CN102921286A - Device and method for removing hydrogen sulfide and recovering sulfur elementary substances in micro-oxygenation method - Google Patents
Device and method for removing hydrogen sulfide and recovering sulfur elementary substances in micro-oxygenation method Download PDFInfo
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- CN102921286A CN102921286A CN201210452317XA CN201210452317A CN102921286A CN 102921286 A CN102921286 A CN 102921286A CN 201210452317X A CN201210452317X A CN 201210452317XA CN 201210452317 A CN201210452317 A CN 201210452317A CN 102921286 A CN102921286 A CN 102921286A
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Abstract
The invention relates to a device for removing hydrogen sulfide in waste water and waste gas and recovering sulfur elementary substances in a micro-oxygenation method. The device comprises an oxidation unit, a circulation unit and a control platform, wherein the top end of the oxidation unit is provided with a probe and a gas exhaust port which are connected with the control platform, the bottom end of the oxidation unit is provided with a gas distribution device, a liquid outlet and a sulfur elementary substance recovering port, and the circulation unit is provided with a waste gas or waste water inlet, an air inlet, a one-way valve and a peristaltic pump. The invention further provides a method utilizing the device to remove the hydrogen sulfide and recover the sulfur elementary substances in the micro-oxygenation method. The device does not need stuffing, chemical reagents or microorganisms, is low in cost, efficient, safe and moderate in condition, and can be used at normal temperature and pressure. The blast volume of an air blower can be controlled by a computer according to desulfuration effect so as to achieve automation control of a system. By means of inputting the quantity of oxygen with a volume ratio of less than 2%, the removal effect that the content of the hydrogen sulfide is lower than 1ppm/V can be achieved, the hydrogen sulfide can be oxidized into elemental sulfur, and therefore secondary pollution which can be possibly caused is avoided.
Description
Technical field:
The present invention relates to a kind of low-level oxidation method and remove the apparatus and method of hydrogen sulfide in waste water, the waste gas, can realize the recovery of elemental sulfur simultaneously, belong to environmental protection technical field.
Background technology:
In natural gas purification, petroleum refining, Coal Chemical Industry, process hides, pharmacy, papermaking, synthetic chemistry fiber, rubber regeneration and the ﹠ Mud process, the H 2 S-containing gas (H of generation
2S), cause very large secondary pollution, had a strong impact on the ambient atmosphere environment.In a large amount of recovered waters and life factory effluent that the oil and natural gas drill-well operation produces, often contain a large amount of dissolubility hydrogen sulfide, consider the toxicity of hydrogen sulfide, the processing of these sulfide hydrogen liquid is subject to increasing attention.Hydrogen sulfide is colourless gas, the hydrogen sulfide of low concentration has strong rotten egg foul odour, they not only directly are detrimental to health, growth to animal is extremely unfavorable, and under aerobic and damp and hot condition, severe corrosion equipment, pipeline and instrument etc., and can accelerate the aging of nonmetallic materials; Therefore, the correlative study of hydrogen sulfide receives much concern in removal waste water, the waste gas.
Summary of the invention:
For the deficiencies in the prior art, the invention provides the device that a kind of low-level oxidation method is removed hydrogen sulfide in waste water, the waste gas, the present invention also provides a kind of and utilizes this device to remove hydrogen sulfide in waste water, the waste gas and realize simultaneously the method for elemental sulfur recovery.Adopt method of the present invention not need filler effectively with the hydrogen sulfide removal in waste water or the waste gas, need not to add chemicals and microorganism, environmental friendliness is easy to engineering and uses.
The term explanation:
ORP value: the abbreviation of oxidation-reduction potential, the relative extent of its characterized medium oxidisability or reproducibility.
ORP/pH probe: the probe that can detect simultaneously ORP value and pH value.
Technical scheme of the present invention is as follows:
A kind of low-level oxidation method is removed hydrogen sulfide and is reclaimed the device of sulphur, comprises oxidation unit, cycling element and control platform; The top of oxidation unit is provided with the ORP/pH probe and is connected with the control platform, and the bottom of oxidation unit is provided with gas pipe, liquid outlet and sulphur simple substance and reclaims mouth; The bottom of cycling element is provided with peristaltic pump, and the bottom of cycling element is communicated with the bottom of oxidation unit, and the top of cycling element is communicated with the top of oxidation unit, and the top of cycling element is provided with gas discharge outlet, and oxidation unit and cycling element consist of the circulatory system; Be provided with the inlet flow rate meter between the top of cycling element and the bottom, be provided with mass air flow sensor between inlet flow rate meter and the peristaltic pump, mass air flow sensor is connected with air blast, is provided with check valve between inlet flow rate meter and the gas discharge outlet fluid in the cycling element can only be flowed by the direction of inlet flow rate meter sensing peristaltic pump.
Gas pipe is used for control and enters the interior air or oxygen amount of oxidation unit, the amount that air blast is used for blasting air and blasts air by mass air flow sensor control, the inlet flow rate meter is used for waste water or the waste gas that control enters cycling element, and peristaltic pump pumps into waste water or waste gas and the air that blasts and carries out oxidation processes in the oxidation unit; The ORP/pH probe is for detection of the pH value in the oxidation unit and ORP value, and transfer data to the control platform, the control platform is controlled inlet flow rate meter, mass air flow sensor and gas pipe automatically according to the pH value in the oxidation unit and ORP value, and realization is controlled waste water or waste gas, the air that blasts and the automation that enters the air or oxygen amount in the oxidation unit.
Preferred according to the present invention, described oxidation unit is straight shape pipe, highly is 0.6 ~ 5m, and internal diameter is 3 ~ 20cm; Particularly preferably highly be 1m, internal diameter is 4cm.
Preferred according to the present invention, described cycling element is that internal diameter is at the pipeline of 1 ~ 5cm.
Preferred according to the present invention, add digestive juice in the described oxidation unit.
Preferred according to the present invention, oxidation unit and cycling element inwall are provided with erosion shield, erosion shield preferably polyethylene, polyvinyl chloride.
A kind of method of utilizing said apparatus low-level oxidation method to remove hydrogen sulfide and recovery sulphur simple substance, step is as follows:
The digestive juice of packing in the oxidation unit, waste water or the waste gas that will contain hydrogen sulfide enter cycling element by the inlet flow rate meter, and air blast blasts air in the cycling element and blasts the amount of air by mass air flow sensor control; Waste water and air, perhaps, waste gas and air pump in the oxidation unit by peristaltic pump, control the air or oxygen amount that enters in the oxidation unit by gas pipe, waste water and air, perhaps, waste gas and air carry out oxidation processes with digestive juice in oxidation unit, hydrogen sulfide after oxidation processes is converted into elemental sulfur and reclaims a mouthful recovery by sulphur simple substance, and not hydrogen sulfide containing gas is discharged by gas discharge outlet, and not hydrogen sulfide containing liquid is discharged by liquid outlet.
Preferred according to the inventive method, waste water and air, perhaps, waste gas and air circular treatment in the circulatory system of oxidation unit and cycling element formation is not less than twice.
Preferred according to the inventive method, enter the volume content that oxygen in the oxidation unit accounts for total gas and be not higher than 2%.
Preferred according to the inventive method, enter that cycling element contains the waste water of hydrogen sulfide or the temperature of waste gas is 15～35 ℃, preferred 20～30 ℃, most preferably 20～25 ℃.
Preferred according to the inventive method, the pH of the digestive juice of packing into is 7.0 ~ 8.0, particularly preferably 7.5.
Preferred according to the inventive method, the flow velocity that blasts air is the 5-30% of sulfide hydrogen waste gas flow velocity, particularly preferably 30%.
Preferred according to the inventive method, the flow velocity that sulfide hydrogen waste gas enters oxidation unit is 0.05 ~ 5L/ minute.
The used digestive juice of the present invention is the digestive juice in the common municipal sewage plant digester in the prior art, also can be the liquid of other wastewater treatment equipments, can realize like this utilization of refuse secondary, this digestive juice can be changed according to the hydrogen sulfide removal effect in good time.
Technical characterstic of the present invention and excellent results are as follows:
1, the low-level oxidation method of the present invention device removing hydrogen sulfide and reclaim sulphur does not need filler, chemical reagent and microorganism, and cost is low, efficient, safety, mild condition, can use under the normal temperature and pressure.
2, air blast of the present invention can be controlled the blow rate required by computer according to desulfurized effect, can realize the automation control of system.
3, low-level oxidation method of the present invention is removed the device inner wall anti-corrosive of hydrogen sulfide and recovery sulphur, prevents the corrosion of sulphur and hydrogen sulfide.
4, the present invention is elemental sulfur with Oxidation of Hydrogen Sulfide, has avoided the secondary pollution that may cause, and desulfuration efficiency can reach more than 98%.
5, low-level oxidation method of the present invention is removed the method for hydrogen sulfide in waste water, the waste gas, and input can realize that less than the amount of oxygen of 2% volume ratio hydrogen sulfide content is lower than the removal effect of 1ppm V.
6, low-level oxidation method of the present invention is removed the method for hydrogen sulfide in waste water, the waste gas, can make minimumization of concentration of hydrogen sulfide by repeatedly circulating.
7, low-level oxidation method of the present invention is removed the method for hydrogen sulfide in waste water, the waste gas, realizes the oxidation of hydrogen sulfide by blasting air, and raw material is easy to get, and is simple to operate.
Description of drawings:
Fig. 1 is the structural representation that low-level oxidation method of the present invention is removed hydrogen sulfide and recovery sulphur device;
Among Fig. 1,1. inlet flow rate meter, 2. air blast, 3. mass air flow sensor, 4. peristaltic pump, 5. sulphur simple substance reclaims mouthful, 6. liquid outlet, 7. gas pipe, 8. oxidation unit, 9.ORP/pH probe, 10. gas discharge outlet, 11. control platforms, 12. check valves, 13. cycling elements.
Fig. 2 is hydrogen sulfide removal effect curve figure under the embodiment of the invention 2 ~ 4 different disposal conditions.
Fig. 3 is hydrogen sulfide removal effect curve figure under the embodiment of the invention 5 ~ 7 different disposal conditions.
The specific embodiment:
Also the present invention will be further described by reference to the accompanying drawings below by specific embodiment, but be not limited to this.
Used digestive juice among the embodiment is taken from the municipal sewage plant; ORP/pH probe among the embodiment is conventional commercial equipment.
Embodiment 1:
A kind of low-level oxidation method is removed hydrogen sulfide and is reclaimed the device of sulphur, comprises oxidation unit 8, cycling element 13 and control platform 11; The top of oxidation unit 8 is provided with ORP/pH probe 9 and is connected with control platform 11, and the bottom of oxidation unit 8 is provided with gas pipe 7, liquid outlet 6 and sulphur simple substance and reclaims mouth 5; The bottom of cycling element 13 is provided with peristaltic pump 4, the bottom of cycling element 13 is communicated with the bottom of oxidation unit 8, the top of cycling element 13 is communicated with the top of oxidation unit 8, and the top of cycling element 13 is provided with gas discharge outlet 10, and oxidation unit 8 consists of the circulatory system with cycling element 13; Be provided with inlet flow rate meter 1 between the top of cycling element 13 and the bottom, be provided with mass air flow sensor 3 between inlet flow rate meter 1 and the peristaltic pump 4, mass air flow sensor 3 is connected with air blast 2, is provided with check valve 12 between inlet flow rate meter 1 and the gas discharge outlet 10 fluid in the cycling element 13 can only be flowed by the direction of inlet flow rate meter 1 sensing peristaltic pump 4.
Gas pipe 7 is used for controlling the air or oxygen amount that enters in the oxidation unit 8, the amount that air blast 2 is used for blasting air and blasts air by mass air flow sensor 3 controls, inlet flow rate meter 1 is used for waste water or the waste gas that control enters cycling element 13, and peristaltic pump 4 pumps into waste water or waste gas and the air that blasts and carries out oxidation processes in the oxidation unit 8; ORP/pH probe 9 is for detection of pH value and ORP value in the oxidation unit 8, and transfer data to control platform 11, control platform 11 is controlled inlet flow rate meter 1, mass air flow sensor 3 and gas pipe 7 automatically according to the pH value in the oxidation unit 8 and ORP values, and realization is controlled waste water or waste gas, the air that blasts and the automation that enters the air or oxygen amount in the oxidation unit.
In the present embodiment, oxidation unit 8 is straight shape pipe, and it highly is 1m, and internal diameter is 4cm; Cycling element is that internal diameter is the pipeline of 2cm.Oxidation unit 8 and cycling element 13 inwalls are provided with the polyethylene anticorrosion erosion resisting coating.
Embodiment 2:
The method that the low-level oxidation method is removed hydrogen sulfide and reclaimed sulphur simple substance is installed in a kind of utilization as described in Example 1, the digestive juice of the 1L that packs in the oxidation unit 8, and the running temperature of control device is 25 ± 2 ° of C; The waste gas that with sulfide hydrogen concentration is 2108ppm V enters cycling element 13 by inlet flow rate meter 1, the circulating reflux speed of control waste gas is 0.2L/min, air blast blasts air in cycling element 13, it is 0.2L/min that the air of control mass air flow sensor 3 blasts flow velocity, waste gas and air pump in the oxidation unit 8 by peristaltic pump, control the air or oxygen amount that enters in the oxidation unit by gas pipe 7, waste gas and air carry out oxidation processes with digestive juice in oxidation unit 8; Concentration of hydrogen sulfide is reduced to below the 10ppmV, and hydrogen sulfide is converted into elemental sulfur, and not hydrogen sulfide containing gas is discharged by gas discharge outlet 10, and elemental sulfur reclaims mouthfuls 5 by sulphur simple substance and reclaims.Concrete effect data is shown in curve among Fig. 22.
Embodiment 3:
The method that the low-level oxidation method is removed hydrogen sulfide and reclaimed sulphur simple substance is installed in a kind of utilization as described in Example 1, the digestive juice of the 1L that packs in the oxidation unit 8, and the running temperature of control device is 25 ± 2 ° of C; The waste gas that with sulfide hydrogen concentration is 2197ppm V enters cycling element 13 by inlet flow rate meter 1, the circulating reflux speed of control waste gas is 0.4L/min, air blast blasts air in cycling element 13, it is 0.2L/min that the air of control mass air flow sensor 3 blasts flow velocity, waste gas and air pump in the oxidation unit 8 by peristaltic pump, control the air or oxygen amount that enters in the oxidation unit by gas pipe 7, waste gas and air carry out oxidation processes with digestive juice in oxidation unit 8; Concentration of hydrogen sulfide is reduced to below the 10ppmV, and hydrogen sulfide is converted into elemental sulfur, and not hydrogen sulfide containing gas is discharged by gas discharge outlet 10, and elemental sulfur reclaims mouthfuls 5 by sulphur simple substance and reclaims.Concrete effect data is shown in curve among Fig. 23.
Embodiment 4:
The method that the low-level oxidation method is removed hydrogen sulfide and reclaimed sulphur simple substance is installed in a kind of utilization as described in Example 1, the digestive juice of the 1L that packs in the oxidation unit 8, and the running temperature of control device is 25 ± 2 ° of C; The waste gas that with sulfide hydrogen concentration is 2197ppmV enters cycling element 13 by inlet flow rate meter 1, the circulating reflux speed of control waste gas is 0.2L/min, air blast blasts air in cycling element 13, it is 0.4L/min that the air of control mass air flow sensor 3 blasts flow velocity, waste gas and air pump in the oxidation unit 8 by peristaltic pump, control the air or oxygen amount that enters in the oxidation unit by gas pipe 7, waste gas and air carry out oxidation processes with digestive juice in oxidation unit 8; Concentration of hydrogen sulfide is reduced to below the 10ppmV, and hydrogen sulfide is converted into elemental sulfur, and not hydrogen sulfide containing gas is discharged by gas discharge outlet 10, and elemental sulfur reclaims mouthfuls 5 by sulphur simple substance and reclaims.Concrete effect data is shown in curve among Fig. 24.
Embodiment 5:
The method that the low-level oxidation method is removed hydrogen sulfide and reclaimed sulphur simple substance is installed in a kind of utilization as described in Example 1, the digestive juice of the 1L that packs in the oxidation unit 8, and the running temperature of control device is 25 ± 2 ° of C; The waste gas that with sulfide hydrogen concentration is 2308ppmV enters cycling element 13 by inlet flow rate meter 1, the circulating reflux speed of control waste gas is 0.4L/min, air blast blasts air in cycling element 13, it is 0.4L/min that the air of control mass air flow sensor 3 blasts flow velocity, waste gas and air pump in the oxidation unit 8 by peristaltic pump, control the air or oxygen amount that enters in the oxidation unit by gas pipe 7, waste gas and air carry out oxidation processes with digestive juice in oxidation unit 8; Concentration of hydrogen sulfide is reduced to below the 10ppmV, and hydrogen sulfide is converted into elemental sulfur, and not hydrogen sulfide containing gas is discharged by gas discharge outlet 10, and elemental sulfur reclaims mouthfuls 5 by sulphur simple substance and reclaims.Concrete effect data is shown in curve among Fig. 35.
Embodiment 6:
The method that the low-level oxidation method is removed hydrogen sulfide and reclaimed sulphur simple substance is installed in a kind of utilization as described in Example 1, the digestive juice of the 1L that packs in the oxidation unit 8, and the running temperature of control device is 25 ± 2 ° of C; The waste gas that with sulfide hydrogen concentration is 2474ppm V enters cycling element 13 by inlet flow rate meter 1, the circulating reflux speed of control waste gas is 0.2L/min, air blast blasts air in cycling element 13, it is 1L/min that the air of control mass air flow sensor 3 blasts flow velocity, waste gas and air pump in the oxidation unit 8 by peristaltic pump, control the air or oxygen amount that enters in the oxidation unit by gas pipe 7, waste gas and air carry out oxidation processes with digestive juice in oxidation unit 8; Concentration of hydrogen sulfide is reduced to below the 10ppmV, and hydrogen sulfide is converted into elemental sulfur, and not hydrogen sulfide containing gas is discharged by gas discharge outlet 10, and elemental sulfur reclaims mouthfuls 5 by sulphur simple substance and reclaims.Concrete effect data is shown in curve among Fig. 36.
Embodiment 7:
The method that the low-level oxidation method is removed hydrogen sulfide and reclaimed sulphur simple substance is installed in a kind of utilization as described in Example 1, the digestive juice of the 1L that packs in the oxidation unit 8, and the running temperature of control device is 25 ± 2 ° of C; The waste gas that with sulfide hydrogen concentration is 2308ppmV enters cycling element 13 by inlet flow rate meter 1, the circulating reflux speed of control waste gas is 0.4L/min, air blast blasts air in cycling element 13, it is 1L/min that the air of control mass air flow sensor 3 blasts flow velocity, waste gas and air pump in the oxidation unit 8 by peristaltic pump, control the air or oxygen amount that enters in the oxidation unit by gas pipe 7, waste gas and air carry out oxidation processes with digestive juice in oxidation unit 8; Concentration of hydrogen sulfide is reduced to below the 10ppmV, and hydrogen sulfide is converted into elemental sulfur, and not hydrogen sulfide containing gas is discharged by gas discharge outlet 10, and elemental sulfur reclaims mouthfuls 5 by sulphur simple substance and reclaims.Concrete effect data is shown in curve among Fig. 37.
Claims (10)
1. a low-level oxidation method is removed hydrogen sulfide and is reclaimed the device of sulphur, comprises oxidation unit, cycling element and control platform; It is characterized in that the top of oxidation unit is provided with the ORP/pH probe and is connected with the control platform, the bottom of oxidation unit is provided with gas pipe, liquid outlet and sulphur simple substance and reclaims mouth; The bottom of cycling element is provided with peristaltic pump, and the bottom of cycling element is communicated with the bottom of oxidation unit, and the top of cycling element is communicated with the top of oxidation unit, and the top of cycling element is provided with gas discharge outlet, and oxidation unit and cycling element consist of the circulatory system; Be provided with the inlet flow rate meter between the top of cycling element and the bottom, be provided with mass air flow sensor between inlet flow rate meter and the peristaltic pump, mass air flow sensor is connected with air blast, is provided with check valve between inlet flow rate meter and the gas discharge outlet fluid in the cycling element can only be flowed by the direction of inlet flow rate meter sensing peristaltic pump.
2. device according to claim 1 is characterized in that: described oxidation unit is straight shape pipe, highly is 0.6 ~ 5m, and internal diameter is 3 ~ 20cm; Described cycling element is that internal diameter is at the pipeline of 1 ~ 5cm.
3. device according to claim 1, it is characterized in that: described oxidation unit and cycling element inwall are provided with polyethylene or polyvinyl chloride erosion shield.
4. one kind is utilized device low-level oxidation method claimed in claim 1 to remove hydrogen sulfide and reclaims the method for sulphur simple substance, it is characterized in that step is as follows: the digestive juice of packing in the oxidation unit, waste water or the waste gas that will contain hydrogen sulfide enter cycling element by the inlet flow rate meter, and air blast blasts air in the cycling element and blasts the amount of air by mass air flow sensor control; Waste water and air, perhaps, waste gas and air pump in the oxidation unit by peristaltic pump, control the air or oxygen amount that enters in the oxidation unit by gas pipe; Waste water and air, perhaps, waste gas and air carry out oxidation processes with digestive juice in oxidation unit, hydrogen sulfide after oxidation processes is converted into elemental sulfur and reclaims a mouthful recovery by sulphur simple substance, not hydrogen sulfide containing gas is discharged by gas discharge outlet, and not hydrogen sulfide containing liquid is discharged by liquid outlet.
5. method according to claim 4 is characterized in that: waste water and air, perhaps, waste gas and air circular treatment in the circulatory system that oxidation unit and cycling element consist of is not less than twice.
6. method according to claim 4 is characterized in that: enter the volume content that oxygen in the oxidation unit accounts for total gas and be not higher than 2%.
7. method according to claim 4 is characterized in that: enter that cycling element contains the waste water of hydrogen sulfide or the temperature of waste gas is 15～35 ℃, preferred 20～25 ℃.
8. method according to claim 4, it is characterized in that: the pH of the digestive juice of packing into is 7.0 ~ 8.0, particularly preferably 7.5.
9. method according to claim 4, it is characterized in that: the flow velocity that blasts air is the 5-30% of sulfide hydrogen waste gas flow velocity.
10. method according to claim 4, it is characterized in that: the flow velocity that sulfide hydrogen waste gas enters oxidation unit is 0.05 ~ 5L/ minute.
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| CN106285618A (en) * | 2015-06-01 | 2017-01-04 | 中国石油化工股份有限公司 | Oil/gas Well hydrogen sulfide automatic processing device |
| CN106824209A (en) * | 2016-12-05 | 2017-06-13 | 上海大学 | The method that porous material processes hydrogen sulfide contamination gas is prepared using mixing sludge |
| CN108319244A (en) * | 2018-02-11 | 2018-07-24 | 吉林建筑大学 | Handle the batch-type Fenton oxidation reaction process control parameter of indegradable industrial effluent |
| CN109908717A (en) * | 2019-03-26 | 2019-06-21 | 四川大学 | Gas circulating type biology bubble tower biogas/natural gas biological desulfurization method |
| CN115090101A (en) * | 2022-07-19 | 2022-09-23 | 华夏碧水环保科技股份有限公司 | Comprehensive treatment method for removing sulfur, water and carbon dioxide from biogas |
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| CN115090101A (en) * | 2022-07-19 | 2022-09-23 | 华夏碧水环保科技股份有限公司 | Comprehensive treatment method for removing sulfur, water and carbon dioxide from biogas |
| CN115090101B (en) * | 2022-07-19 | 2023-09-01 | 华夏碧水环保科技股份有限公司 | Comprehensive treatment method for desulfurizing, dewatering and removing carbon dioxide of biogas |
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