CN115745262A - Desulfurization device and method for sulfur-containing and salt-containing process water - Google Patents
Desulfurization device and method for sulfur-containing and salt-containing process water Download PDFInfo
- Publication number
- CN115745262A CN115745262A CN202211457877.4A CN202211457877A CN115745262A CN 115745262 A CN115745262 A CN 115745262A CN 202211457877 A CN202211457877 A CN 202211457877A CN 115745262 A CN115745262 A CN 115745262A
- Authority
- CN
- China
- Prior art keywords
- tower
- sulfur
- unit
- reaction
- biological oxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 120
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000011593 sulfur Substances 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 150000003839 salts Chemical class 0.000 title claims abstract description 33
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 26
- 230000023556 desulfurization Effects 0.000 title claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 99
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 99
- 239000007789 gas Substances 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 82
- 238000010521 absorption reaction Methods 0.000 claims abstract description 71
- 238000009833 condensation Methods 0.000 claims abstract description 48
- 230000005494 condensation Effects 0.000 claims abstract description 48
- 238000001179 sorption measurement Methods 0.000 claims abstract description 33
- 239000012071 phase Substances 0.000 claims abstract description 28
- 239000007791 liquid phase Substances 0.000 claims abstract description 24
- 238000007872 degassing Methods 0.000 claims abstract description 12
- 238000005273 aeration Methods 0.000 claims description 44
- 239000007788 liquid Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 25
- 239000012295 chemical reaction liquid Substances 0.000 claims description 20
- 239000006228 supernatant Substances 0.000 claims description 19
- 239000003513 alkali Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 229920000297 Rayon Polymers 0.000 claims description 13
- 244000005700 microbiome Species 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000003463 adsorbent Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- 241000607598 Vibrio Species 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 239000007792 gaseous phase Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000009629 microbiological culture Methods 0.000 claims 2
- 241000193375 Bacillus alcalophilus Species 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 abstract description 48
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 11
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 11
- 238000012423 maintenance Methods 0.000 abstract description 3
- 238000011282 treatment Methods 0.000 description 21
- 239000002912 waste gas Substances 0.000 description 8
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 7
- 230000003009 desulfurizing effect Effects 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- XDAHMMVFVQFOIY-UHFFFAOYSA-N methanedithione;sulfane Chemical compound S.S=C=S XDAHMMVFVQFOIY-UHFFFAOYSA-N 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000007380 fibre production Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- -1 sulfur ions Chemical class 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 241000006383 Salimicrobium halophilum Species 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 241000605008 Spirillum Species 0.000 description 2
- 241001148470 aerobic bacillus Species 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241000588986 Alcaligenes Species 0.000 description 1
- 241000193830 Bacillus <bacterium> Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 241000451721 Thiohalophilus Species 0.000 description 1
- VUTSITSGGYCKFP-UHFFFAOYSA-J [C+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [C+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VUTSITSGGYCKFP-UHFFFAOYSA-J 0.000 description 1
- DPSZMPUXFZOWAC-UHFFFAOYSA-N [S].S=O Chemical compound [S].S=O DPSZMPUXFZOWAC-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Treating Waste Gases (AREA)
Abstract
The invention discloses a desulfurization device and a desulfurization method for sulfur-containing and salt-containing process water, wherein the desulfurization device comprises a reaction degassing unit, a condensation unit, an absorption unit, a biological oxidation unit and an adsorption unit, the reaction degassing unit comprises a reaction tower and a release tower, an outlet of the reaction tower is connected with an inlet of the release tower, gas phase inlets of the reaction tower and the release tower are both connected with the condensation unit, a gas phase outlet of the condensation unit is connected with the absorption unit, a liquid phase outlet of the absorption unit is connected with the biological oxidation unit, and gas phase outlets of the reaction tower and the release tower are connected with the adsorption unit. According to the invention, the reaction tower and the release tower are arranged to convert sulfur-containing components in the sulfur-containing and salt-containing process water into sulfur-containing gas, and then the carbon disulfide and the hydrogen sulfide are respectively recovered through the condensation, absorption, biological oxidation and adsorption structure unit arrangement, so that the resource utilization of the sulfur-containing components is realized, the removal rate of sulfur is high, and the gas is discharged after reaching the standard; the device adopts multiple equipment combination to use, and the device operating stability is strong, and the maintenance cost is low, easy operation.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and relates to a desulfurization device and a desulfurization method for sulfur-containing and salt-containing process water.
Background
The viscose fiber is a chemical fiber which is processed by chemical and mechanical methods by utilizing high polymer material wood pulp, cotton pulp and the like containing natural cellulose, is one of important materials of textile industry raw materials, has wide application field, and is often used for producing chemical products by utilizing the viscose fiber, wherein the generated process water contains a large amount of sulfide and carbon disulfide, which easily causes production safety risk and needs to recover the sulfur-containing components and salt in the process water. Because the salinity of the process water is high, the dissolved gas is easy to escape, and the sulfur-containing component is easy to form sulfur-containing gas, thereby increasing the treatment difficulty and the cost and becoming one of the technical problems in the viscose industry.
Carbon disulfide as a key solvent in viscose fiber production can generate a large amount of hydrogen sulfide and carbon disulfide waste gas according to the characteristics of the carbon disulfide and the reaction generated in the production, and the recovery and treatment of the hydrogen sulfide and the carbon disulfide waste gas are currently important research directions. According to different component characteristics, carbon disulfide is generally recovered in a condensation mode, while hydrogen sulfide is recovered in a plurality of modes, such as a spray absorption method, an adsorption method, a chemical oxidation method, a biological oxidation method and the like are commonly used, and a single method is often difficult to achieve a good effect, and is also an important step for wastewater treatment on how to fully convert sulfur-containing components in wastewater into gas.
CN 110467319A discloses a viscose waste water treatment process, which mainly comprises the steps of mixed aeration, air flotation treatment, micro-electrolysis treatment, catalytic oxidation treatment, neutralization and precipitation treatment, aerobic biochemical treatment, precipitation treatment and the like, wherein the micro-electrolysis treatment is to oxidize and remove complex organic matters which are difficult to degrade and have strong stability in waste water in a micro-electrolysis reactor; feeding the electrolyzed wastewater into a catalytic oxidation reactor, adding hydrogen peroxide as an oxidant, and oxidizing and removing refractory organic matters; the wastewater without organic matters is sent into a reaction tank for neutralization treatment, the pH value is adjusted to 9-10, then the wastewater is sent into a primary sedimentation tank for sedimentation, the supernatant is sent into an aerobic biochemical tank, and the organic matters are decomposed into inorganic matters by utilizing the adsorption and degradation effects of activated sludge and aerobic bacteria in the biochemical tank. The viscose waste water treated by the method has high content of organic components, and a plurality of steps are set for treating the organic components, only mixed aeration and air floatation treatment are used for removing hydrogen sulfide and carbon disulfide, but sulfur ions in sulfide salt cannot be effectively removed, and the subsequent treatment of gas is not disclosed.
CN 113058424A discloses a viscose fiber production waste gas treatment method containing hydrogen sulfide and carbon disulfide, which comprises the following steps: carrying out catalytic oxidation treatment on viscose fiber production waste gas containing hydrogen sulfide and carbon disulfide so as to oxidize at least part of hydrogen sulfide; and sequentially performing alkali washing and carbon adsorption treatment on the waste gas obtained by the catalytic oxidation treatment, wherein the alkali washing and carbon adsorption treatment is at least used for recovering carbon disulfide in the waste gas, so that the effective treatment of the waste gas is realized. The method directly treats sulfur-containing waste gas components, but only adopts a catalytic oxidation mode to treat hydrogen sulfide, so that the removal effect is limited, and the treatment operation aiming at carbon disulfide is more complicated.
In summary, for the desulfurization treatment of the sulfur-containing and salt-containing process water, a proper recovery process needs to be selected according to the source and composition of the process water, so that the recovery rate of the sulfur-containing components is improved, and the resource utilization is realized.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a desulfurization device and a desulfurization method for sulfur-containing salt-containing process water.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a desulfurization device for sulfur-containing and salt-containing process water, which comprises a reaction degassing unit, a condensation unit, an absorption unit, a biological oxidation unit and an adsorption unit which are connected in sequence, wherein the reaction degassing unit comprises a reaction tower and a release tower, a liquid-phase outlet of the reaction tower is connected with a liquid-phase inlet of the release tower, gas-phase inlets of the reaction tower and the release tower are both connected with an inlet of the condensation unit, a gas-phase outlet of the condensation unit is connected with an inlet of the absorption unit, a liquid-phase outlet of the absorption unit is connected with an inlet of the biological oxidation unit, and gas-phase outlets of the absorption unit and the biological oxidation unit are connected with an inlet of the adsorption unit.
According to the invention, according to the source and composition of the sulfur-containing salt-containing process water, a reaction tower and a release tower are arranged firstly, sulfur ions in the process water are converted into gas in the form of hydrogen sulfide, carbon disulfide is vaporized by utilizing reaction heat release, so that sulfur-containing components are released in a gas phase form, then according to the characteristics of the sulfur-containing components, the carbon disulfide components are recovered through a condensing unit, the hydrogen sulfide is absorbed through an absorbing unit and oxidized by using microorganisms to form sulfur simple substances, and finally the gas is adsorbed and discharged up to the standard, so that the sulfur-containing components in the process water are respectively recovered, and resource utilization is realized; the device adopts multiple equipment combination to use, and the stability of device operation is strong, can adjust according to actual conditions is nimble, easy operation, and no secondary pollution produces.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferable technical scheme of the invention, the lower part of the reaction tower is provided with a gas phase inlet, and a stirring component is arranged inside the reaction tower.
Preferably, a cooling circulation channel is arranged on the reaction tower.
Preferably, the lower part of the release tower is provided with a gas phase inlet, and the bottom of the release tower is provided with a liquid phase outlet.
Preferably, the outer side of the release tower is provided with a circulating pipeline which is connected to the upper part of the release tower from the lower part of the release tower.
In the invention, concentrated sulfuric acid is used in the reaction tower to release hydrogen sulfide in the process water, the temperature of the process water is raised to be above the boiling point of carbon disulfide by using the heat release of chemical reaction, so that the carbon disulfide is fully released, the reaction is promoted to fully occur by using aeration and mechanical stirring, and sulfur-containing gas is released; and the release tower fully releases the sulfur-containing gas by using a gas stripping mode.
As a preferable technical scheme of the invention, the condensation unit comprises at least one stage of condensation tower.
Preferably, the condensation unit comprises a primary condensation tower and a secondary condensation tower, and a gas phase outlet of the primary condensation tower is connected with a gas phase inlet of the secondary condensation tower.
Preferably, the upper parts of the condensing towers are provided with condensed water inlets, and the lower parts of the condensing towers are provided with condensed liquid outlets.
Preferably, the condensation column is a packed column.
In the invention, the condensation tower is arranged, the characteristics of low boiling point and easy liquefaction of the carbon disulfide are mainly utilized, the carbon disulfide is cooled by low-temperature condensed water, gas is in countercurrent contact with the condensed water, and CS (carbon sulfate) with low boiling point is arranged 2 Condensed into liquid, separated from the gas to form condensate, collected and then sent to a recovery process for CS 2 The recovery operation of (2) realizes the separation and recycle of the carbon disulfide.
In a preferred embodiment of the present invention, the absorption unit includes an absorption tower, and an absorption liquid inlet is provided at an upper portion of the absorption tower.
Preferably, the biological oxidation unit comprises a biological oxidation tower, and an air inlet is formed in the lower part of the biological oxidation tower.
Preferably, the outlet of the biological oxidation tower is connected with the absorption liquid inlet of the absorption tower.
As a preferable technical scheme, the desulfurization device further comprises a settling tower, and a liquid phase outlet of the biological oxidation tower is connected with an inlet of the settling tower.
Preferably, the settling tower separates into supernatant and solid-phase elemental sulfur after settling, and an outlet of the supernatant is connected to the biological oxidation tower.
Preferably, the adsorption tower is packed with an adsorbent.
In the invention, firstly, the alkali liquor is utilized to react H in the sulfur-containing component 2 S is absorbed and then enters a biological oxidation tower, and is oxidized to form elemental sulfur under the action of aerobic microorganisms, and elemental sulfur liquid in the oxidation tower is subjected to sulfur settling separation operation in a settling tower, so that the elemental sulfur is separated and recovered.
In another aspect, the invention provides a method for desulfurizing sulfur-containing salt-containing process water by using the desulfurization device, which comprises the following steps:
(1) Reacting sulfur-containing salt-containing process water with acid, and carrying out aeration stripping on the obtained reaction liquid to obtain sulfur-containing gas;
(2) Condensing the sulfur-containing gas obtained in the step (1), condensing and recovering carbon disulfide, and absorbing uncondensed gas by adopting alkali liquor to obtain sulfur-rich liquid;
(3) Carrying out biological oxidation on the sulfur-rich liquid obtained in the step (2) to obtain elemental sulfur;
(4) And (3) adsorbing the residual gas after absorption in the step (2) and the biologically oxidized tail gas in the step (3) to obtain purified gas.
As a preferable technical scheme of the invention, the source of the sulfur-containing and salt-containing process water in the step (1) comprises a production process in the viscose industry.
Preferably, the process containing sulfur and salt in step (1)The component to be removed in the water comprises S 2- And CS 2 Said S 2- The concentration of (B) is 0 to 6.5g/L, for example 0.1g/L, 0.5g/L, 1g/L, 2g/L, 3g/L, 4g/L, 5g/L, 6g/L or 6.5g/L, etc., but is not limited to the recited values, and other values not recited within the numerical range are also applicable; the CS 2 The concentration of (B) is 0 to 0.5g/L, for example 0.05g/L, 0.1g/L, 0.2g/L, 0.3g/L, 0.4g/L or 0.5g/L, etc., but is not limited to the values listed, and other values not listed in the numerical range are also applicable, and the above concentration range is not 0 at the end.
Preferably, the sulfur-containing and salt-containing process water of step (1) has a pH of 7 to 14, such as 7, 8, 9, 10, 11, 12, 13, or 14, and the like, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the acid in step (1) comprises concentrated sulfuric acid, and the concentrated sulfuric acid is added dropwise.
Preferably, the concentrated sulfuric acid is added at a rate of 0 to 1.0mL/min, such as 0.1mL/min, 0.2mL/min, 0.3mL/min, 0.5mL/min, 0.6mL/min, 0.8mL/min, or 1.0mL/min, but not limited to the recited values, and other values not recited in this range are equally applicable.
In the present invention, the amount of concentrated sulfuric acid added is generally in excess, at least greater than the molar amount required to completely convert the sulfur ions in the process water to hydrogen sulfide.
Preferably, the reaction temperature in step (1) is controlled to be 40 to 70 ℃, for example, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ or 70 ℃, but is not limited to the recited values, and other unrecited values within the range of values are also applicable.
Preferably, the reaction of step (1) is controlled to have a pH of 6.5 to 8.0, such as 6.5, 6.8, 7.0, 7.2, 7.5, 7.8 or 8.0, but not limited to the recited values, and other values not recited within the range are equally applicable.
Preferably, the reaction process in the step (1) is aerated and stirred.
Preferably, the aeration comprises aeration with air at an aeration rate of 1 to 3L/min, such as 1L/min, 1.5L/min, 2L/min, 2.5L/min, or 3L/min, but not limited to the recited values, and other values not recited within the range of values are equally applicable; the stirring rate is 100 to 300rpm, for example, 100rpm, 150rpm, 200rpm, 250rpm or 300rpm, but is not limited to the enumerated values, and other values not enumerated within the range of values are also applicable.
In the invention, the reaction tower is a reaction unit of process water and concentrated sulfuric acid, and promotes H through aeration and stirring action 2 S and CS 2 And the reaction solution is formed and enters a gas phase, the temperature and the pH value are controlled by adjusting the dropping speed of concentrated sulfuric acid in the operation process, and the reaction temperature is adjusted by arranging a cooling circulation channel in the reaction tower.
As a preferable technical scheme of the invention, the aeration stripping in the step (1) is carried out in a release tower.
Preferably, the aeration stripping is as follows: air is introduced from the lower part of the releasing tower at an aeration rate of 1 to 3L/min, for example, 1L/min, 1.5L/min, 2L/min, 2.5L/min or 3L/min, etc., but not limited to the enumerated values, and other values not enumerated within the range of values are also applicable.
Preferably, the reaction liquid is self-circulated in the releasing tower, and is taken out from the lower part of the releasing tower and returned to the upper part of the releasing tower.
Preferably, the rate of self-circulation of the reaction solution is 300 to 750mL/min, such as 300mL/min, 350mL/min, 400mL/min, 450mL/min, 500mL/min, 60mL/min, 700mL/min, or 750mL/min, but is not limited to the recited values, and other values within the range are equally applicable.
Preferably, the self-circulation time of the reaction solution is 15 to 30min, such as 15min, 18min, 20min, 22min, 25min, 27min or 30min, but is not limited to the recited values, and other values not recited within the range of values are also applicable.
Preferably, the sulfur-containing gas of step (1) comprises H 2 S and CS 2 。
In the present invention, the releasing tower is one for releasing sulfur-containing gas from the reaction liquid fullyA unit for dissolving H in the liquid by self-circulation of the liquid and combining with aeration stripping 2 S、CS 2 And the sulfur-containing gas is released fully.
As a preferable technical scheme of the invention, the condensation in the step (2) is to spray condensed water to remove CS in the sulfur-containing gas 2 Condensing and recycling.
Preferably, the condensation in the step (2) comprises primary condensation and secondary condensation in sequence.
Preferably, the temperature of the condensed water is 0 to 10 ℃, for example, 0 ℃,2 ℃,4 ℃,5 ℃,6 ℃, 8 ℃ or 10 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the amount of the condensed water sprayed is 300 to 500mL/min, such as 300mL/min, 350mL/min, 400mL/min, 450mL/min or 500mL/min, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the lye of step (2) comprises Na 2 CO 3 Solutions and/or NaHCO 3 And (3) solution.
Preferably, the pH of the lye of step (2) is in the range of from 8.5 to 10.5, such as 8.5, 9.0, 9.5, 10.0 or 10.5 and the like, but is not limited to the recited values and other values not recited within this range are equally applicable.
Preferably, the flow rate of the alkali solution in step (2) is 50-150 mL/min, such as 50mL/min, 60mL/min, 80mL/min, 100mL/min, 120mL/min, 140mL/min or 150mL/min, but not limited to the recited values, and other non-recited values in the range of the values are also applicable.
In the invention, because the treatment of the sulfur-containing gas needs to use a biological oxidation step, microorganisms need to be used, and correspondingly, a microorganism culture solution needs to be used, and according to the connection relationship between the absorption tower and the biological oxidation tower and the composition of the culture solution suitable for the growth of the microorganisms, the alkaline solution used by the absorption tower can be the microorganism culture solution and contains small amounts of monopotassium phosphate, ammonium chloride, potassium nitrate, magnesium chloride, conventional trace elements and the like besides main components of sodium carbonate and potassium carbonate.
As a preferred technical scheme of the invention, the biological oxidation in the step (3) is carried out in a biological oxidation tower.
Preferably, the aerobic microorganisms in the biological oxidation tower include any one of or a combination of at least two of a pluripotent vibrio thiolyticus D301 strain (CGMCC No. 8497), a micro spirillum oxysulphi BDL05 strain (CGMCC No. 20060) or a bacillus thiohalophilus BDH06 strain (CGMCC No. 20058), typical but non-limiting examples of which include: a combination of a pluripotent Vibrio thiolyticus D301 strain and a Microspirillum oxysulphi BDL05 strain, a combination of a Microspirillum oxysulphi BDL05 strain and a Bacillus halophilus BDH06 strain, a combination of a pluripotent Vibrio thiolyticus D301 strain, a Microspirillum oxysulphi BDL05 strain and a Bacillus halophilus BDH06 strain, and the like.
In the invention, biological oxidation is carried out by mainly utilizing the strong adsorption capacity of a microbial biofilm and sulfur to fully absorb sulfur-containing components in gas, and then treating sulfur-containing substances by utilizing a mixed flora consisting of a plurality of microorganisms to realize efficient removal and conversion of the sulfur-containing components, and the method is green and safe and has no secondary pollution; as the microorganism used in the invention is aerobic bacteria, the biological oxidation tower needs continuous aeration operation.
Preferably, the biological oxidation tower is aerated by introducing air at a rate of 0.2 to 0.6L/min, such as 0.2L/min, 0.25L/min, 0.3L/min, 0.35L/min, 0.4L/min, 0.45L/min, 0.5L/min, 0.55L/min, or 0.6L/min, but not limited to the recited values, and other values not recited in the range of values are equally applicable.
Preferably, the liquid circulation is formed between the absorption column and the biological oxidation column, and the liquid flow rate returned from the biological oxidation column to the absorption column is 50-150 mL/min, such as 50mL/min, 80mL/min, 100mL/min, 120mL/min or 150mL/min, but not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the sulfur-rich liquid obtained after the biological oxidation in the step (3) is subjected to sedimentation separation to obtain elemental sulfur solid and supernatant, and the supernatant is returned to the biological oxidation tower.
Preferably, the adsorption in step (4) is performed by using an adsorption tower.
Preferably, the adsorbent packed in the adsorption column comprises any one of activated carbon, silica gel or activated alumina, or a combination of at least two of them, typical but non-limiting examples of which are: combinations of activated carbon and silica gel, combinations of silica gel and activated alumina, combinations of activated carbon, silica gel and activated alumina, and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the device, the sulfur-containing components in the sulfur-containing and salt-containing process water are fully converted into sulfur-containing gas through the arrangement of the reaction tower and the release tower, and then the carbon disulfide and the hydrogen sulfide are respectively recovered through the arrangement of structural units such as condensation, absorption, biological oxidation and adsorption, so that the resource utilization of the sulfur-containing components is realized, the removal rate of sulfur in the process water reaches more than 99.7%, and the gas is discharged after reaching the standard;
(2) The device provided by the invention is combined by multiple devices, has strong running stability, can be flexibly adjusted according to actual conditions, and is low in maintenance cost and simple to operate.
Drawings
FIG. 1 is a schematic diagram of a desulfurization unit for sulfur-containing brackish process water according to example 1 of the present invention;
wherein, the method comprises the steps of 1-a reaction tower, 2-a release tower, 31-a first-stage condensation tower, 32-a second-stage condensation tower, 4-an absorption tower, 5-a biological oxidation tower, 6-a settling tower and 7-an adsorption tower.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The invention provides a desulfurization device and a desulfurization method for sulfur-containing and salt-containing process water, wherein the desulfurization device comprises a reaction degassing unit, a condensation unit, an absorption unit, a biological oxidation unit and an adsorption unit which are sequentially connected, the reaction degassing unit comprises a reaction tower 1 and a release tower 2, a liquid phase outlet of the reaction tower 1 is connected with a liquid phase inlet of the release tower 2, gas phase inlets of the reaction tower 1 and the release tower 2 are both connected with an inlet of the condensation unit, a gas phase outlet of the condensation unit is connected with an inlet of the absorption unit, a liquid phase outlet of the absorption unit is connected with an inlet of the biological oxidation unit, and gas phase outlets of the absorption unit and the biological oxidation unit are connected with an inlet of the adsorption unit.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a sulfur-containing and salt-containing process water desulfurization device, the structural schematic diagram of the desulfurization device is shown in fig. 1, and the device comprises a reaction degassing unit, a condensation unit, an absorption unit, a biological oxidation unit and an adsorption unit which are connected in sequence, wherein the reaction degassing unit comprises a reaction tower 1 and a release tower 2, a liquid phase outlet of the reaction tower 1 is connected with a liquid phase inlet of the release tower 2, gas phase inlets of the reaction tower 1 and the release tower 2 are connected with an inlet of the condensation unit, a gas phase outlet of the condensation unit is connected with an inlet of the absorption unit, a liquid phase outlet of the absorption unit is connected with an inlet of the biological oxidation unit, and gas phase outlets of the absorption unit and the biological oxidation unit are connected with an inlet of the adsorption unit.
The lower part of the reaction tower 1 is provided with a gas phase inlet, and a stirring component is arranged in the reaction tower.
And a cooling circulation channel is arranged on the reaction tower 1.
The lower part of the release tower 2 is provided with a gas phase inlet, and the bottom of the release tower is provided with a liquid phase outlet.
The outer side of the releasing tower 2 is provided with a circulating pipeline which is connected to the upper part of the releasing tower 2 from the lower part of the releasing tower 2.
The condensing unit comprises two stages of condensing towers, namely a first-stage condensing tower 31 and a second-stage condensing tower 32, wherein a gas phase outlet of the first-stage condensing tower 31 is connected with a gas phase inlet of the second-stage condensing tower 32.
The upper portion of condensing tower all is equipped with the comdenstion water entry, and the lower part all is equipped with the condensate outlet.
The absorption unit comprises an absorption tower 4, and an absorption liquid inlet is formed in the upper part of the absorption tower 4.
The biological oxidation unit comprises a biological oxidation tower 5, and an air inlet is formed in the lower part of the biological oxidation tower 5.
The outlet of the biological oxidation tower 5 is connected with the absorption liquid inlet of the absorption tower 4.
The desulfurization device also comprises a settling tower 6, and a liquid phase outlet of the biological oxidation tower 5 is connected with an inlet of the settling tower 6.
The settling tower 6 is divided into supernatant and solid sulfur after settling, and an outlet of the supernatant is connected to the biological oxidation tower 5.
The adsorption tower 7 is filled with an adsorbent which is activated carbon.
Example 2:
the embodiment provides a sulfur-containing and salt-containing process water's desulphurization unit, desulphurization unit is including the reaction degasification unit, condensing unit, absorption unit, biological oxidation unit and the absorption unit that connect gradually, the reaction degasification unit includes reaction tower 1 and release tower 2, the liquid phase export of reaction tower 1 links to each other with the liquid phase entry of release tower 2, the gaseous phase entry of reaction tower 1 and release tower 2 all links to each other with condensing unit's entry, condensing unit's gaseous phase export links to each other with absorption unit's entry, absorption unit's liquid phase export links to each other with biological oxidation unit's entry, absorption unit and biological oxidation unit's gaseous phase export links to each other with absorption unit's entry.
The lower part of the reaction tower 1 is provided with a gas phase inlet, and a stirring component is arranged in the reaction tower.
And a cooling circulation channel is arranged on the reaction tower 1.
And a gas phase inlet is arranged at the lower part of the release tower 2, and a liquid phase outlet is arranged at the bottom of the release tower.
The outer side of the release tower 2 is provided with a circulating pipeline which is connected to the upper part of the release tower 2 from the lower part of the release tower 2.
The condensing unit comprises a primary condensing tower, a condensed water inlet is formed in the upper portion of the condensing tower, and a condensed liquid outlet is formed in the lower portion of the condensing tower.
The absorption unit comprises an absorption tower 4, and an absorption liquid inlet is formed in the upper part of the absorption tower 4.
The biological oxidation unit comprises a biological oxidation tower 5, and an air inlet is formed in the lower part of the biological oxidation tower 5.
The desulfurization device also comprises a settling tower 6, and a liquid phase outlet of the biological oxidation tower 5 is connected with an inlet of the settling tower 6.
The settling tower 6 is divided into supernatant and solid sulfur after settling, and an outlet of the supernatant is connected to the biological oxidation tower 5.
The adsorption tower 7 is filled with an adsorbent which is silica gel.
Example 3:
the embodiment provides a method for desulfurizing sulfur-containing salt-containing process water, which is carried out by adopting the desulfurizing device in the embodiment 1 and comprises the following steps:
(1) Reacting sulfur-containing salt-containing process water with concentrated sulfuric acid, wherein the sulfur-containing salt-containing process water is obtained from a production process in the viscose industry, and Na is contained in the process water + The concentration is 74.3g/L, S 2- The concentration is 5.8g/L, CS 2 The concentration is 0.11g/L, and the pH is 12.9; adding concentrated sulfuric acid in a dropwise manner, wherein the dropwise adding speed is 0.5mL/min, the reaction temperature is controlled to 65 ℃, the pH value is controlled to 7.5, aerating and stirring are carried out in the reaction process, air is introduced into the reaction process, the aerating speed is 2L/min, the stirring speed is 200rpm, and the obtained reaction liquid is aerated and blown off, wherein the aerating and blowing off is as follows: introducing air from the lower part of the release tower 2, wherein the aeration rate is 2L/min, the reaction liquid performs self-circulation in the release tower 2, the reaction liquid is collected from the lower part of the release tower 2 and returns to the upper part of the release tower 2 from the outside of the release tower, the self-circulation rate of the reaction liquid is 500mL/min, the self-circulation time is 20min, and sulfur-containing gas including H is obtained through reaction and aeration stripping 2 S and CS 2 And the bottom of the releasing tower 2 obtains the water discharged from the releasing tower;
(2) Condensing the sulfur-containing gas obtained in the step (1), wherein the condensation is to spray condensed water and to obtain CS in the sulfur-containing gas 2 Condensing and recovering, wherein the condensing comprises a first stageCondensation and secondary condensation, wherein the temperature of the condensed water is 5 ℃, the spraying amount of the condensed water is 400mL/min, uncondensed gas is absorbed by alkali liquor, and the alkali liquor is Na with the mass ratio of 1:1 2 CO 3 And NaHCO 3 The pH value of the mixed solution is 9.5, and the flow rate of the alkali liquor is 100mL/min, so as to obtain a sulfur-rich solution;
(3) Biologically oxidizing the sulfur-rich liquid obtained in the step (2), wherein the biological oxidation is performed in a biological oxidation tower 5, aerobic microorganisms in the biological oxidation tower 5 are multipotent Vibrio thioalkali D301 strains, air is introduced into the biological oxidation tower for aeration, the aeration rate is 0.4L/min, liquid circulation is formed between an absorption tower 4 and the biological oxidation tower 5, the liquid flow returned to the absorption tower 4 from the biological oxidation tower 5 is 100mL/min, the sulfur-rich liquid after biological oxidation is subjected to sedimentation separation to obtain elemental sulfur solid and supernatant, and the supernatant is returned to the biological oxidation tower 5;
(4) And (3) adsorbing the residual gas after the absorption in the step (2) and the biologically oxidized tail gas in the step (3) by using an adsorption tower 7, wherein an adsorbent filled in the adsorption tower 7 is activated carbon to obtain purified gas.
In this example, according to the detection, the concentration of sulfide in the effluent of the stripping tower was only 4.2mg/L, and CS was not detected 2 The removal rate of sulfur in the process water reaches 99.93 percent; the purified gas obtained contained no H detected 2 S and CS 2 The removal rate almost reaches 100%.
Example 4:
the embodiment provides a method for desulfurizing sulfur-containing salt-containing process water, which is carried out by adopting the desulfurizing device in the embodiment 1 and comprises the following steps:
(1) Reacting sulfur-containing salt-containing process water with concentrated sulfuric acid, wherein the sulfur-containing salt-containing process water is obtained from a production process in the viscose industry, and S 2- The concentration is 4.3g/L, CS 2 The concentration is 0.21g/L, and the pH is 12.1; the concentrated sulfuric acid is added in a dropwise manner, the dropwise adding speed is 1.0mL/min, the reaction temperature is controlled to be 50 ℃, the pH value is controlled to be 6.5, aeration is carried out in the reaction process, air is introduced into the reaction process, the aeration speed is 3L/min, and the stirring speed is 100And (3) performing aeration stripping on the obtained reaction liquid at the rpm, wherein the aeration stripping comprises the following steps: introducing air from the lower part of the release tower 2, wherein the aeration rate is 1L/min, the reaction liquid performs self-circulation in the release tower 2, the reaction liquid is collected from the lower part of the release tower 2 and returns to the upper part of the release tower 2 from the outside of the tower, the self-circulation rate of the reaction liquid is 300mL/min, the self-circulation time is 30min, and sulfur-containing gas including H is obtained through reaction and aeration stripping 2 S and CS 2 And the bottom of the releasing tower 2 obtains the water discharged from the releasing tower;
(2) Condensing the sulfur-containing gas obtained in the step (1), wherein the condensation is to spray condensed water and to obtain CS in the sulfur-containing gas 2 Condensing and recycling, wherein the condensation comprises primary condensation and secondary condensation in sequence, the temperature of the condensed water is 0 ℃, the spraying amount of the condensed water is 300mL/min, uncondensed gas is absorbed by alkali liquor, and the alkali liquor is Na with the mass ratio of 2:1 2 CO 3 Solution and NaHCO 3 The pH value of the solution is 8.5, and the flow rate of the alkali liquor is 150mL/min, so as to obtain a sulfur-rich solution;
(3) Biologically oxidizing the sulfur-rich liquid obtained in the step (2), wherein the biological oxidation is performed in a biological oxidation tower 5, aerobic microorganisms in the biological oxidation tower 5 are micro sulfur oxysulfide micro spirillum BDL05 strains, air is introduced into the biological oxidation tower for aeration, the aeration rate is 0.2L/min, liquid circulation is formed between an absorption tower 4 and the biological oxidation tower 5, the liquid flow returned to the absorption tower 4 from the biological oxidation tower 5 is 150mL/min, the sulfur-rich liquid after biological oxidation is subjected to sedimentation separation to obtain sulfur elementary substance solid and supernatant, and the supernatant is returned to the biological oxidation tower 5;
(4) And (3) adsorbing the residual gas after the absorption in the step (2) and the biologically oxidized tail gas in the step (3) by using an adsorption tower 7, wherein an adsorbent filled in the adsorption tower 7 is activated carbon to obtain purified gas.
In this example, according to the detection, the concentration of sulfide in the effluent of the stripping tower was only 4.0mg/L, and CS was not detected 2 The removal rate of sulfur in the process water reaches 99.91 percent; the purified gas obtained contained no H detected 2 S and CS 2 The removal rate almost reaches 100%.
Example 5:
the embodiment provides a method for desulfurizing sulfur-containing salt-containing process water, which is performed by using the desulfurizing device in the embodiment 2 and comprises the following steps of:
(1) Reacting sulfur-containing salt-containing process water with concentrated sulfuric acid, wherein the sulfur-containing salt-containing process water is obtained from a production process in the viscose industry, and S 2- The concentration is 2.2g/L, CS 2 The concentration is 0.42g/L, and the pH value is 10.3; the concentrated sulfuric acid is added in a dropwise manner, the dropwise adding speed is 0.2mL/min, the reaction temperature is controlled to be 45 ℃, the pH value is controlled to be 8.0, aeration and stirring are carried out in the reaction process, the aeration is carried out by introducing air, the aeration speed is 1L/min, the stirring speed is 300rpm, the obtained reaction liquid is subjected to aeration stripping, and the aeration stripping is as follows: introducing air from the lower part of the release tower 2, wherein the aeration rate is 3L/min, the reaction liquid performs self-circulation in the release tower 2, the reaction liquid is collected from the lower part of the release tower 2 and returns to the upper part of the release tower 2 from the outside of the release tower, the self-circulation rate of the reaction liquid is 700mL/min, the self-circulation time is 10min, and sulfur-containing gas including H is obtained through reaction and aeration stripping 2 S and CS 2 And obtaining the effluent of the releasing tower at the bottom of the releasing tower 2;
(2) Condensing the sulfur-containing gas obtained in the step (1), wherein the condensation is to spray condensed water and to obtain CS in the sulfur-containing gas 2 Condensing and recycling, wherein the condensing comprises primary condensing in sequence, the temperature of the condensed water is 10 ℃, the spraying amount of the condensed water is 500mL/min, uncondensed gas is absorbed by alkali liquor, and the alkali liquor is NaHCO 3 The pH value of the solution is 10, and the flow rate of the alkali liquor is 50mL/min, so that a sulfur-rich solution is obtained;
(3) Biologically oxidizing the sulfur-rich liquid obtained in the step (2), wherein the biological oxidation is performed in a biological oxidation tower 5, aerobic microorganisms in the biological oxidation tower 5 are a pluripotent vibrio thioalkalium D301 strain and a halophilic alcaligenes BDH06 strain, air is introduced into the biological oxidation tower for aeration, the aeration rate is 0.6L/min, liquid circulation is formed between an absorption tower 4 and the biological oxidation tower 5, the liquid flow returned to the absorption tower 4 from the biological oxidation tower 5 is 50mL/min, the sulfur-rich liquid after biological oxidation is subjected to sedimentation separation to obtain elemental sulfur solid and supernatant, and the supernatant is returned to the biological oxidation tower 5;
(4) And (3) adsorbing the residual gas after the absorption in the step (2) and the biologically oxidized tail gas in the step (3) by using an adsorption tower 7, wherein an adsorbent filled in the adsorption tower 7 is silica gel to obtain purified gas.
In this example, according to the detection, the concentration of sulfide in the effluent of the releasing tower is only 5.5mg/L, CS 2 The concentration is 3.5mg/L, the removal rate of sulfide in the process water reaches 99.75 percent, and the content of CS is 2 The removal rate of (2) was 99.2%; the purified gas obtained contained no H detected 2 S and CS 2 The removal rate almost reaches 100%.
Comparative example 1:
this comparative example provides a desulfurization unit and method for sulfur-containing brackish process water, which is comparable to the unit of example 1, except that: the release column 2 is not included.
The process is referred to the process in example 3, with the only difference that: and (2) directly taking the reaction liquid in the step (1) as effluent without aeration stripping.
In this comparative example, since the releasing column was not provided, H was released by heat release of the reaction only through the reaction in the reaction column 2 S and CS 2 The sulfur-containing gas is not released sufficiently, but is still partially dissolved in the reaction solution, and the detection shows that the concentration of the sulfide in the effluent is 1235mg/L, CS 2 The concentration is 25mg/L, the removal rate of the sulfide in the process water is only 78.7 percent, and the CS content is 2 The removal rate of (3) was 77.3%.
It can be seen from the above examples and comparative examples that the device of the invention fully converts the sulfur-containing components in the sulfur-containing and salt-containing process water into sulfur-containing gas through the arrangement of the reaction tower and the release tower, and then respectively recovers the carbon disulfide and the hydrogen sulfide components through the arrangement of the structural units such as condensation, absorption, biological oxidation and adsorption, thereby realizing the resource utilization of the sulfur-containing components, achieving the removal rate of sulfur in the process water to be more than 99.7%, and discharging the gas after reaching the standard; the device adopts multiple equipment combination to use, and the stability of device operation is strong, can adjust according to actual conditions is nimble, and the maintenance cost is low, easy operation.
The present invention is illustrated by the following examples, but the present invention is not limited to the above detailed apparatus and method, that is, the present invention is not meant to be limited to the above detailed apparatus and method. It will be apparent to those skilled in the art that any modifications to the present invention, equivalents of the means for substitution and addition of means for carrying out the invention, selection of specific means, etc., are within the scope and disclosure of the invention.
Claims (10)
1. The utility model provides a sulfur-containing and salt-containing process water's desulphurization unit, its characterized in that, desulphurization unit is including the reaction degasification unit, condensing unit, absorption unit, biological oxidation unit and the absorption unit that connect gradually, the reaction degasification unit includes reaction tower and release tower, the liquid phase export of reaction tower links to each other with the liquid phase entry of release tower, the gaseous phase entry of reaction tower and release tower all links to each other with condensing unit's entry, condensing unit's gaseous phase export links to each other with absorption unit's entry, absorption unit's liquid phase export links to each other with biological oxidation unit's entry, absorption unit and biological oxidation unit's gaseous phase export links to each other with absorption unit's entry.
2. The desulfurization device of claim 1, wherein the reaction tower is provided with a gas phase inlet at the lower part and a stirring component inside;
preferably, a cooling circulation channel is arranged on the reaction tower;
preferably, the lower part of the release tower is provided with a gas phase inlet, and the bottom of the release tower is provided with a liquid phase outlet;
preferably, the outer side of the releasing tower is provided with a circulating pipeline which is connected to the upper part of the releasing tower from the lower part of the releasing tower.
3. The desulfurization apparatus according to claim 1 or 2, wherein the condensation unit comprises at least one stage of a condensation tower;
preferably, the condensation unit comprises a primary condensation tower and a secondary condensation tower, and a gas phase outlet of the primary condensation tower is connected with a gas phase inlet of the secondary condensation tower;
preferably, the upper parts of the condensing towers are respectively provided with a condensed water inlet, and the lower parts of the condensing towers are respectively provided with a condensed liquid outlet.
4. The desulfurization apparatus according to any one of claims 1 to 3, wherein the absorption unit comprises an absorption tower, an absorption liquid inlet is provided at an upper portion of the absorption tower;
preferably, the biological oxidation unit comprises a biological oxidation tower, and an air inlet is formed in the lower part of the biological oxidation tower;
preferably, the outlet of the biological oxidation tower is connected with the absorption liquid inlet of the absorption tower.
5. The desulfurization apparatus according to any one of claims 1 to 4, further comprising a settling tower, wherein the liquid phase outlet of the biological oxidation tower is connected to the inlet of the settling tower;
preferably, the settled settling tower is divided into a supernatant and a solid-phase elemental sulfur, and an outlet of the supernatant is connected to the biological oxidation tower;
preferably, the adsorption tower is packed with an adsorbent.
6. A method for desulphurisation of sulphur containing brackish process water by a desulphurisation plant according to any of claims 1 to 5 comprising the steps of:
(1) Reacting sulfur-containing salt-containing process water with acid, and carrying out aeration stripping on the obtained reaction liquid to obtain sulfur-containing gas;
(2) Condensing the sulfur-containing gas obtained in the step (1), condensing and recovering carbon disulfide, and absorbing uncondensed gas by adopting alkali liquor to obtain sulfur-rich liquid;
(3) Carrying out biological oxidation on the sulfur-rich liquid obtained in the step (2) to obtain elemental sulfur;
(4) And (3) adsorbing the residual gas after absorption in the step (2) and the biologically oxidized tail gas in the step (3) to obtain purified gas.
7. The method of claim 6 wherein the source of sulfur-containing brackish process water of step (1) comprises a viscose industry production process;
preferably, the component to be removed in the sulfur-containing and salt-containing process water in the step (1) comprises S 2- And CS 2 Said S 2- The concentration of (A) is 0 to 6.5g/L, and the CS is 2 The concentration of (A) is 0-0.5 g/L;
preferably, the pH value of the sulfur-containing and salt-containing process water in the step (1) is 7-14;
preferably, the acid in the step (1) comprises concentrated sulfuric acid, and the concentrated sulfuric acid is added dropwise;
preferably, the dropping speed of the concentrated sulfuric acid is 0-1.0 mL/min;
preferably, the temperature of the reaction in the step (1) is controlled to be 40-70 ℃;
preferably, the pH of the reaction in the step (1) is controlled to be 6.5-8.0;
preferably, aerating and stirring are carried out during the reaction in the step (1);
preferably, the aeration comprises air aeration, the aeration rate is 1-3L/min, and the stirring rate is 100-300 rpm.
8. The process according to claim 6 or 7, wherein the aeration stripping of step (1) is carried out in a release column;
preferably, the aeration stripping is as follows: introducing air from the lower part of the release tower, wherein the aeration rate is 1-3L/min;
preferably, the reaction liquid is self-circulated in the releasing tower, and is extracted from the lower part of the releasing tower and returned to the upper part of the releasing tower from the outside of the releasing tower;
preferably, the self-circulation rate of the reaction liquid is 300-750 mL/min;
preferably, the self-circulation time of the reaction liquid is 15-30 min;
preferably, the sulfur-containing gas of step (1) comprises H 2 S and CS 2 。
9. The method according to any one of claims 6 to 8, wherein the condensing in step (2) is performed by spraying the condensed water to remove CS in the sulfur-containing gas 2 Condensing and recovering;
preferably, the condensation in the step (2) comprises primary condensation and secondary condensation in sequence;
preferably, the temperature of the condensed water is 0-10 ℃;
preferably, the spraying amount of the condensed water is 300-500 mL/min.
Preferably, the alkaline solution in step (2) is a microbial culture solution, and the main component of the microbial culture solution comprises Na 2 CO 3 Solutions and/or NaHCO 3 A solution;
preferably, the pH value of the alkali liquor in the step (2) is 8.5-10.5;
preferably, the flow rate of the alkali liquor in the step (2) is 50-150 mL/min.
10. The method according to any one of claims 6 to 9, wherein the biological oxidation of step (3) is carried out in a biological oxidation tower;
preferably, the aerobic microorganisms in the biological oxidation tower comprise any one of or a combination of at least two of a pluripotent vibrio thiolyticus D301 strain, a vibrio thiolyticus BDL05 strain or a bacillus alcalophilus BDH06 strain;
preferably, air is introduced into the biological oxidation tower for aeration, and the aeration rate is 0.2-0.6L/min;
preferably, liquid circulation is formed between the absorption tower and the biological oxidation tower, and the flow rate of liquid returned to the absorption tower from the biological oxidation tower is 50-150 mL/min;
preferably, the sulfur-rich liquid obtained after the biological oxidation in the step (3) is subjected to sedimentation separation to obtain sulfur elementary substance solid and supernatant, and the supernatant is returned to the biological oxidation tower;
preferably, the adsorption of the step (4) is carried out by using an adsorption tower;
preferably, the adsorbent filled in the adsorption tower comprises any one of or a combination of at least two of activated carbon, silica gel or activated alumina.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211457877.4A CN115745262A (en) | 2022-11-21 | 2022-11-21 | Desulfurization device and method for sulfur-containing and salt-containing process water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211457877.4A CN115745262A (en) | 2022-11-21 | 2022-11-21 | Desulfurization device and method for sulfur-containing and salt-containing process water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115745262A true CN115745262A (en) | 2023-03-07 |
Family
ID=85333871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211457877.4A Pending CN115745262A (en) | 2022-11-21 | 2022-11-21 | Desulfurization device and method for sulfur-containing and salt-containing process water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115745262A (en) |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0852159B1 (en) * | 1997-01-06 | 2003-05-21 | Haldor Topsoe A/S | Process for the desulphurization of gaseous substrate |
| JP2009172541A (en) * | 2008-01-26 | 2009-08-06 | Chugoku Electric Power Co Inc:The | Air supply amount control method for oxidization of wet-type flue gas desulfurization apparatus |
| CN102399040A (en) * | 2010-09-10 | 2012-04-04 | 沈阳工业大学 | Process for comprehensively treating sulfur dye waste water |
| CN103772250A (en) * | 2014-01-03 | 2014-05-07 | 宜宾丝丽雅股份有限公司 | Method for recovery processing sulfur-containing mixed waste gas in production of viscose |
| CN103920363A (en) * | 2014-03-31 | 2014-07-16 | 龚䶮 | Method and device for treating sulfurous industrial waste gas |
| CN105152490A (en) * | 2015-09-28 | 2015-12-16 | 天津市环境保护科学研究院 | Treatment method and device for tendency of zero liquid discharge of viscose wastewater in inland area |
| CN106310890A (en) * | 2015-06-17 | 2017-01-11 | 中国石油化工股份有限公司 | Method for removing acidic gases through biological technology |
| CN108821429A (en) * | 2018-06-12 | 2018-11-16 | 中国科学院过程工程研究所 | A kind of apparatus system and its processing method of sulfate wastewater treatment |
| CN110155957A (en) * | 2019-06-18 | 2019-08-23 | 赛得利（福建）纤维有限公司 | A method of sulfuric acid is prepared using viscose rayon factory zinc-containing water and NaHS waste liquid |
| CN110467319A (en) * | 2019-09-05 | 2019-11-19 | 山东银鹰化纤有限公司 | A kind of Viscose Waste Water treatment process |
-
2022
- 2022-11-21 CN CN202211457877.4A patent/CN115745262A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0852159B1 (en) * | 1997-01-06 | 2003-05-21 | Haldor Topsoe A/S | Process for the desulphurization of gaseous substrate |
| JP2009172541A (en) * | 2008-01-26 | 2009-08-06 | Chugoku Electric Power Co Inc:The | Air supply amount control method for oxidization of wet-type flue gas desulfurization apparatus |
| CN102399040A (en) * | 2010-09-10 | 2012-04-04 | 沈阳工业大学 | Process for comprehensively treating sulfur dye waste water |
| CN103772250A (en) * | 2014-01-03 | 2014-05-07 | 宜宾丝丽雅股份有限公司 | Method for recovery processing sulfur-containing mixed waste gas in production of viscose |
| CN103920363A (en) * | 2014-03-31 | 2014-07-16 | 龚䶮 | Method and device for treating sulfurous industrial waste gas |
| CN106310890A (en) * | 2015-06-17 | 2017-01-11 | 中国石油化工股份有限公司 | Method for removing acidic gases through biological technology |
| CN105152490A (en) * | 2015-09-28 | 2015-12-16 | 天津市环境保护科学研究院 | Treatment method and device for tendency of zero liquid discharge of viscose wastewater in inland area |
| CN108821429A (en) * | 2018-06-12 | 2018-11-16 | 中国科学院过程工程研究所 | A kind of apparatus system and its processing method of sulfate wastewater treatment |
| CN110155957A (en) * | 2019-06-18 | 2019-08-23 | 赛得利（福建）纤维有限公司 | A method of sulfuric acid is prepared using viscose rayon factory zinc-containing water and NaHS waste liquid |
| CN110467319A (en) * | 2019-09-05 | 2019-11-19 | 山东银鹰化纤有限公司 | A kind of Viscose Waste Water treatment process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2096660C (en) | Process for the removal of sulphur compounds from gases | |
| CN104860474B (en) | Method for carbon sequestration and biological treatment of sulfur-containing waste alkali liquor | |
| CN102040302B (en) | Treatment method of nitrochlorobenzene production wastewater | |
| CN107537293B (en) | Closed cycle microbial desulfurization and elemental sulfur recovery method | |
| RU2664929C1 (en) | Method of biological transformation of bisulphide into elemental sulfur | |
| JP2011523671A (en) | Biogas purification method and system for methane extraction | |
| JP2006081963A (en) | Method and apparatus for treating sludge-containing returned water | |
| CN109293148B (en) | Treatment device and treatment method for sulfur-containing and salt-containing wastewater | |
| CN104548934A (en) | Oxidative desulfurization process for continuous regeneration of desulfurizing agent | |
| CN110643403A (en) | Chemical absorption combined biological removal hydrogen sulfide and sulfur resource technology in methane | |
| CN112142150A (en) | Device and method for synchronously recovering nitrogen and phosphorus in biogas slurry with high efficiency and low consumption | |
| CN112125319A (en) | Process for recovering all components of desulfurization waste liquid | |
| CN101979130B (en) | Method for removing hydrogen sulfide from industrial gas in recycling way | |
| CN110155957B (en) | Method for preparing sulfuric acid by using zinc-containing wastewater and NaHS waste liquid in viscose fiber factory | |
| CN115745262A (en) | Desulfurization device and method for sulfur-containing and salt-containing process water | |
| CN111977915A (en) | Efficient biological decarbonization and denitrification method and system | |
| CN105000745B (en) | A kind of sulfur Gas Fields produced water treatment system | |
| CN212504492U (en) | High-efficient biological decarbonization nitrogen removal system | |
| CN109896692A (en) | A kind of coal-to-olefin and its technique of sewage treatment coupling | |
| CN111097273B (en) | Method and device for treating FCC (fluid catalytic cracking) regenerated flue gas | |
| CN110467312B (en) | Recycling treatment process for white carbon black production wastewater | |
| CN110255688B (en) | Treatment method of high-concentration ammonia nitrogen wastewater | |
| CN209957454U (en) | Pure oxygen circulation system ozone sewage treatment device | |
| JP6113611B2 (en) | Organic wastewater treatment system | |
| CN112194103A (en) | Method for removing odor of acetylene-cleaning waste sulfuric acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |