture 501 of desorption apparatus 500 is connected with the outlet 402 of absorption plant 400, for the sulfur dioxide to absorbing, regenerates, in order to obtain the sulfur dioxide of high concentration; The charging aperture 601 of sulfur dioxide liquefaction device 600 is connected with the discharging opening 502 of desorption apparatus 500, for receiving the high concentration sulfur dioxide gas of discharging from desorption apparatus 500, and the sulfur dioxide gas of high concentration is converted into to sulfur dioxide liquid.According to a particular embodiment of the invention, sulfur dioxide liquid in sulfur dioxide liquefaction device 600 both can be used as product and had directly utilized, also it can be back to acid making system, for the large high-concentration fume that fluctuates is carried out to tonifying Qi, thus the continuity that helps sulfuric acid to prepare.
In the said equipment, utilize the absorbent in absorption plant 400 to absorb the sulfur dioxide comprised in relieving haperacidity tail gas, thereby reached the purpose of enrichment sulfur dioxide, obtain the absorbent of sulfur dioxide absorption.Here the term used " absorbent " refers to can be from catching the preparation of sulfur dioxide flue gas, can be both the physical property (for example the solubility of sulfur dioxide in absorbent is higher) of utilizing sulfur dioxide, can be also the chemical property (for example sulfur dioxide can react with absorbent) of utilizing sulfur dioxide.In one embodiment of the invention, use the Diamines absorbent.In concrete example of the present invention, described diamines is selected from ethylenediamine and hexamethylene diamine, and it has, and uptake is large, stability, high specific and legibility absorption.It will be appreciated by those skilled in the art that described absorbent can be single compound, can be also the combination of two kinds or more compounds.Use in some embodiments of the invention absorbent for example methyl diethanolamine and the 2-methyl-2-amino-1-propyl alcohol be different from diamines.Utilize the chemical reaction of sulfur dioxide and compound, sulfur dioxide absorption specifically, and be convenient to desorb in follow-up desorption apparatus 300 and reclaim sulfur dioxide, realize enrichment and reclaim sulfur dioxide thereby improve, and improve purity and the concentration of resulting sulfur dioxide.
In addition, broad understanding should be made in the term " flue gas " used in the present invention, can be need to can be gaseous state from the material of the arbitrary form that wherein reclaims sulfur dioxide arbitrarily, liquid, or even solid-state.For example, can be the waste gas that contains sulfur dioxide produced in field of metallurgy, can be also the waste gas that contains sulfur dioxide that coal-burning power plant produces.Can enrichment sulfur dioxide according to the flue gas purifying equipment of the embodiment of the present invention, thereby it is low to be particularly suitable for sulfur dioxide concentration, be not suitable for and directly carry out flue gas prepared by sulfuric acid, nonferrous metallurgy flue gas for example, the flue gas that the sulfur dioxide concentration of thermal power plant and steel plant is low.In an embodiment of the present invention, the content of sulfur dioxide in flue gas is more than 3%, can reduce thus the flue gas fluctuation and further improve relieving haperacidity efficiency.
According to one embodiment of present invention, the above-mentioned equipment for preparing sulfuric acid can further include low-concentration flue gas feedway 120, this low-concentration flue gas feedway 120 is connected with the charging aperture 401 of absorption plant 400, and to absorption plant 400, supply with low-concentration flue gas, in order in absorption plant 400, low-concentration flue gas is carried out to the desulfurization processing.
According to a particular embodiment of the invention, the type of above-mentioned low-concentration flue gas is not subjected to special standby restriction, and according to concrete example of the present invention, the content that the flue gas of low concentration is specifically as follows sulfur dioxide is lower than 1% flue gas.Such flue gas is not suitable for directly preparing sulfuric acid, therefore can utilize above-mentioned double absorption equipment (absorption plant and desorption apparatus) to carry out the desulfurization processing to such flue gas and for the preparation of the relieving haperacidity tail gas of sulfuric acid, so that small part sulfur dioxide recovery that will be wherein.
Above-mentioned sulfur dioxide for recovery can be again for the preparation of sulfuric acid, for this reason, according to a particular embodiment of the invention, above-mentioned sulfur dioxide liquefaction device 600 be selected from being connected by valve one of at least of high-concentration fume feedway 100, Sulphur Dioxide device 200 and dedusting and purifying device 700.Thus can be by the high concentration sulfur dioxide of recovery for the preparation of sulfuric acid or sulfur dioxide liquid, simultaneously can utilize this part sulfur dioxide to regulate the sulfur dioxide concentration in the flue gas for the preparation of sulfuric acid, make it remain state more stably, reach simultaneously the requirement that contact method prepares sulfuric acid.Thereby, through the flue gas purifying equipment of the embodiment of the present invention, process, realize originally can not meeting large or sulfur dioxide flue gas low concentration of noncontinuity, fluctuation that contact method prepares the sulfuric acid requirement and become stable, as can to prepare continuously sulfuric acid flue gas.
In order to make the flue gas for preparing sulfuric acid maintain all the time certain sulfur dioxide concentration, in order to meet the requirement that contact method prepares sulfuric acid.According to one embodiment of present invention, the above-mentioned equipment for preparing sulfuric acid can further include sulfur dioxide concentration supervising device (not shown), being connected one of at least of this sulfur dioxide concentration supervising device and sulfur dioxide liquefaction device 600, high-concentration fume feedway 100, Sulphur Dioxide device 200 and dedusting and purifying device 700.In order to monitor the sulfur dioxide concentration in said apparatus.Simultaneously according to a particular embodiment of the invention, the above-mentioned equipment for preparing sulfuric acid can further include the valve control device (not shown), this valve control device is connected with the sulfur dioxide concentration supervising device with valve respectively, for the monitored results based on the sulfur dioxide concentration supervising device, above-mentioned valve is controlled.In order to close or open the valve between sulfur dioxide liquefaction device 600 and high-concentration fume feedway 100, Sulphur Dioxide device 200 or dedusting and purifying device 600, realize thus the sulfur dioxide of high concentration is mixed with the high-concentration fume for preparing sulfuric acid, regulate the concentration of the sulfur dioxide in high-concentration fume, it is met and stablize, prepare continuously sulfuric acid.Simultaneously the tail gas of above-mentioned relieving haperacidity is carried out to the desulfurization processing, not only can reclaim the purification that wherein sulfur dioxide has also been realized relieving haperacidity tail gas, make it meet the flue gas requirement that can discharge, avoid environmental pollution.
According to a particular embodiment of the invention, utilize above-mentioned absorption equipment (absorption plant and desorption apparatus) not only can realize recovery and the tail gas clean-up of relieving haperacidity sulfur dioxide in tail gas are processed, this equipment or a kind of buffer device, utilize it sulfur dioxide of the high concentration of recovery can be carried out to buffer memory simultaneously.According to a particular embodiment of the invention, utilize simultaneously the high concentration liquid sulfur dioxide that above-mentioned absorption equipment prepares directly as product, to use or to sell, can further improve thus the additional output value of acid preparation method.When sulfur dioxide concentration requires lower than relieving haperacidity, valve control device will be opened sulfur dioxide liquefaction device 600 and high-concentration fume concentration monitor device monitoring to the valve between high-concentration fume feedway 100, Sulphur Dioxide device 200 or dedusting and purifying device feedway 100, Sulphur Dioxide device 200 or dedusting and purifying device 700, and the high concentration thermal oxide sulphur of buffer memory in sulfur dioxide liquefaction device 600 is delivered in above-mentioned arbitrary device and is mixed for preparing sulfuric acid with the flue gas of high concentration.
Thus, the present invention also provides a kind of method for preparing sulfuric acid from flue gas.Below with reference to Fig. 3, the method from preparing sulfuric acid flue gas of the embodiment of the present invention is described in detail.The method specifically comprises: the sulfur dioxide in high-concentration fume is carried out to conversion processing, in order to obtain sulfur trioxide; And utilize sulfuric acid to absorb processing to sulfur trioxide, in order to obtain sulfuric acid and relieving haperacidity tail gas; Utilize the sulfur dioxide absorbent to absorb relieving haperacidity tail gas, in order to be absorbed product; Absorption product is carried out to desorb, in order to obtain high concentration sulfur dioxide.
Utilize said method can effectively prepare sulfuric acid, simultaneously in said method by the further desulfurization of relieving haperacidity tail gas after relieving haperacidity, and the high concentration sulfur dioxide of recovery is back to for relieving haperacidity, not only greatly reduce thus the discharge capacity of sulfur dioxide, make its relieving haperacidity tail gas meet the policy of current national saving energy, lowering energy consumption and reducing pollutants discharge.Enterprise discontinuous for producing, fluctuate large or low concentration sulphur dioxide flue gas solves the difficult problem of environmental protection simultaneously provides good approach.
In addition, the applicant finds that content of sulfur dioxide is higher than the 3.0%(percent by volume) namely can realize preparing sulfuric acid by contact method.Thereby, according to embodiments of the invention, before the Sulphur Dioxide by high concentration is sulfur trioxide, the sulfur dioxide of described high concentration is mixed with flue gas (can be undressed flue gas), obtain mixed flue gas, then mixed flue gas is converted into to sulfur trioxide, can greatly be reduced in thus the cost of the cost consumed in sulfur dioxide absorption-desorb, especially steam.In addition due to, can control by control system the amount of the absorbent that enters the sulfur dioxide absorption in sulfur dioxide desorption device 300 in the present invention, thereby the amount of the sulfur dioxide of the high concentration that can produce by control, and then regulate the concentration of mixed sulfur dioxide in flue gas.In a concrete example, in mixed flue gas, the content of sulfur dioxide reaches the 3.0%(percent by volume) more than.Thereby greatly reduce operating cost and project investment.Prepare the tail gas that contains sulfur dioxide of discharging after sulfuric acid and can again enter sulfur dioxide absorption-desorption apparatus and further reclaim sulfur dioxide, loop above-mentioned processing.After the sulfur dioxide concentration of tail gas is far below discharging standards, can directly discharge.
According to a particular embodiment of the invention, for the preparation of the concentration of sulfur dioxide in the high-concentration fume of sulfuric acid and be not particularly limited, be specifically as follows content of sulfur dioxide at 3～11% high-concentration fume.Can further improve the efficiency for preparing sulfuric acid thus.According to a particular embodiment of the invention, said method comprises relieving haperacidity tail gas is carried out to double absorption, can further improve thus the qualification rate of emission, simultaneously remaining a small amount of sulfur dioxide in relieving haperacidity tail gas is recycled.According to a particular embodiment of the invention, before relieving haperacidity tail gas is carried out to double absorption, relieving haperacidity tail gas can also be mixed with low-concentration flue gas.Can reclaim being unsuitable for being directly used in the sulfur dioxide contained in the low-concentration flue gas for preparing sulfuric acid thus, thereby the sulfur dioxide in these two parts is concentrated, can obtain thus the sulfur dioxide of high concentration.
According to a particular embodiment of the invention, the type of above-mentioned low-concentration flue gas also is not particularly limited, according to concrete example of the present invention, this low-concentration flue gas can be for content of sulfur dioxide lower than 1% flue gas, this flue gas is unsuitable for directly preparing sulfuric acid because sulfur dioxide concentration is low, utilize said method that the flue gas of above-mentioned low concentration is carried out not only can reaching discharge index after pretreatment, recovery sulfur dioxide wherein, for the preparation of sulfuric acid, is avoided the wasting of resources simultaneously.
According to one embodiment of present invention, before high-concentration fume is carried out to conversion processing, can also carry out the udst separation processing to high-concentration fume, and will carry out conversion processing through the flue gas that udst separation is processed.Can improve the purity of high-concentration fume thus, be convenient to follow-up relieving haperacidity operation.
According to a particular embodiment of the invention, can also utilize above-mentioned through absorbing the high concentration preparing sulfuric acid by using sulfur dioxide reclaimed, specifically can be before the flue gas of processing through udst separation carry out described conversion processing, the flue gas that udst separation is processed mixes with the high concentration sulfur dioxide of above-mentioned recovery.Can utilize thus the high concentration sulfur dioxide of this part to regulate the sulfur dioxide concentration in high-concentration fume, realize thus originally can not meeting large or sulfur dioxide flue gas low concentration of noncontinuity, fluctuation that contact method prepares the sulfuric acid requirement and become stable, as can to prepare continuously sulfuric acid flue gas.
According to one embodiment of present invention, can also monitor the flue gas through the udst separation processing and the sulfur dioxide concentration in high concentration sulfur dioxide, in order to control the startup that the flue gas of udst separation processing is mixed with high concentration sulfur dioxide and close.Be specifically as follows sulfur dioxide flue gas concentration in monitoring the flue gas of processing through udst separation when too low, high concentration sulfur dioxide is mixed with high-concentration fume, when the sulfur dioxide flue gas concentration in monitoring the flue gas of processing through udst separation can reach relieving haperacidity and requires, temporarily, by high concentration sulfur dioxide buffer memory, stop mixing with high-concentration fume.
According to one embodiment of present invention, above-mentionedly be used to absorbing the sulfur dioxide absorbent that low-concentration flue gas and relieving haperacidity sulfur dioxide in tail gas use, be the Diamines absorbent.In concrete example of the present invention, described diamines is for being selected from ethylenediamine and hexamethylene diamine, and it has, and uptake is large, stability, high specific and legibility absorption.It will be appreciated by those skilled in the art that this absorbent can be single compound, can be also the combination of two kinds or more compounds.Use in some embodiments of the invention absorbent for example methyl diethanolamine and the 2-methyl-2-amino-1-propyl alcohol be different from diamines.Utilize the chemical reaction of sulfur dioxide and compound, sulfur dioxide absorption specifically, and be convenient to desorb in follow-up desorption apparatus 300 and reclaim sulfur dioxide, realize enrichment and reclaim sulfur dioxide thereby improve, and improve purity and the concentration of resulting sulfur dioxide.
Contact method relieving haperacidity conversion process mainly is divided into double contact and singly turns single suction conversion acid-making process.The content of double contact system General Requirements sulfur dioxide is more than 6%, and the content of sulfur dioxide that singly turns single suction generally just can normally produced more than 3%, and requires all more stable operating modes of tolerance and sulfur dioxide concentration.
But for exhaust gas volumn and the king-sized situation of sulfur dioxide in flue gas concentration cyclic fluctuation of intermittent flue gas during smelting, and if adopted traditional acid-making process under this fluctuation operating mode system can't normally produce.For this problem, the present invention has provided a new acid-making process technology path, namely singly turns single suction relieving haperacidity technology and adds and can resolve desulfurizing agent and process intermittence and contain sulfur dioxide flue gas, produces sulfuric acid.
Singly turn the single suction acid making system and have stronger adaptability than double contact acid making system, can under lower sulfur dioxide concentration operating mode, normally produce sulfuric acid.Can resolve desulfurizing agent can be when removing sulfur dioxide in flue gas, by-product high-purity sulfur dioxide.This technology is utilized these characteristics that can resolve desulfurizing agent just, flue gas after relieving haperacidity can be resolved absorbent and be washed, the high-purity sulfur dioxide of desulfurization by-product fills into acid making system, makes to enter the sulfur dioxide in flue gas concentration stabilize of acid making system, has guaranteed that acid making system normally produces.Flue gas after relieving haperacidity simultaneously also can qualified discharge after desulfurization is processed.So singly turn single suction relieving haperacidity technology+can resolve desulfurizing agent technique to be more applicable for sulfur dioxide concentration and the large flue gas condition of exhaust gas volumn fluctuation.
Can resolve desulfurizing agent and be and take the aqueous solution that organic cation, inorganic anion form as a small amount of activator of main interpolation, antioxidant and corrosion inhibiter, this absorbent has good absorption and desorption ability to sulfur dioxide gas.And absorbent can be used by circular regeneration, and the high-purity sulfur dioxide that desorb is got off can return to acid making system relieving haperacidity, do not have byproduct to produce, can not cause secondary pollution.And realized recycling of sulphur resource.
According to one embodiment of present invention, after can resolving the sulfur dioxide in desulfurizing agent (sulfur dioxide absorbent) absorption flue gas, desulfurizing agent enters regenerator and is heated by steam to heat up and makes sulfur dioxide gas from desulfurizing agent, parsing, sulfur dioxide gas obtains highly purified sulfur dioxide gas after refrigerated separation, this gas is stored in the sulfur dioxide wet tank after liquefaction, after the evaporator evaporation of sulfur dioxide liquid by back, fill into when the SO 2 from fume concentration that enters acid making system is low.Be specially on acid making system drying tower inlet flue gas pipeline the sulfur dioxide concentration analyzer is set, this signal and evaporimeter recirculated water come the waterpipe movable valve that powers on chain, when entering the acid making system content of sulfur dioxide lower than 6.3% the time, electrically operated valve is opened the upper water of circulation and is opened the evaporator temperature rising, the sulfur dioxide liquid evaporation is sulfur dioxide gas, and on the evaporator outlet flue, valve is automatically opened sulfur dioxide gas and filled into acid making system.Higher than 6.3% the time, evaporimeter recirculated water comes the waterpipe movable valve that powers on to close, and is sulfur dioxide gas without the sulfur dioxide liquid evaporation, valve closing on the evaporator outlet flue when content of sulfur dioxide.Thereby guaranteed the normal production of acid making system.
According to one embodiment of present invention, minute two parts of the flue gas of the present invention by will contain sulfur dioxide are processed: relieving haperacidity and desulfurization.The sulfur dioxide flue gas of high concentration is for relieving haperacidity, and low-concentration flue gas can not relieving haperacidity need to adopt desulfurization to remove sulfur dioxide.The existing high-concentration fume of common pending flue gas also has low-concentration flue gas, and in high-concentration fume, the sulfur dioxide fluctuation is larger usually, can't meet relieving haperacidity.Therefore the present inventor has proposed new approaches: by the sulfur dioxide in low-concentration flue gas (comprising relieving haperacidity tail gas) by absorbing-resolve enrichment, the highly purified sulfur dioxide gas produced goes to make up the problem of sulfur dioxide fluctuation in high-concentration fume, thereby guarantee the sulfur dioxide in flue gas constant concentration that enters acid making system, solved because sulfur dioxide fluctuation in high-concentration fume can't meet a great problem of relieving haperacidity more greatly.
Embodiment
Below with reference to the shown in Figure 4 equipment for preparing sulfuric acid, be described the idiographic flow for preparing sulfuric acid.
1, as shown in table 1 for the preparation of the composition of the high concentration sulfur dioxide flue gas of sulfuric acid:
Table 1
SO as can be seen from Table 1
2The fluctuation range of concentration is larger, is specially the SO of oxidation period
2Content can reach 7.65%, and the SO of slagging period
2Content is minimum namely only has 0.03%.Oxidation period content is 7.65%, reduction period one SO
2Content 3.5% acid making system can normally be produced; Reduction periods two SO
2Content is 1.07%, slagging period SO
2Content 0.03%.Therefore, the relieving haperacidity conversion system can not autothermal equilibrium, needs by means such as concurrent heatings, conversion system is normally produced.
2, the low-concentration flue gas for the preparation of high concentration sulfur dioxide mainly comprises: the flue gas of discharging in the flue gas of the oxidation panel in above-mentioned high-concentration fume, relieving haperacidity tail gas and fuming furnace, specifically the content of each composition sees the following form.
Table 2 oxidation period (Nm
3/ h), 15h/d
| ? | SO 2 | SO 3 | O 2 | CO | CO 2 | N 2 | H 2O | Add up to |
| Oxidation panel | 402.00 | 0.00 | 460.00 | 0.00 | 408.00 | 3730.00 | 0.00 | 5000.00 |
| Relieving haperacidity tail gas | 95.00 | 1.00 | 1582.00 | 0.00 | 2420.00 | 22399.00 | 0.00 | 26497.00 |
| Fuming furnace | 24.00 | 0.00 | 2595.00 | 328.00 | 2942.00 | 23410.00 | 1931.00 | 31230.00 |
| Add up to | 521.00 | 1.00 | 4637.00 | 328.00 | 5770.00 | 49539.00 | 1931.00 | 62727.00 |
| % | 0.83 | ? | 7.39 | 0.52 | 9.20 | 78.98 | 3.08 | 100.00 |
Table 3 reduction period (Nm
3/ h), 6h/d
| ? | SO 2 | SO 3 | O 2 | CO | CO 2 | N 2 | H 2O | Add up to |
| The oxidation period | 314 | ? | 415 | ? | 615 | 3656 | ? | 5000 |
| Relieving haperacidity tail gas | 83 | 1 | 1752 | 0 | 4070 | 24191 | 0 | 30097 |
| Fuming furnace | 24.00 | 0.00 | 2595.00 | 328.00 | 2942.00 | 23410.00 | 1931.00 | 31230.00 |
| Add up to | 421 | 1 | 4762 | 328 | 7627 | 51257 | 1931 | 66327 |
| % | 0.63 | ? | 7.18 | 0.49 | 11.50 | 77.28 | 2.91 | 100.00 |
Table 4 slagging period (Nm
3/ h), 3h/d
| ? | SO 2 | SO 3 | O 2 | CO | CO 2 | N 2 | H 2O | Add up to |
| Relieving haperacidity tail gas | 8 | 0.5 | 249 | 0 | 245 | 2497 | 0 | 2999.5 |
| Fuming furnace | 24.00 | 0.00 | 2595.00 | 328.00 | 2942.00 | 23410.00 | 1931.00 | 31230.00 |
| Add up to | 32 | 0.5 | 2844 | 328 | 3187 | 25907 | 1931 | 34229.5 |
| % | 0.1 | ? | 8.31 | 0.96 | 9.316 | 75.69 | 5.64 | 100 |
The content of sulfur dioxide that day part enters the conversion system flue gas maintains more than 5%, guarantee the normal production of sulfate system, above flue gas is entered to desulphurization system, by absorption plant-desorption apparatus, prepare high-purity sulfur dioxide, this part high-purity sulfur dioxide is for making up the above-mentioned high-concentration fume SO for preparing sulfuric acid
2The fluctuation of concentration, this high-purity sulfur dioxide can also directly be used as product simultaneously, can further improve thus the additional output value of acid preparation method and equipment.
In the present embodiment, in the flue gas of above-mentioned low concentration, adopted the high concentration sulfur dioxide flue gas of the oxidation period of part, the flue gas content of this part can reach 7.65%, can effectively prepare thus high-purity sulfur dioxide be used to making up the fluctuation of concentration of high-concentration fume reduction period and slagging period.
By tonifying Qi sulfur dioxide in flue gas content range, be controlled at 5%～11%, fluctuation range significantly reduces, and tolerance is at 3300-35000Nm
3/ h.Adopt thus the method and apparatus for preparing sulfuric acid of the present invention can effectively keep carrying out sustainedly and stably of the interior reaction of acid making system, and then can significantly improve the efficiency for preparing sulfuric acid.In the present embodiment, can produce approximately 7.2 ten thousand t/a of sulfuric acid; The high-purity sulfur dioxide that low-concentration flue gas prepares by absorption plant-desorption apparatus, about 0.96 ten thousand t/a sulfur dioxide liquid product after this high-purity sulfur dioxide liquefaction.
In the description of this specification, the description of reference term " embodiment ", " some embodiment ", " illustrative examples ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or example in conjunction with specific features, structure, material or the characteristics of this embodiment or example description.In this manual, the schematic statement of above-mentioned term not necessarily referred to identical embodiment or example.And the specific features of description, structure, material or characteristics can be with suitable mode combinations in any one or more embodiment or example.
Although the above has illustrated and has described embodiments of the invention; be understandable that; above-described embodiment is exemplary; can not be interpreted as limitation of the present invention; those of ordinary skill in the art is not in the situation that break away from principle of the present invention and aim can change above-described embodiment within the scope of the invention, modification, replacement and modification, and these all drop on the scope of the present invention.
Claims (19)
1. the equipment for the preparation of sulfuric acid, is characterized in that, comprising:
The high-concentration fume feedway;
The Sulphur Dioxide device, described Sulphur Dioxide device is connected with the high-concentration fume feedway, is sulfur trioxide for the Sulphur Dioxide by high-concentration fume;
The sulfur trioxide absorption plant, described sulfur trioxide absorption plant is connected with described Sulphur Dioxide device, for the relieving haperacidity tail gas that obtains sulfuric acid and contain sulfur dioxide by the sulfuric acid absorption sulfur trioxide;
Absorption plant, be provided with the sulfur dioxide absorbent for absorbing the sulfur dioxide to described relieving haperacidity tail gas in described absorption plant;
Desorption apparatus, described desorption apparatus is connected with described absorption plant, for the sulfur dioxide to absorbing, regenerates, in order to obtain the high concentration sulfur dioxide gas; And
The sulfur dioxide liquefaction device, described sulfur dioxide liquefaction device is connected with described desorption apparatus, for described high concentration sulfur dioxide gas is liquefied, in order to obtain sulfur dioxide liquid.
2. equipment according to claim 1, is characterized in that, in described high-concentration fume, the content of sulfur dioxide is 3%-11%.
3. equipment according to claim 1, it is characterized in that, further comprise the low-concentration flue gas feedway, described low-concentration flue gas feedway is connected with described absorption plant, and to described absorption plant, supply with low-concentration flue gas, in order in described absorption plant, described low-concentration flue gas is carried out to the desulfurization processing.
4. equipment according to claim 3, is characterized in that, in described low-concentration flue gas, the content of sulfur dioxide is lower than 1%.
5. equipment according to claim 1, is characterized in that, further comprises:
Dedusting and purifying device, described dedusting and purifying device is connected with described Sulphur Dioxide device, for described high-concentration fume was carried out to the purifying and dedusting processing before input Sulphur Dioxide device.
6. equipment according to claim 5, is characterized in that, described sulfur dioxide liquefaction device be selected from being connected by valve one of at least of described high-concentration fume feedway, Sulphur Dioxide device and described dedusting and purifying device.
7. equipment according to claim 6, it is characterized in that, further comprise the sulfur dioxide concentration supervising device, being connected one of at least of described sulfur dioxide concentration supervising device and described sulfur dioxide liquefaction device, described high-concentration fume feedway, Sulphur Dioxide device and described dedusting and purifying device.
8. equipment according to claim 7, it is characterized in that, further comprise valve control device, described valve control device is connected with described sulfur dioxide concentration supervising device with described valve respectively, for the monitored results based on described sulfur dioxide concentration supervising device, described valve is controlled.
9. equipment according to claim 1, is characterized in that, described absorbent is the Diamines absorbent.
10. equipment according to claim 9, is characterized in that, described absorbent is hexamethylene diamine.
11. a method for preparing sulfuric acid, is characterized in that, comprising:
Sulfur dioxide in high-concentration fume is carried out to conversion processing, in order to obtain sulfur trioxide; And
Utilize sulfuric acid to absorb processing to described sulfur trioxide, in order to obtain sulfuric acid and relieving haperacidity tail gas;
Utilize the sulfur dioxide absorbent to absorb described relieving haperacidity tail gas, in order to be absorbed product;
Described absorption product is carried out to desorb, in order to obtain the high concentration sulfur dioxide gas;
Described high concentration sulfur dioxide gas is liquefied, in order to obtain sulfur dioxide liquid.
12. method according to claim 11, is characterized in that, in described high-concentration fume, the content of sulfur dioxide is 3%-11%.
13. method according to claim 11, is characterized in that, before described relieving haperacidity tail gas is absorbed, described relieving haperacidity tail gas mixed with low-concentration flue gas.
14. method according to claim 13, is characterized in that, in described low-concentration flue gas, content of sulfur dioxide is lower than 1%.
15. method according to claim 11, is characterized in that, before described conversion processing, described high-concentration fume carried out to the udst separation processing, and will carry out conversion processing through the flue gas that udst separation is processed.
16. method according to claim 11, is characterized in that, before by described conversion processing, the flue gas that described udst separation is processed mixes with described high concentration sulfur dioxide.
17. method according to claim 11, it is characterized in that, described flue gas through the udst separation processing and the sulfur dioxide concentration in high concentration sulfur dioxide are monitored, in order to control the startup that the flue gas of described udst separation processing is mixed with described high concentration sulfur dioxide and close.
18. method according to claim 11, is characterized in that, described sulfur dioxide absorbent is the Diamines absorbent.
19. method according to claim 18, is characterized in that, described sulfur dioxide absorbent is hexamethylene diamine.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103405997A (en) * | 2013-07-29 | 2013-11-27 | 中国恩菲工程技术有限公司 | Equipment for preparing sulfuric acid |
| CN105439104A (en) * | 2015-12-09 | 2016-03-30 | 中国瑞林工程技术有限公司 | Equipment for co-production of industrial sulphuric acid and liquid sulfur dooxode and method thereof |
| CN110935265A (en) * | 2019-12-25 | 2020-03-31 | 贵州圣济堂制药有限公司 | Harmless and pollution-free treatment system for pharmaceutical emissions |
| CN113082946A (en) * | 2021-04-08 | 2021-07-09 | 成都达奇环境科技有限公司 | Method for treating waste gas from non-ferrous metal smelting |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1268484A (en) * | 2000-04-06 | 2000-10-04 | 应燮堂 | Improvement of high-concentration sulfur dioxide three-conversion three-absorption acid-making process |
| JP2003517419A (en) * | 1999-11-01 | 2003-05-27 | フアルマシア・コーポレーシヨン | Method for producing sulfur trioxide, sulfuric acid and oleum from sulfur dioxide |
| CN102059039A (en) * | 2010-12-03 | 2011-05-18 | 中国瑞林工程技术有限公司 | Fume purification equipment and preparation method of sulfuric acid |
| CN103405997A (en) * | 2013-07-29 | 2013-11-27 | 中国恩菲工程技术有限公司 | Equipment for preparing sulfuric acid |
| CN203494364U (en) * | 2013-07-29 | 2014-03-26 | 中国恩菲工程技术有限公司 | Sulfuric acid preparing device |
-
2013
- 2013-07-29 CN CN2013103229018A patent/CN103405998A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003517419A (en) * | 1999-11-01 | 2003-05-27 | フアルマシア・コーポレーシヨン | Method for producing sulfur trioxide, sulfuric acid and oleum from sulfur dioxide |
| CN1268484A (en) * | 2000-04-06 | 2000-10-04 | 应燮堂 | Improvement of high-concentration sulfur dioxide three-conversion three-absorption acid-making process |
| CN102059039A (en) * | 2010-12-03 | 2011-05-18 | 中国瑞林工程技术有限公司 | Fume purification equipment and preparation method of sulfuric acid |
| CN103405997A (en) * | 2013-07-29 | 2013-11-27 | 中国恩菲工程技术有限公司 | Equipment for preparing sulfuric acid |
| CN203494364U (en) * | 2013-07-29 | 2014-03-26 | 中国恩菲工程技术有限公司 | Sulfuric acid preparing device |
Non-Patent Citations (1)
| Title |
|---|
| 郑永铭等: "《硫酸与硝酸》", 30 April 1998 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103405997A (en) * | 2013-07-29 | 2013-11-27 | 中国恩菲工程技术有限公司 | Equipment for preparing sulfuric acid |
| CN105439104A (en) * | 2015-12-09 | 2016-03-30 | 中国瑞林工程技术有限公司 | Equipment for co-production of industrial sulphuric acid and liquid sulfur dooxode and method thereof |
| CN110935265A (en) * | 2019-12-25 | 2020-03-31 | 贵州圣济堂制药有限公司 | Harmless and pollution-free treatment system for pharmaceutical emissions |
| CN113082946A (en) * | 2021-04-08 | 2021-07-09 | 成都达奇环境科技有限公司 | Method for treating waste gas from non-ferrous metal smelting |
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