CN114367173A - Liquid sponge desulfurizer - Google Patents
Liquid sponge desulfurizer Download PDFInfo
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- CN114367173A CN114367173A CN202011105092.1A CN202011105092A CN114367173A CN 114367173 A CN114367173 A CN 114367173A CN 202011105092 A CN202011105092 A CN 202011105092A CN 114367173 A CN114367173 A CN 114367173A
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- liquid sponge
- desulfurizer
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- 239000007788 liquid Substances 0.000 title claims abstract description 95
- 125000005113 hydroxyalkoxy group Chemical group 0.000 claims abstract description 23
- 239000004480 active ingredient Substances 0.000 claims abstract description 22
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 21
- 125000004464 hydroxyphenyl group Chemical group 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 4
- 238000005260 corrosion Methods 0.000 claims description 26
- 230000007797 corrosion Effects 0.000 claims description 26
- 239000003112 inhibitor Substances 0.000 claims description 25
- 230000003009 desulfurizing effect Effects 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- -1 hydroxypropyl Chemical group 0.000 claims description 16
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 10
- SRUQIHYBCMXLBN-UHFFFAOYSA-N 2-piperazin-1-ylethane-1,1-diol Chemical compound OC(O)CN1CCNCC1 SRUQIHYBCMXLBN-UHFFFAOYSA-N 0.000 claims description 6
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 claims description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 6
- 229960002887 deanol Drugs 0.000 claims description 6
- 239000012972 dimethylethanolamine Substances 0.000 claims description 6
- GPEOAEVZTOQXLG-UHFFFAOYSA-N 4-piperazin-1-ium-1-ylphenolate Chemical compound C1=CC(O)=CC=C1N1CCNCC1 GPEOAEVZTOQXLG-UHFFFAOYSA-N 0.000 claims description 5
- SHSJRWFDPXXVIG-UHFFFAOYSA-N 1-(4-phenylpiperazin-1-yl)propan-1-ol Chemical compound C1CN(C(O)CC)CCN1C1=CC=CC=C1 SHSJRWFDPXXVIG-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 3
- LWEOFVINMVZGAS-UHFFFAOYSA-N 3-piperazin-1-ylpropan-1-ol Chemical compound OCCCN1CCNCC1 LWEOFVINMVZGAS-UHFFFAOYSA-N 0.000 claims description 3
- VXZSWRSWKVGLJG-UHFFFAOYSA-N 3-piperazin-1-ylpropane-1,1-diol Chemical compound OC(O)CCN1CCNCC1 VXZSWRSWKVGLJG-UHFFFAOYSA-N 0.000 claims description 3
- SASIFHOHGBPKMK-UHFFFAOYSA-N 4-piperazin-2-ylphenol Chemical compound C1=CC(O)=CC=C1C1NCCNC1 SASIFHOHGBPKMK-UHFFFAOYSA-N 0.000 claims description 3
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 claims description 3
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 106
- 238000003795 desorption Methods 0.000 abstract description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052717 sulfur Inorganic materials 0.000 abstract description 30
- 239000011593 sulfur Substances 0.000 abstract description 30
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 26
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 23
- 238000006477 desulfuration reaction Methods 0.000 abstract description 14
- 230000023556 desulfurization Effects 0.000 abstract description 14
- 239000007789 gas Substances 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 235000010269 sulphur dioxide Nutrition 0.000 description 52
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 50
- 239000003546 flue gas Substances 0.000 description 50
- 238000010521 absorption reaction Methods 0.000 description 27
- 239000000243 solution Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 238000004064 recycling Methods 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000007853 buffer solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000004291 sulphur dioxide Substances 0.000 description 2
- KDKGWGUUUVROTO-UHFFFAOYSA-N 1-hydroxypiperazine Chemical compound ON1CCNCC1 KDKGWGUUUVROTO-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1468—Removing hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
- B01D53/1481—Removing sulfur dioxide or sulfur trioxide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
The invention provides a liquid sponge desulfurizer. The liquid sponge desulfurizer comprises active ingredients, wherein the active ingredients comprise one or more compounds shown in the following general formula I: rn(NH)mIn the general formula I, R represents alkylene, n is an integer of 1-20, optionally, hydrogen atoms in each R group and each-NH-are independently substituted by hydroxyalkyl, hydroxyalkoxy, hydroxyphenyl or phenyl, and at least one hydrogen atom in n R groups and m-NH-is substituted by hydroxyalkyl, hydroxyalkoxy or hydroxyphenyl; m is an integer of 1 to 6. The liquid sponge desulfurizer provided by the invention has good stability, high selectivity to sulfur dioxide and hydrogen sulfide, low desorption energy consumption and high desulfurization efficiency, and can realize valuable resource utilization of sulfur while meeting the standard emission of sulfur-containing tail gas.
Description
Technical Field
The invention relates to the technical field of flue gas desulfurization, and particularly relates to a liquid sponge desulfurizer.
Background
In the industrial field, there are many substances containing sulfur, such as coal, ore, petroleum, natural gas, etc., and the existence state of sulfur in them is diversified, such as the sulfur can exist in oxidation state, reduction state, elemental sulfur, etc. During processing (combustion, smelting, processing, etc.) of these sulfur-containing materials, the sulfur content may appear in various forms in various parts of the production process or in the tail gas thereof, with the most significant emissions being in the form of gaseous sulfur dioxide and hydrogen sulfide in the tail gas.
Since hydrogen sulfide is a toxic gas, the country has very strict requirements on the emission concentration of hydrogen sulfide. The sulfur dioxide is an important driver of atmospheric pollution, and the emission of the sulfur dioxide is more and more strict along with the increasing strictness of the national standards on environmental protection. Therefore, the emission of sulfur-containing tail gas must meet the national environmental emission standards.
In addition, sulfur dioxide and hydrogen sulfide in the flue gas are pollutants, but are also resources, and if the sulfur can be recycled and recycled in the desulfurization treatment process, the method has great significance for environmental protection and sustainable utilization of resources.
Disclosure of Invention
The invention mainly aims to provide a liquid sponge desulfurizer, which can realize effective desulfurization of flue gas and sulfur recovery.
In order to achieve the above object, according to one aspect of the present invention, there is provided a liquid sponge desulfurizing agent comprising an active ingredient including one or more compounds represented by the following general formula I:
Rn(NH)m
general formula I
In the general formula I, R represents alkylene, n is an integer of 1-20, optionally, hydrogen atoms in each R group and each-NH-are independently substituted by hydroxyalkyl, hydroxyalkoxy, hydroxyphenyl or phenyl, and at least one hydrogen atom in n R groups and m-NH-is substituted by hydroxyalkyl, hydroxyalkoxy or hydroxyphenyl; m is an integer of 1 to 6.
Further, in the general formula I, m is an integer of 1-4, and n is an integer of 4-12.
Further, in the general formula I, at least two R groups are separated between two adjacent-NH-.
Further, when hydrogen atoms in each R group and each-NH-are independently substituted, the number of hydroxyalkyl groups is 0 to 4, the number of hydroxyalkoxy groups is 0 or 1, the number of hydroxyphenyl groups is 0 or 1, the number of phenyl groups is 0 or 1, and the total number of hydroxyalkyl groups, hydroxyalkoxy groups, and hydroxyphenyl groups is not equal to 0.
Further, hydroxyalkyl is C1～C6Hydroxyalkyl of (2), hydroxyalkoxy being C1～C6A hydroxyalkoxy group of (a).
Further, the hydroxyalkyl is one or more of hydroxymethyl, hydroxyethyl and hydroxypropyl, and the hydroxyalkoxyl is one or more of hydroxymethoxy, hydroxyethoxy and hydroxypropoxyl.
Further, the active ingredient comprises one or more of N-hydroxyethyl piperazine, N-dihydroxyethyl piperazine, N-dihydroxypropyl piperazine, N-hydroxypropyl piperazine, 2-p-hydroxyphenyl piperazine, 1-hydroxypropyl-4-phenyl piperazine, and 1-p-hydroxyphenyl piperazine; preferably, the active ingredient further comprises piperazine.
Further, the liquid sponge desulfurizer also comprises a corrosion inhibitor.
Further, the corrosion inhibitor is an aliphatic alcohol amine compound, preferably one or more of 2-hydroxyethylamine, methylethanolamine, dimethylethanolamine and diethylethanolamine.
Furthermore, the weight ratio of the active component to the corrosion inhibitor is (97-99) to (1-3).
The invention provides a liquid sponge desulfurizer which can remove sulfur dioxide and hydrogen sulfide in flue gas with high selectivity to generate elemental sulfur (sulfur) suspended in a liquid sponge solution, and the sulfur can be separated from the liquid sponge desulfurizer by an external separator; meanwhile, the sulfur dioxide absorbed by the liquid sponge desulfurizer as a buffer solution can be desorbed through low-pressure steam to obtain pure sulfur dioxide, and the liquid sponge desulfurizer can be sent back to the absorption end for recycling after being desorbed through the steam. The liquid sponge desulfurizer provided by the invention has good stability, high selectivity to sulfur dioxide and hydrogen sulfide, low desorption energy consumption and high desulfurization efficiency, and can realize valuable resource utilization of sulfur while meeting the standard emission of sulfur-containing tail gas.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background section, the existing desulfurizing agents cannot achieve sulfur recovery while removing sulfur dioxide and hydrogen sulfide from flue gas.
In order to solve the problems, the invention provides a liquid sponge desulfurizer, which comprises active ingredients, wherein the active ingredients comprise one or more compounds shown in the following general formula I:
Rn(NH)m
general formula I
In the general formula I, R represents alkylene, n is an integer of 1-20, optionally, hydrogen atoms in each R group and each-NH-are independently substituted by hydroxyalkyl, hydroxyalkoxy, hydroxyphenyl or phenyl, and at least one hydrogen atom in n R groups and m-NH-is substituted by the hydroxyalkyl, hydroxyalkoxy or hydroxyphenyl; m is an integer of 1 to 6.
The invention provides a liquid sponge desulfurizer which can remove sulfur dioxide and hydrogen sulfide in flue gas with high selectivity to generate elemental sulfur (sulfur) suspended in a liquid sponge solution, and the sulfur can be separated from the liquid sponge desulfurizer by an external separator; meanwhile, the sulfur dioxide absorbed by the liquid sponge desulfurizer as a buffer solution can be desorbed through low-pressure steam to obtain pure sulfur dioxide, and the liquid sponge desulfurizer can be sent back to the absorption end for recycling after being desorbed through the steam. The liquid sponge desulfurizer provided by the invention has good stability, high selectivity to sulfur dioxide and hydrogen sulfide, low desorption energy consumption and high desulfurization efficiency, and can realize valuable resource utilization of sulfur while meeting the standard emission of sulfur-containing tail gas.
In addition to the above advantages, the liquid sponge desulfurizing agent of the present invention is represented by Rn(NH)mIs an active ingredient, is not easy to volatilize, has high recycling performance and relatively low cost.
It should be noted that the above-mentioned "liquid sponge" refers to a liquid desulfurizer which has an absorption function for sulfur in flue gas, and can also decompose the absorbed sulfur, and is similar to a sponge, and is an image description.
In the practical use process, the liquid sponge desulfurizer preferably also comprises water, and more preferably the effective components (including active components and the corrosion inhibitor) of the liquid sponge desulfurizer account for 5-50% of the total mass concentration, preferably 10-40%; more preferably 15 to 30%.
With the above desulfurizing agent, the sulfur dioxide in the flue gas undergoes hydration and ionization reactions, which can be represented by the following formula:
the basic hydroxyl group (here, the basic hydroxyl group refers to the hydroxyl group in the hydroxypiperazine) in the liquid sponge desulfurizing agent is combined with hydrogen ions, so that the reaction is accelerated to the right side.
Rn(NH)m+H+→Rn(NH)mH+ (3)
When hydrogen sulfide gas enters the liquid sponge desulfurizer, the hydrogen sulfide and sulfite radical, bisulfite radical and hydrogen ion dissolved in the liquid sponge desulfurizer are subjected to centering reaction to generate solid sulfur.
H2S+SO3 2-+2HSO3 -+7H+→4S+9H2O (4)
Of course, as the above reaction (3) proceeds, the pH of the liquid sponge desulfurizing agent gradually decreases, thereby making the dissolution of sulfur dioxide more and more difficult. In order to keep the dissolution rate of sulfur dioxide in a high range, the reaction of (3), (2) and (1) can be reversed by steam stripping the liquid sponge desulfurizer in practical application, thereby releasing sulfur dioxide. The liquid sponge desulfurizer after stripping can continuously and circularly absorb sulfur dioxide. The desorption temperature is generally between 100 and 130 ℃.
In order to further improve the absorption effect of sulfur dioxide and hydrogen sulfide in the flue gas, in a preferred embodiment, in the general formula I, m is an integer of 1-4, and n is an integer of 4-12. Preferably, in formula I, two adjacent-NH-groups are separated by at least two R groups. More preferably, when the hydrogen atoms in each R group and each-NH-are independently substituted, the number of hydroxyalkyl groups is 0 to 4, the number of hydroxyalkoxy groups is 0 or 1, the number of hydroxyphenyl groups is 0 or 1, the number of phenyl groups is 0 or 1, and the total number of hydroxyalkyl groups, hydroxyalkoxy groups, and hydroxyphenyl groups is not equal to 0.
In a preferred embodiment, the hydroxyalkyl group is C1～C6Hydroxyalkyl of (2), hydroxyalkoxy being C1～C6A hydroxyalkoxy group of (a). Preferably, the hydroxyalkyl is one or more of hydroxymethyl, hydroxyethyl and hydroxypropyl, and the hydroxyalkoxy is one or more of hydroxymethoxy, hydroxyethoxy and hydroxypropoxy. By adopting the active ingredients, on one hand, the sulfur absorption efficiency is higher, on the other hand, the resolving power is stronger, and the recycling performance of the desulfurizer is better.
More preferably, the active ingredient comprises one or more of N-hydroxyethyl piperazine, N-dihydroxyethyl piperazine, N-dihydroxypropyl piperazine, N-hydroxypropyl piperazine, 2-p-hydroxyphenyl piperazine, 1-hydroxypropyl-4-phenyl piperazine, 1-p-hydroxyphenyl piperazine. The liquid organic matters are used as active ingredients, have better desulfurization and regeneration effects, are not easy to volatilize, have small loss and can be applied for a long time. In addition, in order to further promote the absorption of sulfur dioxide by the active ingredient, it is preferable that the active ingredient further includes piperazine.
The above active ingredients and corrosion inhibitors are known compounds in the prior art, and can also be prepared according to known methods in the prior art, and are not described in detail herein.
In a preferred embodiment, the liquid sponge desulfurizing agent further comprises a corrosion inhibitor. The desulfurizer is alkaline and acidic in the actual operation process, the pH value is 4-6, and the corrosion inhibitor can protect equipment materials, especially can reduce the corrosion to metal materials. More preferably, the corrosion inhibitor is an aliphatic alcohol amine compound, preferably one or more of 2-hydroxyethylamine, methylethanolamine, dimethylethanolamine, diethylethanolamine.
In order to more fully exert the functions of the active component and the corrosion inhibitor, so as to more effectively absorb the sulfur in the flue gas and then analyze the sulfur, in a preferred embodiment, the weight ratio of the active component to the corrosion inhibitor is (97-99): 1-3.
According to another aspect of the present invention, there is also provided a method of flue gas desulfurization, comprising the steps of:
and introducing the flue gas into the liquid sponge desulfurizer to absorb sulfur dioxide and hydrogen sulfide therein.
For more complete absorption of hydrogen sulphide, it is more preferred that the ratio of sulphur dioxide to hydrogen sulphide in the flue gas is close to 1:2 but greater than 1:2, such as a molar ratio of sulphur dioxide to hydrogen sulphide > 1:2, < 3: 2.
In a preferred embodiment, the method for desulfurizing flue gas further includes a desorption process, which is as follows: and (3) sequentially separating sulfur and steam stripping sulfur dioxide from the liquid sponge desulfurizer absorbing sulfur dioxide and hydrogen sulfide by using a separator to obtain the regenerated liquid sponge desulfurizer.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
In the embodiment, a liquid sponge desulfurizer is used for desulfurizing flue gas, and comprises active ingredients, a corrosion inhibitor and water, wherein the active ingredients comprise piperazine, N-hydroxyethyl piperazine, dihydroxyethyl piperazine and 1-hydroxypropyl-4-phenylpiperazine in a weight ratio of 1:2:3:1, and the corrosion inhibitor is dimethylethanolamine. Wherein the weight ratio of the active component to the corrosion inhibitor is 97:3, and the total mass concentration of the active component and the corrosion inhibitor is 30%.
The flue gas (containing sulfur dioxide and no hydrogen sulfide) is introduced into an adsorption tower filled with the liquid sponge desulfurizer for desulfurization, so that the outlet of the absorption tower is 100mg/Nm3The environmental protection and emission requirements. The flue gas is firstly subjected to initial washing, then the temperature of the flue gas is reduced to 38 ℃, the flue gas enters the absorption tower from a flue gas inlet at the lower part of the absorption tower, and the flue gas is sprayed with a liquid sponge desulfurizer barren solution from top to bottomReverse contact is carried out, the flow velocity of the flue gas is kept at 2.5-2.7m/s, the flue gas and the liquid sponge desulfurizer carry out mass transfer reaction, in order to achieve more ideal reaction effect, the pH value of the barren liquor of the liquid sponge desulfurizer is controlled between 5.4-5.9, sulfur dioxide in the flue gas is captured by the liquid sponge desulfurizer, and the following desulfurization effect is achieved:
the liquid sponge desulfurizer (rich liquid) after absorbing sulfur dioxide is sent to a desorption tower through a pipeline for desorption, which comprises the following steps: the liquid sponge desulfurizer (rich liquid) absorbing sulfur dioxide in the absorption tower is sent to a heat exchanger through a rich liquid discharge pump to be preheated to 95 ℃ and then sent to a desorption tower, in order to improve the desorption effect of the desorption tower, the pressure of the desorption tower is maintained between 50kpa and 70kpa, the sulfur dioxide is desorbed from the rich liquid under the condition that the rich liquid in the desorption tower is heated (120 ℃) through a steam heat exchanger, and a cooler and a gas-liquid separator are arranged at the outlet of the desorption tower to separate the sulfur dioxide and water in the tower top gas saturated with water. The desorbed rich liquid of the liquid sponge desulfurizer is changed into barren liquor, the barren liquor is filtered by a filter to filter particles larger than 1 mu m, and then is sent into an ion exchanger to remove heat stability salt, and the obtained purified barren liquor returns to an absorption tower to react with sulfur dioxide flue gas for recycling. In the desorption process, the desorption rate of the sulfur dioxide is as high as 99.9 percent.
Example 2
The reagents were the same as in example 1, except that the flue gas contained sulfur. The flue gas contains 1200-1500mg/Nm besides the sulfur dioxide gas components listed in the table below3Hydrogen sulfide gas. The liquid sponge absorbent can well remove sulfur dioxide and hydrogen sulfide in operation, and simultaneously meets the environment-friendly discharge requirement of 200 mg/Nm. The flue gas is firstly pre-washed by a pre-washing tower before entering an absorption tower, so that dust particles in the flue gas are removed, and the flue gas is quenched to 40 ℃. The flue gas after pre-washing treatment enters an absorption tower, the flow rate of the flue gas is controlled to be 2.5-2.7m/s, and the flue gas and liquid are mixedThe sponge desulfurizer barren solution is in reverse contact, the pH value of the liquid sponge desulfurizer barren solution is maintained at about 5.7, sulfur dioxide and hydrogen sulfide in the flue gas are removed by the liquid sponge desulfurizer, and the clean flue gas is discharged out of the tower. The desulfurization results were as follows:
and the rich solution of the sponge desulfurizer at the bottom of the absorption tower is discharged out of the absorption tower through a rich solution discharge pump. Meanwhile, a filter is arranged at the outlet of the discharge pump of the absorption tower, the generated sulfur is separated from the rich liquid of the liquid sponge desulfurizer, and the sulfur is further refined after washing and spin-drying. The rich liquid of the liquid sponge absorbent is preheated to 85 ℃ by a heat exchanger and then enters a desorption tower for desorption. The pressure of the desorption tower is maintained between 50kpa and 70kpa, sulfur dioxide is desorbed from the rich liquid in the desorption tower under the condition that the rich liquid in the desorption tower is heated (140 ℃) through a steam heat exchanger, and a cooler and a gas-liquid separator are arranged at the outlet of the desorption tower to separate the sulfur dioxide and water in the tower top gas saturated with water. The desorbed rich liquid of the liquid sponge desulfurizer is changed into barren liquor, the barren liquor is filtered by a filter to remove solid particles with the particle size of 1-10 mu m, suspended particles with the particle size of 1-10 mu m are further removed by a candle filter, heat-stable salt is removed by an ion exchange mode, and the obtained purified barren liquor returns to an absorption tower to react with flue gas containing sulfur dioxide and hydrogen sulfide. In the desorption process, the desorption rate of the sulfur dioxide is as high as 99.9 percent.
Example 3
The process and reagents were the same as in example 1, except that the flue gas contained sulfur, and the results were as follows:
example 4
In the embodiment, a liquid sponge desulfurizer is used for desulfurizing flue gas, and comprises active ingredients, a corrosion inhibitor and water, wherein the active ingredients comprise piperazine, N-hydroxyethyl piperazine, dihydroxyethyl piperazine and 1-p-hydroxyphenyl piperazine in a weight ratio of 1:2:1:1, and the corrosion inhibitor is dimethylethanolamine. Wherein the weight ratio of the active component to the corrosion inhibitor is 99:1, and the total mass concentration of the active component and the corrosion inhibitor is 15%.
The flue gas (containing sulfur dioxide and no hydrogen sulfide) was introduced into an adsorption tower containing the above liquid sponge desulfurizing agent to conduct desulfurization in the same manner as in example 1 so that the outlet of the absorption tower became 100mg/Nm3The environmental protection and emission requirements. The specific desulfurization effect is as follows:
desorbing the absorbed liquid sponge desulfurizer specifically as follows: the desulfurizing agent (rich liquid) absorbing sulfur dioxide in the absorption tower is preheated to 90 ℃ by a heat exchanger and then is sent to a desorption tower through a pipeline, the sulfur dioxide is desorbed from the rich liquid under the condition that the rich liquid in the desorption tower is heated by steam (130 ℃), a cooler and a gas-liquid separator are arranged at the outlet of the desorption tower, and the sulfur dioxide and the water in the tower top gas saturated by water are separated. And (3) converting the desorbed rich solution into a barren solution, filtering the barren solution by a filter to remove solid particles larger than 1 mu m, further removing heat-stable salt by an electrodialysis mode, returning to the absorption tower and reacting with sulfur dioxide. In the desorption process, the desorption rate of the sulfur dioxide is as high as 99.9 percent.
Example 5
In the embodiment, a liquid sponge desulfurizer is used for desulfurizing flue gas, and comprises active ingredients, a corrosion inhibitor and water, wherein the active ingredients comprise N-hydroxyethyl piperazine, dihydroxyethyl piperazine and 1-p-hydroxyphenyl piperazine in a weight ratio of 2:1:1, and the corrosion inhibitor is dimethylethanolamine. Wherein the weight ratio of the active component to the corrosion inhibitor is 97:3, and the total mass concentration of the active component and the corrosion inhibitor is 30%.
Introducing flue gas (containing sulfur dioxide and no hydrogen sulfide) into an adsorption tower filled with the liquid sponge desulfurizerDesulfurization so that the outlet of the absorption column is 100mg/Nm3The environmental protection and emission requirements. The flue gas is firstly pre-washed by a pre-washing tower before entering an absorption tower, so that dust particles in the flue gas are removed, and the flue gas is quenched to 40 ℃. The flue gas after the pre-washing treatment enters an absorption tower, the flow rate of the flue gas is controlled to be 2.5-2.7m/s, the flue gas reversely contacts with the liquid sponge desulfurizer barren solution, the pH value of the liquid sponge desulfurizer barren solution is maintained to be about 5.7, sulfur dioxide in the flue gas is removed by the liquid sponge desulfurizer, and clean flue gas is discharged out of the tower. The specific desulfurization effect is as follows:
the rich solution of the sponge desulfurizer at the bottom of the absorption tower is discharged from the absorption tower through a rich solution discharge pump and enters a desorption tower for desorption. The pressure of the desorption tower is maintained between 50kpa and 70kpa, sulfur dioxide is desorbed from the rich liquid in the desorption tower under the condition that the rich liquid in the desorption tower is heated (130 ℃) through a steam heat exchanger, and a cooler and a gas-liquid separator are arranged at the outlet of the desorption tower to separate the sulfur dioxide and water in the tower top gas saturated with water. The desorbed rich liquid of the liquid sponge desulfurizer is changed into barren liquor, and the barren liquor returns to the absorption tower to react with the flue gas containing sulfur dioxide. In the desorption process, the desorption rate of the sulfur dioxide is as high as 99.9 percent.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The liquid sponge desulfurizer is characterized by comprising an active component, wherein the active component comprises one or more compounds shown in the following general formula I:
Rn(NH)m
general formula I
In the general formula I, R represents alkylene, n is an integer of 1-20, optionally, hydrogen atoms in each R group and each-NH-are independently substituted by hydroxyalkyl, hydroxyalkoxy, hydroxyphenyl or phenyl, and at least one hydrogen atom in n R groups and m-NH-is substituted by the hydroxyalkyl, the hydroxyalkoxy or the hydroxyphenyl; m is an integer of 1 to 6.
2. The liquid sponge desulfurizer according to claim 1, wherein in the general formula I, m is an integer of 1 to 4, and n is an integer of 4 to 12.
3. The liquid sponge desulfurizing agent according to claim 2, wherein in the general formula I, at least two R groups are spaced between two adjacent-NH-.
4. The liquid sponge desulfurizing agent according to claim 2, wherein when hydrogen atoms in each R group and each-NH-are independently substituted, the number of the hydroxyalkyl groups is 0 to 4, the number of the hydroxyalkoxyl groups is 0 or 1, the number of the hydroxyphenyl groups is 0 or 1, the number of the phenyl groups is 0 or 1, and the total number of the hydroxyalkyl groups, the hydroxyalkoxyl groups and the hydroxyphenyl groups is not equal to 0.
5. The liquid sponge desulfurizing agent according to any one of claims 1 to 4, wherein the hydroxyalkyl group is C1～C6The hydroxyalkyl of (A), the hydroxyalkoxy is C1～C6A hydroxyalkoxy group of (a).
6. The liquid sponge desulfurizing agent according to claim 5, wherein the hydroxyalkyl group is one or more of hydroxymethyl, hydroxyethyl and hydroxypropyl, and the hydroxyalkoxy group is one or more of hydroxymethoxy, hydroxyethoxy and hydroxypropoxy.
7. The liquid sponge desulfurizing agent according to any one of claims 1 to 4, wherein the active ingredient includes one or more of N-hydroxyethylpiperazine, N-dihydroxyethylpiperazine, N-dihydroxypropylpiperazine, N-hydroxypropylpiperazine, 2-p-hydroxyphenylpiperazine, 1-hydroxypropyl-4-phenylpiperazine, 1-p-hydroxyphenylpiperazine; preferably, the active ingredient further comprises piperazine.
8. The liquid sponge desulfurizing agent according to any one of claims 1 to 4, wherein the liquid sponge desulfurizing agent further comprises a corrosion inhibitor.
9. The liquid sponge desulfurizing agent according to claim 8, wherein the corrosion inhibitor is an aliphatic alcohol amine compound, preferably one or more of 2-hydroxyethylamine, methylethanolamine, dimethylethanolamine, diethylethanolamine.
10. The liquid sponge desulfurizing agent according to claim 8, wherein the weight ratio of the active component to the corrosion inhibitor is (97-99): 1-3.
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