CN102476893B - Biological desulphurization processing reactor, biological desulphurization processing system, and processing method - Google Patents
Biological desulphurization processing reactor, biological desulphurization processing system, and processing method Download PDFInfo
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Abstract
The invention provides a biological desulphurization processing reactor, a biological desulphurization processing system, and a processing method. The reactor comprises a three phase separator and a reaction zone. The reaction zone comprises an outer cylinder, a gas guiding cylinder and a lower flow guiding cylinder, such that the reaction zone is separated into an air-lift zone, an anoxic zone, and a descent zone. The three phase separator comprises an outer frustum, an inner inverted frustum, an outer sedimentation tank, an inner sedimentation tank, and an overflow groove, such that the three phase separator is separated into three sedimentation zones. Sulfide-containing wastewater is mixed with oxygen-containing water from the air-lift zone in the anoxic zone; under the effect of immobilized microorganisms, the sulfide is partially oxidized into elementary sulfur; the mixture is delivered through the three phase separator arranged above, such that the immobilized carrier is separated from a water phase and a gas phase, and sulfur particles flow out with water. According to the invention, with the structure of the reactor and the processing method, a good fluidized state is maintained, and the loss of the immobilized carrier is inhibited. The reactor, the system and the method are advantaged in high elementary sulfur production rate, good processing capacity, hydraulic load impact resistance, substrate load impact resistance, simple structure, and easy amplification.
Description
Technical field
The invention belongs to field of environment engineering, relate to equipment and technology that a kind of biological desulphurization that is used for sulfur compound liquid is handled, particularly a kind of biological desulphurization treatment reactor and biological desulphurization treatment system and treatment process that is used for sulphide-containing waste water or chemical plant tail gas and selexol process hydrogen absorption liquid.
Background technology
Hydrogen sulfide is the sour gas of a kind of stench, severe toxicity and highly corrosive, but sucks interior just causing death of short period of time on a small quantity, and materials such as metal and cement are all had very strong corrodibility.Sweet natural gas and biogas are green clean energies, often contain a certain amount of hydrogen sulfide, will handle through desulfurization before the pipeline transportation.China's sulfur-containing gas reserves are abundant, and hydrogen sulfide content accounts for 1/4th of national natural gas reserves greater than 1% natural gas reserves, mainly is distributed in the Sichuan Basin, basin, Erdos and basin, Bohai Sea Gulf.Verify Sichuan Basin Tenth Five-Year Plan Period that 990 billion cubic meters are arranged in the Sweet natural gas is high-hydrogen sulfide, particularly fly the extensive discovery of celestial pass group high-hydrogen sulfide natural-gas field in recent years at northeast, the river Triassic system.Along with China's energy consumption constantly increases, sulfur-containing gas is develop and useedd and is imminent.Anaerobic methane production gas technology is to handle the main method of industry and life organic waste water, owing to sulphate reducing bacteria to the avidity of going back protohydrogen far above methanobacteria, must contain a certain proportion of hydrogen sulfide in the biogas, the content of hydrogen sulfide is relevant with sulphate content in the waste water.
It is the most simple and effective method of acid cure hydrogen in Sweet natural gas and the biogas that carbonate alkali lye absorbs, but has but produced the waste water of sulfur compound, and how handling sulfur compound is the matter of utmost importance that the alkali lye desulfurization will solve.Biological desulphurization is a technology of handling the most economical and environmental protection of sulphide-containing waste water, having its ultimate principles of characteristics such as reaction conditions gentleness, less energy-consumption, non-secondary pollution is, under the sulfur oxidizing bacterium effect, sulfide is elemental sulfur by partial oxidation, sulfur granules is removed with coprecipitation mode, alkali obtains regeneration, can be reused for hydrogen sulfide absorption.The reaction formula of this process is as follows:
2OH
-+H
2S→S
2-+2H
2O
The elemental sulfur that generates is an important chemical material, can be used for process industry sulfuric acid, rubber item, sterilant, sulfa, explosive etc.2008, China's sulphur total quantity consumed reached 1,080 ten thousand tons, and wherein import is 9,140,000 tons, and externally interdependency surpasses 90%.
The biological desulfurization process key of set up producing elemental sulfur is 2 points: one, the partial oxidation of sulfide must restriction oxygen (redox-potential-100～-carry out under 300mV) the condition, otherwise sulfide will be vitriol by complete oxidation; Two, elemental sulfur will in time separate, and avoids the inside reactor precipitation to cause obstruction, guarantees the reactor long-time steady operation.At present, biological desulfurization apparatus and technology can not satisfy above two requirements simultaneously.The tradition airlift reactor is that aerobic process is designed, for obtaining higher dissolved oxygen and oxygen transfer speed, often adopts high air flow, and structure of reactor adopts single gas cylinder or multilayer gas cloth device more, and this structure is under low air flow and limit oxygen condition, and cycle efficiency is low.In addition, what is more important, because no effective solid and gas liquid triphase separator, solid retention time is short, fixation support runs off serious.
In addition, bacteria bed is the major equipment of biological desulphurization, fixedly the filler elemental sulfur that causes generating rests in the reactor, not only increased elemental sulfur separation and purification difficulty, and there is an elemental sulfur blockage problem, equipment can't long-time running, and processing power is limited, can not satisfy the needs of the biological desulphurization of extensive Sweet natural gas or biogas.
Summary of the invention
In order to address the above problem, the equipment and the technology that the object of the present invention is to provide a kind of biological desulphurization that is used for sulfur compound liquid to handle specifically provide a kind of biological desulphurization treatment reactor and biological desulphurization treatment system and treatment process that is used for sulphide-containing waste water or chemical plant tail gas and selexol process hydrogen absorption liquid.Utilize equipment of the present invention and treatment process, not only can satisfy the biological desulphurization requirement, can also solve the problem that the sulfide partial oxidation produces elemental sulfur, and can be applied to large-scale industrialization and handle continuously.
For achieving the above object, a kind of biological desulphurization treatment reactor that is used for sulfur compound liquid of the present invention, it is characterized in that, adopt the upflowing inner circulation structure, comprising: be positioned at the reaction zone of bottom, superposed triphase separator and water inlet pipe (31) and rising pipe (22).
Described reaction zone is the inside and outside sleeve structure, by the following guide shell (32) that is positioned at the center, be sleeved on the gas cylinder (33) in described down guide shell (32) outside and be positioned at outermost urceolus (37) and form, reaction zone is divided into three zones: the oxygen-starved area (35) between gas lift district (34), described gas cylinder (33) and the described urceolus (37) between described guide shell (32) down and the described gas cylinder (33), and the described inner decline district (36) of guide shell (32) down.Wherein, described guide shell (32) down is 3:4～4:5 with the diameter ratio of described gas cylinder (33).
In addition, described gas cylinder (33) bottom opening and by stent support in described urceolus, its inboard also is provided with gas distributor (40), this gas distributor (40) be fixed on described urceolus (37) the tube end on, be positioned at described gas lift district under, its air outlet circular array.
Described in addition guide shell down is made up of the cylindrical shell of straight-tube shape and the truncated cone (38) two portions that fall down, the described awl truncated cone (38) down bottom is provided with opening (39), and this bottom opening is close at the bottom of the reactor, diameter of this bottom opening (39) and described gas distributor (40) diameter ratio are between 1:2～2:3, enter down the one-tenth internal recycle interruption that guide shell is made to avoid gas.
Described triphase separator is by the outer truncated cone (29), the interior truncated cone (30), outer settlement barrel (26), interior settlement barrel (23) and overflow groove (21) are formed, wherein, the lower end of the described interior truncated cone (30) is connected with the described upper end of guide shell (32) down of described reaction zone, the described interior upper end of the truncated cone (30) links to each other with the bottom of described outer settlement barrel (26), the upper end of the described outer truncated cone (29) is connected with described outer settlement barrel (26) outside, and, the upper end of the truncated cone outside described (29) is provided with venting port (28) near a side of settlement barrel (26) outside described, leave the gap between the lower end of the described outer truncated cone (29) and the described urceolus (37), described overflow groove (21) is positioned at described settlement barrel (23) inside, described water inlet pipe (31) passes described urceolus (37) and the outer truncated cone (29) stretches into described oxygen-starved area (35), and described rising pipe (22) passes described urceolus (37) and is connected with overflow groove (21) and interior settlement barrel (23).
And the formation of above-mentioned described triphase separator is divided into three negative areas: secondary negative area (27) and the inner three grades of negative areas (24) of interior settlement barrel (23) between the first grade subsides district (25) between described outer settlement barrel (26) and the described urceolus (37), described interior settlement barrel (23) and the described interior truncated cone (30) and the outer settlement barrel (26).
Sulfur compound liquid enters the oxygen-starved area (35) of described reaction zone through described water inlet pipe (31), mix with the oxygen-containing water that comes from described gas lift district (34), under the effect of immobilized microorganism, sulfide is elemental sulfur by partial oxidation, through described triphase separator, and fixation support and water and gas phase separation, wherein, through described first grade subsides district (25), the oxygen-starved area is returned in most of carrier sedimentation, the separated discharge of gas; Through described secondary negative area (27), all the other most carrier sedimentations and warp guide shell (32) down return described reaction zone; Through three grades of negative areas (24), simple substance sulphur granule separates with the few carrier of residue, discharges with water outlet through overflow groove (21), obtains highly purified elemental sulfur through precipitation.
In addition, a kind of biological desulphurization treatment system that is used for sulfur compound liquid of the present invention, it is characterized in that this system comprises: controller (1), air compressor machine (2), upflowing internal recycle biological desulphurization reactor (3), redox-potential electrode (4), pH electrode (5), blender (6), feed supplement pump (7), nutritive medium storage tank (8), pH regulator pump (9), pH regulator storage tank (10), settling tank (11) and flooding velocity controller (12).Wherein, described upflowing internal recycle biological desulphurization reactor has the structure that above-mentioned comprising is positioned at the reaction zone and the superposed triphase separator of bottom.
Described controller (1) is controlled redox-potential and the water inlet pH value in the described reactor (3), described redox-potential electrode (4) records the interior redox-potential of described reactor (3), described air compressor machine of feedback control (2) and described flooding velocity controller (12).When redox-potential is lower than preset value, reduce flooding velocity earlier, the back increases the air input of described air compressor machine (2), the pH value of water inlet records by described pH electrode (5), the described pH regulator pump of feedback control (9), regulate water inlet pH value to 7.0～8.0, when nitrogen content is low in the water inlet, then regularly in water inlet, replenish the nitrogenous source that comprises nitrate or ammonium salt by described feed supplement pump (7), water outlet is through described settling tank (11) post precipitation repeatedly, elemental sulfur is the flocculation precipitation progressively, separates obtaining the biological sulphur of product through dehydration.
In addition, the biological desulphurization treatment process of a kind of sulfur compound liquid of the present invention, it is characterized in that, be above-mentioned treatment process with described biological desulphurization treatment system of the reactor that comprises the reaction zone that is positioned at the bottom and superposed triphase separator structure, specifically comprises the steps:
1) adsorbs fixedly thiobacillus with process for fixation such as activated carbon or biological ceramic particles, under 30 ℃ of environment, carry out 5～10 days pre-cultivation, make thiobacillus cover with fixation support;
2) will be through the pre-incubated immobilization thiobacillus biological desulphurization reactor of packing into, by air flow control redox-potential in the reactor is controlled at-150mV～-100mV, 25 ℃～30 ℃ of temperature are when redox-potential surpasses preset value, reduce earlier flooding quantity, after progressively increase air flow;
3) comprise that the sulfur compound liquid of sulphide-containing waste water or chemical plant tail gas and selexol process hydrogen absorption liquid is through preconditioning pH to 7.5～8.0, enter reactor, according to the different hydraulic detention times of adjusting reactor of water inlet sulfide content, make reactor load maintain 18kgS/ (m
3D);
4) water outlet is through post precipitation repeatedly, and elemental sulfur is the flocculation precipitation progressively, separates obtaining the biological sulphur of product through dehydration.
In sum, a kind of biological desulphurization treatment reactor that is used for sulphide-containing waste water and selexol process hydrogen absorption liquid of the present invention comprises top triphase separator and lower reaction zone two portions.Reaction zone is made up of gas lift district and oxygen-starved area, and sulfide is immobilized the sulfur oxidizing bacterium partial oxidation in the oxygen-starved area be elemental sulfur.By guide shell under middle the increasing in gas cylinder, dwindled the cross-sectional area in gas lift district, make it under low air flow, still keep good flowability.Elemental sulfur is in fluidized state, flows out with water outlet easily.Following guide shell is connected with triphase separator, make gas lift district, first grade subsides district, secondary negative area and following guide shell form the closed loop, thereby forming the self-suction that descends in the guide shell down, improved the settling efficiency of secondary negative area, greatly prolonged solid retention time.
The principle of work that is used for the biological desulphurization treatment reactor of sulphide-containing waste water or chemical plant tail gas and selexol process hydrogen absorption liquid of the present invention: sulphide-containing waste water enters the hypoxia response district by water inlet pipe (31), mix with the current that carry oxygen that come from the gas lift district, under the effect of sulfur-oxidizing bacteria, the sulfide partial oxidation is an elemental sulfur.The elemental sulfur that generates enters the circulation between gas lift district and the oxygen-starved area, is brought in the triphase separator with water outlet, separates with the partial fixing carrier in the one-level settling region, enters the two-stage precipitation district.In the two-stage precipitation district, because the downward suction that following thrust-augmenting nozzle forms, the fixation support that density is bigger is inhaled into down thrust-augmenting nozzle, and the less simple substance sulphur granule of density enters three grades of settling regions with the water outlet rising.In three grades of settling regions, separate once more between simple substance sulphur granule and the surplus fixation support not, reach fully and separate.Sulfur granules enter overflow groove (21) with water outlet, outflow reactor obtains highly purified sulphur through precipitation.
The invention has the advantages that:
A kind of biological desulphurization treatment reactor that is used for sulphide-containing waste water or chemical plant tail gas and selexol process hydrogen absorption liquid of the present invention and biological desulphurization treatment system and treatment process possess following characteristic: have good fluidized state under (1) low air flow, not only provide The optimum reaction conditions, and avoided the accumulation of elemental sulfur in reactor to cause obstruction for sulfide transforms elemental sulfur; (2) even high effective three phase separator under high fluidized and short hydraulic detention time, still can effectively stop fixation support to run off, prolong solid retention time, and the less elemental sulfur of density can be discharged smoothly, just can obtain highly purified elemental sulfur through simple precipitation; (3) owing to realized the elemental sulfur ON-LINE SEPARATION, so this equipment continuously-running, the Operation and Maintenance cost is low, can be used for the biological desulphurization of gases such as extensive Sweet natural gas and biogas.
Description of drawings
Fig. 1 is the structural representation of upflowing internal recycle biological desulphurization reactor of the present invention.
Fig. 2 utilizes the biological desulphurization treatment system of upflowing internal recycle biological desulphurization reactor of the present invention to constitute synoptic diagram.
Fig. 3 is the result curve figure that utilizes the simulation sulphide-containing waste water biological desulphurization that biological desulfurization process of the present invention carries out.
Reference numeral
1 controller
2 air compressor machines
3 upflowing internal recycle biological desulphurization reactors
4 redox-potential electrodes
5 pH electrode
6 blenders
7 feed supplement pumps
8 nutritive medium storage tanks
9 pH regulator pumps
10 pH regulator storage tanks
11 settling tanks
12 flooding velocity controllers
21 overflow grooves
22 rising pipes
Settlement barrel in 23
24 3 grades of negative areas
25 first grade subsides districts
26 outer settlement barrels
27 secondary negative areas
28 venting ports
The 29 outer truncateds cone
The 30 interior truncateds cone
31 water inlet pipes
32 times guide shells
33 gas cylinders
34 gas lift districts
35 oxygen-starved areas
36 descend distinguishes
37 urceolus
Fall the truncated cone for 38 times
39 times bottom openings of falling the truncated cone
40 gas distributors
Embodiment
Below in conjunction with the drawings and specific embodiments biological desulphurization reactor of the present invention and biological desulphurization treatment system and treatment process are described in detail.
Fig. 1 is the structural representation of upflowing internal recycle biological desulphurization reactor of the present invention., as shown in Figure 1, biological desulphurization reactor 3 of the present invention is made of the reaction zone that is positioned at the bottom, superposed triphase separator, water inlet pipe 31 and rising pipe 22.
Reaction zone by the following guide shell 32 that is positioned at the center, be sleeved on the gas cylinder 33 in described down guide shell 32 outsides and be positioned at outermost urceolus 37 and constitute, the concentric sleeve of three floor is divided into three zones with reaction zone: the oxygen-starved area 35 between gas lift district 34, described gas cylinder 33 and the described urceolus 37 between described guide shell 32 down and the described gas cylinder 33, and the described decline district 36 of guide shell 32 inside down.In addition, gas cylinder 33 bottom openings and by stent support urceolus 37 the tube end on, also be provided with gas distributor 40 in the inboard of gas cylinder 33, this gas distributor 40 be fixed on urceolus 37 the tube end on, be positioned at gas lift district 34 under, its air outlet circular array.Wherein, following guide shell 32 is 3:4～4:5 with the diameter ratio of gas cylinder 33, to obtain best upper lifting force.
In addition, following guide shell 32 is made up of the cylindrical shell of straight-tube shape and the truncated cone 38 two portions that fall down, the bottom of the described truncated cone 38 of awl down is provided with opening 39, and this bottom opening 39 is close at the bottom of the reactor, the diameter of this bottom opening 39 and gas distributor 40 diameter ratios are between 1:2～2:3, cause internal recycle to interrupt to avoid gas to enter down guide shell 32.
In reaction zone, pressurized air is 34 risings in the gas lift district, form internal recycle between gas lift district 34 and oxygen-starved area 35, and gas is discharged from venting port 28.Because the following guide shell 32 in the gas cylinder 33 has reduced the cross-sectional area in gas lift district 34, under less air flow, also can obtain higher apparent gas speed.
Triphase separator is by overflow groove 21, interior settlement barrel 23, outer settlement barrel 26, the outer truncated cone 29, the interior truncated cone 30 is formed, wherein, the lower end of the interior truncated cone 30 is connected with the described upper end of guide shell 32 down of described reaction zone, the interior upper end of the truncated cone 30 links to each other with outer settlement barrel 26 bottoms, the upper end of the outer truncated cone 29 is connected with outer settlement barrel 26 outsides, and, the upper end of the truncated cone 29 is provided with venting port 28 near a side of outer settlement barrel 26 outside, leave the gap between the lower end of the outer truncated cone 29 and the described urceolus 37, overflow groove 21 is positioned at described settlement barrel 23 inside, water inlet pipe 31 passes urceolus 37 and the outer truncated cone 29 stretches into oxygen-starved area 35, and rising pipe 22 passes urceolus 37 and is connected with overflow groove 21 and interior settlement barrel 23.
Sulphide-containing waste water enters oxygen-starved area 35 through water inlet pipe 31, mixes with the oxygen-containing water stream that comes from gas lift district 34, issues first portion oxidation generation elemental sulfur in the effect of immobilization sulfur oxidizing bacterium.Elemental sulfur arrives triphase separator with internal recycle, enter first grade subsides district 25 through venting port 28, after the partial fixing carrier separates, flow into secondary negative area 27 with water outlet, separate with most of fixation support, rising enters three grades of negative areas 24, after a small amount of fixation support of remainder separates, enters overflow groove 21 and discharges reactor with water outlet.
In the triphase separator structure of reactor 3, the interior truncated cone 30 links to each other with following guide shell 32, mainly plays to change the gas motion direction and collect secondary negative area 27 sedimentary effects.The top of the outer truncated cone 29 links to each other with the interior truncated cone 30 and outer settlement barrel 26, and a side of settlement barrel 26 is provided with venting port 28 outside the top is close.Multistage negative area makes reactor have long solid retention time when having the active fluidization attitude.Gas lift district 34 upper lifting forces pass through 39 pairs of following guide shells 32 interior suction that form of following reverse taper 38 bottom openings of guide shell 32 down, forming katabatic drainage in the guide shell 32 down, decline suction appears in the secondary negative area 27 that guide shell 32 tops are connected, and strengthens the secondary negative area.Between gas lift district 34, first grade subsides district 25, secondary negative area 27, decline district 36, form second circulation, effectively prolonged solid retention time.The truncated cone 38 that falls down can effectively stop gas to enter down guide shell 32.The upper end of following guide shell 32 links to each other with the interior truncated cone 30 of triphase separator, make gas lift district 34, first grade subsides district 25, secondary negative area 27 and following guide shell 32 form the closed loop, thereby, improved the settling efficiency of secondary negative area forming the self-suction that descends in the guide shell 32 down.
Fig. 2 utilizes the biological desulphurization treatment system that is used for sulphide-containing waste water of upflowing internal recycle biological desulphurization reactor of the present invention to constitute synoptic diagram.As shown in Figure 2, biological desulphurization treatment system of the present invention comprises: controller 1, air compressor machine 2, upflowing internal recycle biological desulphurization reactor 3, redox-potential electrode 4, pH electrode 5, blender 6, feed supplement pump 7, nutritive medium storage tank 8, pH regulator pump 9, pH regulator storage tank 10, settling tank 11 and flooding velocity controller 12.
Redox-potential in the controller 1 major control reactor 3 and water inlet pH value, redox-potential electrode 4 records redox-potential, feedback control air compressor machine 2 and flooding velocity controller 12 in the reactor.When redox-potential is lower than preset value, reduce flooding velocity earlier, the back increases the air input of air compressor machine 2.The pH value records by pH value electrode 5, and feedback control pH regulator pump 9 extracts regulator solution from pH regulator with storage tank 10, regulates water inlet pH value to 7.0～8.0.If nitrogen content is low in the water inlet, need regularly from nutritive medium storage tank 8, in water inlet, to replenish nitrogenous sources such as nitrate or ammonium salt by feed supplement pump 7.Water outlet is through more than 11 post precipitation of settling tank, and elemental sulfur is the flocculation precipitation progressively, separates obtaining the biological sulphur of product through dehydration.
In addition, the biological desulphurization treatment process that is used for sulphide-containing waste water of utilizing upflowing internal recycle biological desulphurization reactor of the present invention of the present invention specifically comprises the steps:
1) adsorbs fixedly thiobacillus with process for fixation such as activated carbon or biological ceramic particles, under 30 ℃ of environment, carry out 5～10 days pre-cultivation, make thiobacillus cover with fixation support.
2) will be through the pre-incubated immobilization thiobacillus biological desulphurization reactor of packing into, by air flow control redox-potential in the reactor is controlled at-100mV～-200mV, 25 ℃～30 ℃ of temperature are when redox-potential surpasses preset value, reduce earlier flooding quantity, after progressively increase air flow.
3) comprise that the sulfur compound liquid of sulphide-containing waste water or chemical plant tail gas and selexol process hydrogen absorption liquid is through preconditioning pH to 7.5～8.0, enter reactor, according to the different hydraulic detention times of adjusting reactor of water inlet sulfide content, make reactor load maintain 18kgS/ (m
3D).
4) water outlet is through post precipitation repeatedly, and elemental sulfur is the flocculation precipitation progressively, separates obtaining the biological sulphur of product through dehydration.
Embodiment 1: the simulation sulphide-containing waste water
1) immobilization thiobacillus is with Na
2S
2O
35～10g/L, KNO
35～10g/L, NaHCO
32g/L, KH
2PO
40.1g/L 30 ℃ of static cultivations of substratum 14 days mix bacterium liquid with fixation support, continue to cultivate 10～14 days with aforesaid method per 3～4 days replacing one subcultures;
2) reactor start-up places reactor with activatory immobilization thiobacillus, and the reactor initial load is controlled at 1～3kgS/ (m
3D), per 3 days loads are heightened 2kgS/ (m
3D).
3) 30～35 ℃ of water temperatures of water inlet, redox potential value (redox-potential) be controlled at-150～-100mV, when the redox-potential value is lower than set(ting)value, increases air flow and reduce water inlet; When the redox-potential value is higher than set(ting)value, increases flooding quantity and reduce air flow.
Be parameter and the result of embodiment 1 below:
Simulated wastewater (mg/L): Na
2S100～500, NaHCO
320, K
2HPO
410, KNO
320, pH7.0
Reactor load: 0.96～4.8kgS/ (m
3D)
Redox potential :-200～-150mV
Elemental sulfur production rate: 84～92%
The sulfide decreasing ratio:〉98%
Fig. 3 is the result curve figure that utilizes the simulation sulphide-containing waste water biological desulphurization that biological desulfurization process of the present invention carries out.As seen from Figure 3, handle through the present invention, the sulfide 98% or more is removed, and most of form with elemental sulfur is recovered, and elemental sulfur is a kind of important chemical basic material, the innoxious and recycling treatment of realization sulfide.
Embodiment 2: the absorption liquid of gas removal hydrogen sulfide
Simulation H 2 S-containing gas (v/v): 4%H
2S, 96%N
2
1) with pH10～11,0.1M NaHCO
3/ Na
2CO
3Be absorption liquid, the concentration that forms sulfide after the material filling type gas-liquid exchange tower absorbs is the 100mmolS/L absorption liquid, pH7.5～8.0, and sulfide content 60～100mmol, this absorption liquid is pumped to blender, enters reactor.
2) according to the concentration of water inlet sulfide, the hydraulic detention time of conditioned reaction device keeps the bio-desulfurization device load at 12kgS/ (m
3D) about, through handling the sulfide decreasing ratio of absorption liquid〉98%, the elemental sulfur production rate 〉 80%, the absorption liquid pH value after the processing rises to 10, can be used for the H 2 S-containing gas absorption cleaning once more.
The sulphide-containing waste water treatment process that the present invention announced, not only can be used for industrial sulphide-containing waste water such as paper mill, tannery handles, the manipulation of regeneration that also can be used for H 2 S-containing gas alkaline process absorption liquids such as Sweet natural gas or chemical industry tail gas, generating biological sulphur in the sweetening process is a kind of important chemical basic raw material, realizes the innoxious and recycling treatment of sulfide.Processing sulphide-containing waste water sulfide content through this sulfur removal technology is reduced to below the 0.01mM, reaches state sewage emission standard, realizes alkali regeneration when H 2 S-containing gas alkaline process absorption liquid is removed sulfide, can be used for gas absorption once more.
It should be noted last that above embodiment is only unrestricted in order to technical scheme of the present invention to be described.Although the present invention is had been described in detail with reference to embodiment, those of ordinary skill in the art is to be understood that, technical scheme of the present invention is made amendment or is equal to replacement, do not break away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (5)
1. a biological desulphurization treatment reactor that is used for sulfur compound liquid is characterized in that, adopts the upflowing inner circulation structure, comprising: be positioned at the reaction zone of bottom, superposed triphase separator and water inlet pipe (31) and rising pipe (22),
Described reaction zone is the inside and outside sleeve structure, by the following guide shell (32) that is positioned at the center, be sleeved on the gas cylinder (33) in described down guide shell (32) outside and be positioned at outermost urceolus (37) and form, reaction zone is divided into three zones: the oxygen-starved area (35) between gas lift district (34), described gas cylinder (33) and the described urceolus (37) between described guide shell (32) down and the described gas cylinder (33), and the inner decline district (36) of described guide shell (32) down
Wherein, described gas cylinder (33) bottom opening and by stent support in described urceolus, its inboard also is provided with gas distributor (40), this gas distributor (40) be fixed on described urceolus (37) the tube end on, be positioned at described gas lift district under, its air outlet circular array;
Described triphase separator is by the outer truncated cone (29), the interior truncated cone (30), outer settlement barrel (26), interior settlement barrel (23) and overflow groove (21) are formed, wherein, the lower end of the described interior truncated cone (30) is connected with the described upper end of guide shell (32) down of described reaction zone, the described interior upper end of the truncated cone (30) links to each other with the bottom of described outer settlement barrel (26), the upper end of the described outer truncated cone (29) is connected with described outer settlement barrel (26) outside, and, the upper end of the truncated cone outside described (29) is provided with venting port (28) near a side of settlement barrel (26) outside described, leave the gap between the lower end of the described outer truncated cone (29) and the described urceolus (37), described overflow groove (21) is positioned at described settlement barrel (23) inside, described water inlet pipe (31) passes described urceolus (37) and the outer truncated cone (29) stretches into described oxygen-starved area (35), described rising pipe (22) passes described urceolus (37) and is connected with overflow groove (21) and interior settlement barrel (23)
The formation of above-mentioned triphase separator is divided into three negative areas with described triphase separator: secondary negative area (27) and the inner three grades of negative areas (24) of interior settlement barrel (23) between the first grade subsides district (25) between described outer settlement barrel (26) and the described urceolus (37), described interior settlement barrel (23) and the described interior truncated cone (30) and the outer settlement barrel (26);
Sulfur compound liquid enters the oxygen-starved area (35) of described reaction zone through described water inlet pipe (31), mix with the oxygen-containing water that comes from described gas lift district (34), under the effect of immobilized microorganism, sulfide is elemental sulfur by partial oxidation, through described triphase separator, and fixation support and water and gas phase separation, wherein, through described first grade subsides district (25), the oxygen-starved area is returned in most of carrier sedimentation, the separated discharge of gas; Through described secondary negative area (27), all the other most carrier sedimentations and warp guide shell (32) down return described reaction zone; Through three grades of negative areas (24), simple substance sulphur granule separates with the few carrier of residue, discharges with water outlet through overflow groove (21), obtains highly purified elemental sulfur through precipitation;
Described guide shell down is made up of straight barrel and the following truncated cone (38) two portions, and the described truncated cone (38) bottom of falling down is provided with opening (39).
2. the biological desulphurization treatment reactor that is used for sulfur compound liquid as claimed in claim 1 is characterized in that, described guide shell down is 3:4～4:5 with the diameter ratio of described gas cylinder.
3. the biological desulphurization treatment reactor that is used for sulfur compound liquid as claimed in claim 1 or 2, it is characterized in that, the diameter of described bottom opening (39) and described gas distributor (40) diameter ratio are between 1:2～2:3, enter down the one-tenth internal recycle interruption that guide shell is made to avoid gas.
4. biological desulphurization treatment system of utilizing any described reactor in the claim 1～3, it is characterized in that, this system comprises: controller (1), air compressor machine (2), any described upflowing internal recycle biological desulphurization reactor (3) in the claim 1～3, redox-potential electrode (4), pH electrode (5), blender (6), feed supplement pump (7), nutritive medium storage tank (8), pH regulator pump (9), pH regulator storage tank (10), settling tank (11) and flooding velocity controller (12)
Described controller (1) is controlled redox-potential and the water inlet pH value in the described reactor (3), described redox-potential electrode (4) records the interior redox-potential of described reactor (3), described air compressor machine of feedback control (2) and described flooding velocity controller (12), when redox-potential is lower than preset value, reduce flooding velocity earlier, the back increases the air input of described air compressor machine (2), the pH value of water inlet records by described pH value electrode (5), the described pH regulator pump of feedback control (9) extracts regulator solution from pH regulator with storage tank (10), regulate water inlet pH value to 7.0～8.0, when nitrogen content is low in the water inlet, then regularly to water inlet, replenish the nitrogenous source that comprises nitrate or ammonium salt from nutritive medium storage tank (8) by described feed supplement pump (7), water outlet is through described settling tank (11) post precipitation repeatedly, elemental sulfur is the flocculation precipitation progressively, separates obtaining the biological sulphur of product through dehydration.
5. the biological desulphurization treatment process of a sulfur compound liquid is characterized in that, is the described treatment process of utilizing the biological desulphurization treatment system of any described reactor in the claim 1～3 of claim 4, specifically comprises the steps:
1) adsorbs fixedly thiobacillus with process for fixation such as activated carbon or biological ceramic particles, under 30 ℃ of environment, carry out 5～10 days pre-cultivation, make thiobacillus cover with fixation support;
2) will be through the pre-incubated immobilization thiobacillus biological desulphurization reactor of packing into, by air flow control redox-potential in the reactor is controlled at-150mV～-100mV, 25 ℃～30 ℃ of temperature are when redox-potential surpasses preset value, reduce earlier flooding quantity, after progressively increase air flow;
3) comprise that the sulfur compound liquid of sulphide-containing waste water or chemical plant tail gas and selexol process hydrogen absorption liquid is through preconditioning pH to 7.5～8.0, enter reactor, according to the different hydraulic detention times of adjusting reactor of water inlet sulfide content, make reactor load maintain 18kgS/ (m
3D);
4) water outlet is through post precipitation repeatedly, and elemental sulfur is the flocculation precipitation progressively, separates obtaining the biological sulphur of product through dehydration.
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| CN103288205B (en) * | 2013-06-19 | 2014-10-22 | 河南城建学院 | Integrated composite type bio-membrane reactor |
| CN104628488B (en) * | 2013-11-08 | 2017-12-01 | 安琪酵母股份有限公司 | A kind of biological sulfur fertilizer and preparation method thereof |
| CN105060470B (en) * | 2015-09-16 | 2017-09-29 | 中国环境科学研究院 | A kind of high load capacity metabolic regulation bioreactor and method of wastewater treatment |
| CN107162198B (en) * | 2017-07-20 | 2023-06-02 | 重庆阳正环保科技股份有限公司 | High-difficulty wastewater purification device |
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| CN108905599B (en) * | 2018-09-04 | 2023-09-01 | 浙江大学 | Internal circulation biological desulfurization reactor and method |
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Application publication date: 20120530 Assignee: Yabang green process and new materials research institute Nanjing Co., Ltd Assignor: Institute of Process Engineering, Chinese Academy of Sciences Contract record no.: X2019110000014 Denomination of invention: Biological desulphurization processing reactor, biological desulphurization processing system, and processing method Granted publication date: 20130731 License type: Common License Record date: 20191227 |