CN102921286B - 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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- CN102921286B CN102921286B CN201210452317.XA CN201210452317A CN102921286B CN 102921286 B CN102921286 B CN 102921286B CN 201210452317 A CN201210452317 A CN 201210452317A CN 102921286 B CN102921286 B CN 102921286B
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Abstract
The invention relates to a device for removing hydrogen sulfide 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 the apparatus and method that low-level oxidation method is removed hydrogen sulfide and reclaimed sulphur simple substance, 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 Treatment of Sludge disposal process, the H 2 S-containing gas (H of generation
2s), cause very large secondary pollution, had a strong impact on ambient atmosphere environment.In a large amount of recovered waters and life factory effluent that 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 are not only directly detrimental to health, extremely unfavorable to the growth of animal, and under aerobic and damp and hot condition, severe corrosion equipment, pipeline and instrument etc., and can accelerate the aging of nonmetallic materials; Therefore, in removal waste water, waste gas, the correlative study of hydrogen sulfide receives much concern.
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 and reclaimed sulphur simple substance, the present invention also provides a kind of and utilizes hydrogen sulfide in this device removal waste water, waste gas also to realize the method that elemental sulfur reclaims simultaneously.Adopt method of the present invention effectively by the hydrogen sulfide removal in waste water or waste gas, not need filler, without adding chemicals and microorganism, environmental friendliness is easy to engineering application.
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 simultaneously detect ORP value and pH value.
Technical scheme of the present invention is as follows:
Low-level oxidation method is removed hydrogen sulfide and is reclaimed a device for sulphur simple substance, comprises oxidation unit, cycling element and control platform; The top of oxidation unit is provided with ORP/pH probe and is connected with 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 form the circulatory system; Between the top of cycling element and bottom, be provided with inlet flow rate meter, between inlet flow rate meter and peristaltic pump, be provided with mass air flow sensor, mass air flow sensor is connected with air blast, is provided with check valve the fluid in cycling element can only be flowed by the direction of inlet flow rate meter sensing peristaltic pump between inlet flow rate meter and gas discharge outlet.
Gas pipe is for controlling the air or oxygen amount entering in oxidation unit, air blast is used for the amount that blasts air and blast air by mass air flow sensor control, inlet flow rate meter is for controlling the waste water or the waste gas that enter cycling element, and peristaltic pump pumps into waste water or waste gas and the air that blasts in oxidation unit, to carry out oxidation processes; ORP/pH probe is for detection of the pH value in oxidation unit and ORP value, and transfer data to control platform, control platform according to the automatic control of the pH value in oxidation unit and ORP value inlet flow rate meter, mass air flow sensor and gas pipe, realization is to waste water or waste gas, the air blasting and enter the automation control of the air or oxygen amount in oxidation unit.
Preferred according to the present invention, described oxidation unit is straight shape pipe, is highly 0.6 ~ 5m, and internal diameter is 3 ~ 20cm; Be highly particularly preferably 1m, internal diameter is 4cm.
Preferred according to the present invention, described cycling element is the pipeline of internal diameter at 1 ~ 5cm.
Preferred according to the present invention, in described oxidation unit, add digestive juice.
Preferred according to the present invention, oxidation unit and cycling element inwall are provided with erosion shield, erosion shield preferably polyethylene, polyvinyl chloride.
Utilize said apparatus low-level oxidation method to remove a method for hydrogen sulfide and recovery sulphur simple substance, step is as follows:
In oxidation unit, pack digestive juice into, the waste water that contains hydrogen sulfide or waste gas are entered to cycling element by inlet flow rate meter, air blast is to blasting air in cycling element and blasting the amount of air by mass air flow sensor control; Useless water and air, or, waste gas and air pump in oxidation unit by peristaltic pump, enter the air or oxygen amount in oxidation unit by gas pipe control, useless water and air, or, 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, useless water and air, or 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 oxygen accounts for total gas in oxidation unit volume content not higher than 2%.
Preferred according to the inventive method, entering waste water that cycling element contains hydrogen sulfide or the temperature of waste gas is 15～35 ℃, preferably 20～30 ℃, and most preferably 20～25 ℃.
Preferred according to the inventive method, the pH that packs digestive juice 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 present invention's digestive juice used is the digestive juice in common municipal sewage plant digester in 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 hydrogen sulfide removal effect in good time.
Technical characterstic of the present invention and excellent results are as follows:
1, the device that low-level oxidation method of the present invention is removed hydrogen sulfide and reclaimed sulphur simple substance does not need filler, chemical reagent and microorganism, and cost is low, efficient, safety, mild condition, under normal temperature and pressure, can use.
2, air blast of the present invention can, according to desulfurized effect by the computer control blow rate required, can be realized 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 simple substance, prevents the corrosion of sulphur and hydrogen sulfide.
4, the present invention is elemental sulfur by 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 and recovery sulphur simple substance, and input is less than the amount of oxygen of 2% volume ratio can realize the removal effect of hydrogen sulfide content lower than 1ppm V.
6, low-level oxidation method of the present invention is removed the method for hydrogen sulfide and recovery sulphur simple substance, can be by repeatedly circulating and make minimumization of concentration of hydrogen sulfide.
7, low-level oxidation method of the present invention is removed the method for hydrogen sulfide and recovery sulphur simple substance, realizes the oxidation of hydrogen sulfide by blasting air, and raw material is easy to get, simple to operate.
Accompanying drawing explanation:
Fig. 1 is the structural representation that low-level oxidation method of the present invention is removed the device of hydrogen sulfide and recovery sulphur simple substance;
In Fig. 1,1. inlet flow rate meter, 2. air blast, 3. mass air flow sensor, 4. peristaltic pump, 5. sulphur simple substance reclaims mouth, 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 present invention 2 ~ 4 different disposal conditions.
Fig. 3 is hydrogen sulfide removal effect curve figure under the embodiment of the present invention 5 ~ 7 different disposal conditions.
The specific embodiment:
Below by specific embodiment, also the present invention will be further described by reference to the accompanying drawings, but be not limited to this.
Digestive juice used in embodiment, takes from municipal sewage plant; ORP/pH probe in embodiment is conventional commercial equipment.
Embodiment 1:
Low-level oxidation method is removed hydrogen sulfide and is reclaimed a device for sulphur simple substance, comprises oxidation unit 8, cycling element 13 and controls 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 forms the circulatory system with cycling element 13; Between the top of cycling element 13 and bottom, be provided with inlet flow rate meter 1, between inlet flow rate meter 1 and peristaltic pump 4, be provided with mass air flow sensor 3, mass air flow sensor 3 is connected with air blast 2, is provided with the direction that check valve 12 makes fluid in cycling element 13 point to peristaltic pump 4 by inlet flow rate meter 1 and flows between inlet flow rate meter 1 and gas discharge outlet 10.
Gas pipe 7 is for controlling the air or oxygen amount entering in oxidation unit 8, air blast 2 is for blasting air and controlling by mass air flow sensor 3 amount that blasts air, inlet flow rate meter 1 is for controlling the waste water or the waste gas that enter cycling element 13, and peristaltic pump 4 pumps into waste water or waste gas and the air that blasts in oxidation unit 8, to carry out oxidation processes; ORP/pH probe 9 is for detection of the pH value in oxidation unit 8 and ORP value, and transfer data to control platform 11, control platform 11 according to the automatic control of the pH value in oxidation unit 8 and ORP value inlet flow rate meter 1, mass air flow sensor 3 and gas pipe 7, realization is to waste water or waste gas, the air blasting and enter the automation control of the air or oxygen amount in oxidation unit.
In the present embodiment, oxidation unit 8 is straight shape pipe, and it is highly 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 polyethylene anticorrosion erosion resisting coating.
Embodiment 2:
The method that low-level oxidation method is removed hydrogen sulfide and reclaimed sulphur simple substance is installed in utilization as described in Example 1, and to the digestive juice that packs 1L in oxidation unit 8 into, the running temperature of control device is 25 ± 2 ° of C; The waste gas that by sulfide hydrogen concentration is 2108ppm V enters cycling element 13 by inlet flow rate meter 1, the circulating reflux speed of controlling 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 oxidation unit 8 by peristaltic pump, control by gas pipe 7 the air or oxygen amount entering in oxidation unit, waste gas and air carry out oxidation processes with digestive juice in oxidation unit 8; After the oxidation processes of approximately 7 hours, make concentration of hydrogen sulfide in waste gas reduce to below 10ppmV, hydrogen sulfide is converted into elemental sulfur, and not hydrogen sulfide containing gas is discharged by gas discharge outlet 10, and elemental sulfur reclaims mouthful 5 recovery by sulphur simple substance.Concrete effect data is as shown in curve in Fig. 22.
Embodiment 3:
The method that low-level oxidation method is removed hydrogen sulfide and reclaimed sulphur simple substance is installed in utilization as described in Example 1, and to the digestive juice that packs 1L in oxidation unit 8 into, the running temperature of control device is 25 ± 2 ° of C; The waste gas that by sulfide hydrogen concentration is 2197ppm V enters cycling element 13 by inlet flow rate meter 1, the circulating reflux speed of controlling 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 oxidation unit 8 by peristaltic pump, control by gas pipe 7 the air or oxygen amount entering in oxidation unit, waste gas and air carry out oxidation processes with digestive juice in oxidation unit 8; After the oxidation processes of approximately 6.5 hours, make concentration of hydrogen sulfide in waste gas reduce to below 10ppmV, hydrogen sulfide is converted into elemental sulfur, and not hydrogen sulfide containing gas is discharged by gas discharge outlet 10, and elemental sulfur reclaims mouthful 5 recovery by sulphur simple substance.Concrete effect data is as shown in curve in Fig. 23.
Embodiment 4:
The method that low-level oxidation method is removed hydrogen sulfide and reclaimed sulphur simple substance is installed in utilization as described in Example 1, and to the digestive juice that packs 1L in oxidation unit 8 into, the running temperature of control device is 25 ± 2 ° of C; The waste gas that is 2197ppmV by sulfide hydrogen concentration enters cycling element 13 by inlet flow rate meter 1, the circulating reflux speed of controlling 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 oxidation unit 8 by peristaltic pump, control by gas pipe 7 the air or oxygen amount entering in oxidation unit, waste gas and air carry out oxidation processes with digestive juice in oxidation unit 8; After the oxidation processes of approximately 5.5 hours, make concentration of hydrogen sulfide in waste gas reduce to below 10ppmV, hydrogen sulfide is converted into elemental sulfur, and not hydrogen sulfide containing gas is discharged by gas discharge outlet 10, and elemental sulfur reclaims mouthful 5 recovery by sulphur simple substance.Concrete effect data is as shown in curve in Fig. 24.
Embodiment 5:
The method that low-level oxidation method is removed hydrogen sulfide and reclaimed sulphur simple substance is installed in utilization as described in Example 1, and to the digestive juice that packs 1L in oxidation unit 8 into, the running temperature of control device is 25 ± 2 ° of C; The waste gas that by sulfide hydrogen concentration is 2308ppm V enters cycling element 13 by inlet flow rate meter 1, the circulating reflux speed of controlling 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 oxidation unit 8 by peristaltic pump, control by gas pipe 7 the air or oxygen amount entering in oxidation unit, waste gas and air carry out oxidation processes with digestive juice in oxidation unit 8; After the oxidation processes of approximately 4.5 hours, make concentration of hydrogen sulfide in waste gas reduce to below 10ppmV, hydrogen sulfide is converted into elemental sulfur, and not hydrogen sulfide containing gas is discharged by gas discharge outlet 10, and elemental sulfur reclaims mouthful 5 recovery by sulphur simple substance.Concrete effect data is as shown in curve in Fig. 35.
Embodiment 6:
The method that low-level oxidation method is removed hydrogen sulfide and reclaimed sulphur simple substance is installed in utilization as described in Example 1, and to the digestive juice that packs 1L in oxidation unit 8 into, the running temperature of control device is 25 ± 2 ° of C; The waste gas that is 2474ppmV by sulfide hydrogen concentration enters cycling element 13 by inlet flow rate meter 1, the circulating reflux speed of controlling 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 oxidation unit 8 by peristaltic pump, control by gas pipe 7 the air or oxygen amount entering in oxidation unit, waste gas and air carry out oxidation processes with digestive juice in oxidation unit 8; After the oxidation processes of approximately 3.2 hours, make concentration of hydrogen sulfide in waste gas reduce to below 10ppmV, hydrogen sulfide is converted into elemental sulfur, and not hydrogen sulfide containing gas is discharged by gas discharge outlet 10, and elemental sulfur reclaims mouthful 5 recovery by sulphur simple substance.Concrete effect data is as shown in curve in Fig. 36.
Embodiment 7:
The method that low-level oxidation method is removed hydrogen sulfide and reclaimed sulphur simple substance is installed in utilization as described in Example 1, and to the digestive juice that packs 1L in oxidation unit 8 into, the running temperature of control device is 25 ± 2 ° of C; The waste gas that by sulfide hydrogen concentration is 2308ppm V enters cycling element 13 by inlet flow rate meter 1, the circulating reflux speed of controlling 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 oxidation unit 8 by peristaltic pump, control by gas pipe 7 the air or oxygen amount entering in oxidation unit, waste gas and air carry out oxidation processes with digestive juice in oxidation unit 8; After the oxidation processes of approximately 3.5 hours, make concentration of hydrogen sulfide in waste gas reduce to below 10ppmV, hydrogen sulfide is converted into elemental sulfur, and not hydrogen sulfide containing gas is discharged by gas discharge outlet 10, and elemental sulfur reclaims mouthful 5 recovery by sulphur simple substance.Concrete effect data is as shown in curve in Fig. 37.
Claims (11)
1. low-level oxidation method is removed a method for hydrogen sulfide and recovery sulphur simple substance, it is characterized in that the device that the method utilizes low-level oxidation method to remove hydrogen sulfide and recovery sulphur simple substance completes, and described device comprises oxidation unit, cycling element and control platform; The top of oxidation unit is provided with ORP/pH probe and is connected with 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 form the circulatory system; Between the top of cycling element and bottom, be provided with inlet flow rate meter, between inlet flow rate meter and peristaltic pump, be provided with mass air flow sensor, mass air flow sensor is connected with air blast, is provided with check valve the fluid in cycling element can only be flowed by the direction of inlet flow rate meter sensing peristaltic pump between inlet flow rate meter and gas discharge outlet;
Step is as follows:
In oxidation unit, pack digestive juice into, the waste water that contains hydrogen sulfide or waste gas are entered to cycling element by inlet flow rate meter, air blast is to blasting air in cycling element and blasting the amount of air by mass air flow sensor control; Useless water and air, or waste gas and air pump in oxidation unit by peristaltic pump, enter the air or oxygen amount in oxidation unit by gas pipe control; Useless water and air, or, 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.
2. low-level oxidation method according to claim 1 is removed the method for hydrogen sulfide and recovery sulphur simple substance, it is characterized in that: described oxidation unit is straight shape pipe, is highly 0.6 ~ 5m, and internal diameter is 3 ~ 20cm; Described cycling element is the pipeline of internal diameter at 1 ~ 5cm.
3. low-level oxidation method according to claim 1 is removed the method for hydrogen sulfide and recovery sulphur simple substance, it is characterized in that: described oxidation unit and cycling element inwall are provided with polyethylene or polyvinyl chloride erosion shield.
4. low-level oxidation method according to claim 1 is removed the method for hydrogen sulfide and recovery sulphur simple substance, it is characterized in that: useless water and air, or waste gas and air circular treatment in the circulatory system of oxidation unit and cycling element formation is not less than twice.
5. low-level oxidation method according to claim 1 is removed hydrogen sulfide and is reclaimed the method for sulphur simple substance, it is characterized in that: enter volume content that in oxidation unit, oxygen accounts for total gas not higher than 2%.
6. low-level oxidation method according to claim 1 is removed hydrogen sulfide and is reclaimed the method for sulphur simple substance, it is characterized in that: entering waste water that cycling element contains hydrogen sulfide or the temperature of waste gas is 15～35 ℃.
7. low-level oxidation method according to claim 6 is removed hydrogen sulfide and is reclaimed the method for sulphur simple substance, it is characterized in that: entering waste water that cycling element contains hydrogen sulfide or the temperature of waste gas is 20～25 ℃.
8. low-level oxidation method according to claim 1 is removed the method for hydrogen sulfide and recovery sulphur simple substance, it is characterized in that: the pH that packs digestive juice into is 7.0 ~ 8.0.
9. low-level oxidation method according to claim 8 is removed the method for hydrogen sulfide and recovery sulphur simple substance, it is characterized in that: the pH that packs digestive juice into is 7.5.
10. low-level oxidation method according to claim 1 is removed the method for hydrogen sulfide and recovery sulphur simple substance, it is characterized in that: the flow velocity that blasts air is the 5-30% of sulfide hydrogen waste gas flow velocity.
11. low-level oxidation methods according to claim 1 are removed hydrogen sulfide and are reclaimed the method for sulphur simple substance, it is characterized in that: the flow velocity that sulfide hydrogen waste gas enters oxidation unit be 0.05 ~ 5 L/minute.
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| CN106285618B (en) * | 2015-06-01 | 2019-04-09 | 中国石油化工股份有限公司 | Oil/gas well hydrogen sulfide automatic processing device |
| CN106824209B (en) * | 2016-12-05 | 2019-07-23 | 上海大学 | The method for preparing porous material processing hydrogen sulfide contamination gas 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 |
| CN109908717B (en) * | 2019-03-26 | 2021-09-24 | 四川大学 | Biogas/natural gas biological desulfurization method for gas circulation type biological bubble tower |
| 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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| CN1144782A (en) * | 1995-09-05 | 1997-03-12 | 农业部成都沼气科学研究所 | Oxydation removing hydrogen sulfide technology in methane-generating pit |
| CN101003364A (en) * | 2007-01-22 | 2007-07-25 | 桂林工学院 | Process for recovering elemental sulfur from molasses alcohol wastewater |
| CN101696055A (en) * | 2009-10-24 | 2010-04-21 | 桂林理工大学 | Process for processing molasses alcohol wastewater microaerophile by utilizing oxygen from air |
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