CN111003910A - Method for treating waste sulfonated mud from drilling - Google Patents
Method for treating waste sulfonated mud from drilling Download PDFInfo
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- CN111003910A CN111003910A CN201911416019.3A CN201911416019A CN111003910A CN 111003910 A CN111003910 A CN 111003910A CN 201911416019 A CN201911416019 A CN 201911416019A CN 111003910 A CN111003910 A CN 111003910A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/06—Treatment of sludge; Devices therefor by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/143—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/143—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances
- C02F11/145—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using inorganic substances using calcium compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F11/00—Treatment of sludge; Devices therefor
- C02F11/12—Treatment of sludge; Devices therefor by de-watering, drying or thickening
- C02F11/14—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents
- C02F11/147—Treatment of sludge; Devices therefor by de-watering, drying or thickening with addition of chemical agents using organic substances
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention provides a method for treating waste sulfonated mud from drilling, which belongs to the field of petroleum and natural gas.A pH value of the waste sulfonated mud from drilling is adjusted by a pH regulator; adding an oxidant into the slurry after pH adjustment to oxidize the slurry; adding a heavy metal stabilizer into the oxidized slurry to form a stable complex by heavy metal ions in the slurry; adding inorganic flocculant or organic flocculant into the slurry forming the stable complex, performing gel breaking flocculation on the slurry, and then performing solid-liquid separation. By adding the substances with specific amount, the waste sulfonated mud from drilling is subjected to oxidation, complex reaction, flocculation, solid-liquid separation and other treatments, so that the harmful components of the sulfonated mud can be thoroughly removed, and the pollution of the sulfonated mud to the environment is solved.
Description
Technical Field
The invention belongs to the field of petroleum and natural gas, and particularly relates to a method for treating waste sulfonated mud from drilling.
Background
The drilling mud of the sulfonated mud system is water-based mud which takes drilling mud additives such as sulfonated phenolic resin (SMP), sulfonated lignite (SMC), sulfonated baking gum (SMK) and the like as main treating agents, and has the advantages of strong high-temperature resistance, strong filtration reduction capability and low cost.
In recent years, due to the increase of the drilling depth, the drilling process has more and more advocated the use of sulfonated mud; during the process of oil and gas exploitation, drilling and well repair, a large amount of waste sulfonated drilling mud is generated, and the pollution to the surrounding environment is more serious. Due to the fluidity and the dispersibility of drilling production, the sulfonated mud has large pollution area and wide area; meanwhile, the contents of soluble salt, chemical oxygen demand, pH, heavy metal and the like in the sulfonated mud are far larger than those in the surrounding environment, so that the sulfonated mud causes serious pollution to surrounding soil and underground (surface) water and influences the normal growth of surrounding animals and plants.
With the improvement of living standard and the enhancement of environmental awareness of people, the harm and pollution of the waste sulfonated mud generated by drilling to the environment are concerned; at present, the processing technology of the waste sulfonated mud for drilling mainly comprises safe landfill, solidification and flocculation sedimentation, and although the processing technology can control the environment pollution expansion of the sulfonated mud, the processing technology cannot eliminate the pollution.
Disclosure of Invention
Aiming at the problems, the invention provides a method for treating the waste sulfonated mud from drilling, which can thoroughly remove the harmful components of the sulfonated mud and solve the pollution of the sulfonated mud to the environment by carrying out oxidation, complex reaction, flocculation, solid-liquid separation and other treatments on the waste sulfonated mud from drilling.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for treating waste sulfonated mud from drilling comprises the following steps:
collecting waste sulfonated mud from drilling, and adjusting the pH value of the mud to 6-9 by using a pH regulator;
adding 30-50 wt% of oxidant into the slurry after pH adjustment, wherein the addition amount is 0.5-1% of the volume of the slurry, and oxidizing the slurry;
adding a heavy metal stabilizer with the concentration of 0.2-0.8 wt% into the oxidized slurry, wherein the addition amount is 2-5% of the volume of the slurry, so that heavy metal ions in the slurry form a stable complex;
adding 10-20 wt% inorganic flocculant or 0.2-0.5 wt% organic flocculant into the slurry to form stable complex, the addition amount is 10-20% of the volume of the slurry, performing gel breaking flocculation on the slurry, and performing solid-liquid separation.
Further, a tank with a stirrer is used to collect the drilling waste sulfonated mud.
Further, the pH adjusting agent includes citric acid, dilute sulfuric acid, dilute hydrochloric acid, hydrofluoric acid, sulfamic acid, tartaric acid, glycolic acid, or organic phosphoric acid, and the like.
Further, the oxidizing agent includes chlorate, perchlorate, permanganate, dichromate, inorganic peroxide, manganese dioxide (MnO)2) Iron chloride (FeCl)3) Nitrate, sodium hypochlorite, etc., and two or more kinds of oxidizing agents may be used in combination, wherein the inorganic peroxide includes sodium peroxide (Na)2O2) Potassium peroxide (K)2O2) Magnesium peroxide (MgO)2) Calcium peroxide (CaO)2) Barium peroxide (BaO)2) Hydrogen peroxide (H)2O2)。
Further, heavy metal stabilizers include ethylenediaminetetraacetic acid (EDTA), ethylenediaminetetramethylenephosphonic acid (EDTMPS), polymaleic acid (HPMA), polyacrylic acid (PAA), sodium thioantimonate (TMT, i.e., Na)3(C3N3S3)·9H2O), polyhydroxyacrylic acid, maleic acrylic acid copolymer, polyacrylamide, or the like.
Further, the inorganic flocculant includes ferrous sulfate, ferrous chloride, alum, polyaluminium chloride, basic aluminium chloride, aluminium sulfate or calcium chloride, etc.
Furthermore, the organic flocculant is mainly a polymeric flocculant, mainly comprising sodium polyacrylate, polyacrylamide, polystyrene sulfonate or polyethylene oxide.
Further, a vacuum belt filter, a centrifuge, a plate-and-frame filter press or a screw filter press is used for solid-liquid separation.
The method of the invention pre-adjusts the pH value to the range of 6-9, can effectively improve the drug effect of the added drugs in the subsequent steps, reduce the drug consumption and optimize the treatment effect. The oxidant with the concentration of 30-50 wt% and accounting for 0.5-1% of the volume of the slurry is added, so that the COD (chemical oxygen demand) value of the slurry can be effectively greatly reduced, the COD of the mud cake after solid-liquid separation can be reduced by 50-130mg/L from 600-2000mg/L, and the effect is remarkable. By adding the heavy metal stabilizer with the concentration of 0.2-0.8 wt% which is 2-5% of the volume of the slurry into the slurry, the heavy metal ions in the slurry can completely form a stable complex, if the heavy metal ions are too little to form a complete stable complex, if the heavy metal ions are too much to form a complete stable complex, the COD value of the slurry can be affected, and the COD value of a mud cake after solid-liquid separation is greatly improved. The flocculation can lead the solid-liquid separation to be more thorough, reduce the water content in the solid phase and the value of insoluble suspended matters in the liquid phase, and lead the water content in the solid phase to be less than 40 percent by adding 10 to 20 percent by weight of inorganic flocculant or 0.2 to 0.5 percent by weight of organic flocculant which is 10 to 20 percent by weight of the volume of the slurry. By adjusting the pH value within a specific range and adding a specific amount of an oxidant, a heavy metal stabilizer and a flocculating agent, harmful components in the waste sulfonated mud can be effectively drilled, and the effect is remarkable. After the waste sulfonated mud for drilling is treated, the obtained solid phase can be used for well site recovery, paving, brick making and the like, and the liquid phase is sent to a centralized treatment point for treatment, so that the harm of the sulfonated mud to the environment can be solved at one time.
Drawings
FIG. 1 is a flow chart of a method for treating drilling waste sulfonated mud according to an embodiment.
FIG. 2 is a graph showing the solid-phase water content of slurries treated at different pH values.
FIG. 3 is a graph of solid phase COD values of slurries treated at different pH values.
FIG. 4 is a graph of solid-phase water content of slurries treated with different amounts of oxidant.
FIG. 5 is a graph of solid phase COD values of slurries treated with different amounts of oxidant.
FIG. 6 is a graph of solid phase water content of mud treated by different heavy metal stabilizer addition amounts.
FIG. 7 is a graph of solid phase COD values of slurries treated by different heavy metal stabilizer addition amounts.
FIG. 8 is a graph of solid phase water content of slurry treated by different amounts of inorganic flocculant.
FIG. 9 is a graph of solid phase COD values of slurries treated by different amounts of inorganic flocculant.
FIG. 10 is a graph of solid phase water content of slurry treated with different amounts of organic flocculant.
FIG. 11 is a graph of COD values of solid phases of slurries treated by different organic flocculant addition amounts.
Detailed Description
In order to make the aforementioned and other features and advantages of the invention more comprehensible, embodiments accompanied with figures are described in detail below.
The following six embodiments each provide a method for treating drilling waste sulfonated mud, the general flow of which is shown in fig. 1, and the details of which are as follows.
Example 1
1) Collecting waste sulfonated mud from drilling, and adjusting the pH value of the mud to 7 by using dilute sulfuric acid;
2) adding 30 wt% of hydrogen peroxide into the slurry after pH adjustment, wherein the addition amount of the hydrogen peroxide is 0.8% of the volume of the slurry, and oxidizing the slurry;
3) adding EDTA with the concentration of 0.6 wt% into the oxidized slurry, wherein the addition amount is 4% of the volume of the slurry, so that heavy metal ions in the slurry form a stable complex;
4) adding 15 wt% of ferrous chloride into the slurry which forms the stable complex, wherein the adding amount is 20% of the volume of the slurry, and carrying out gel breaking and flocculation on the slurry;
5) and (4) carrying out solid-liquid separation by adopting a vacuum belt filter.
Example 2
1) Collecting waste sulfonated mud from drilling, and adjusting the pH value of the mud to 6 by using citric acid;
2) adding permanganate with the concentration of 40 wt% into the slurry after the pH adjustment, wherein the adding amount is 1% of the volume of the slurry, and oxidizing the slurry;
3) adding TMT with the concentration of 0.8 wt% into the oxidized slurry, wherein the addition amount is 5% of the volume of the slurry, so that heavy metal ions in the slurry form a stable complex;
4) adding polyoxyethylene with the concentration of 0.4 wt% into the slurry which forms the stable complex, wherein the addition amount is 15% of the volume of the slurry, and carrying out gel breaking flocculation on the slurry;
5) and (4) performing solid-liquid separation by using a centrifugal machine.
Example 3
1) Collecting waste sulfonated mud from drilling, and adjusting the pH value of the mud to 9 by using organic phosphoric acid;
2) adding H with the concentration of 50 wt% into the slurry after pH adjustment2O2The adding amount is 0.5 percent of the volume of the slurry, and the slurry is oxidized;
3) adding 0.2 wt% of maleic acid acrylic acid copolymer into the oxidized slurry, wherein the addition amount is 2% of the volume of the slurry, so that heavy metal ions in the slurry form a stable complex;
4) adding 20 wt% of aluminum sulfate into the slurry forming the stable complex, wherein the adding amount is 10% of the volume of the slurry, and performing gel breaking and flocculation on the slurry;
5) and (4) performing solid-liquid separation by adopting a plate-and-frame filter press.
Example 4
1) Collecting waste sulfonated mud from drilling, and adjusting the pH value of the mud to 7 by using dilute sulfuric acid;
2) adding 30 wt% of hydrogen peroxide into the slurry after pH adjustment, wherein the addition amount of the hydrogen peroxide is 0.8% of the volume of the slurry, and oxidizing the slurry;
3) adding EDTA with the concentration of 0.6 wt% into the oxidized slurry, wherein the addition amount is 4% of the volume of the slurry, so that heavy metal ions in the slurry form a stable complex;
4) adding 10 wt% of ferrous chloride into the slurry which forms the stable complex, wherein the adding amount is 20% of the volume of the slurry, and carrying out gel breaking and flocculation on the slurry;
5) and (4) carrying out solid-liquid separation by adopting a vacuum belt filter.
Example 5
1) Collecting waste sulfonated mud from drilling, and adjusting the pH value of the mud to 6 by using citric acid;
2) adding permanganate with the concentration of 40 wt% into the slurry after the pH adjustment, wherein the adding amount is 1% of the volume of the slurry, and oxidizing the slurry;
3) adding TMT with the concentration of 0.8 wt% into the oxidized slurry, wherein the addition amount is 5% of the volume of the slurry, so that heavy metal ions in the slurry form a stable complex;
4) adding sodium polyacrylate with the concentration of 0.2 wt% into the slurry forming the stable complex, wherein the adding amount is 15% of the volume of the slurry, and performing gel breaking and flocculation on the slurry;
5) and (4) performing solid-liquid separation by using a centrifugal machine.
Example 6
1) Collecting waste sulfonated mud from drilling, and adjusting the pH value of the mud to 9 by using organic phosphoric acid;
2) adding H with the concentration of 50 wt% into the slurry after pH adjustment2O2The adding amount is 0.5 percent of the volume of the slurry, and the slurry is oxidized;
3) adding 0.2 wt% of maleic acid acrylic acid copolymer into the oxidized slurry, wherein the addition amount is 2% of the volume of the slurry, so that heavy metal ions in the slurry form a stable complex;
4) adding 0.5 wt% of polyacrylamide into the slurry which forms the stable complex, wherein the adding amount is 10% of the volume of the slurry, and carrying out gel breaking and flocculation on the slurry;
5) and (4) performing solid-liquid separation by adopting a plate-and-frame filter press.
The results of the solid-liquid separation of the three examples 1 to 6 were measured and found to be as follows:
example 1: the COD of the solid phase is reduced to 117mg/L, and the water content of the solid phase of the mud after separation is 32 percent.
Example 2: the COD of the solid phase is reduced to 92mg/L, and the water content of the solid phase of the slurry after separation is 30 percent.
Example 3: the COD of the solid phase is reduced to 72mg/L, and the water content of the solid phase of the slurry after separation is 37 percent.
Example 4: the COD of the solid phase is reduced to 109mg/L, and the water content of the solid phase of the mud after separation is 34 percent.
Example 5: the COD of the solid phase is reduced to 99mg/L, and the water content of the solid phase of the slurry after separation is 31 percent.
Example 6: the COD of the solid phase is reduced to 82mg/L, and the water content of the solid phase of the slurry after separation is 37 percent.
According to the structure, after solid-liquid separation by the method, the COD of the solid phase can be reduced to 50-130mg/L, and the water content of the solid phase of the slurry after separation is less than 40%.
Table 1: statistical table for different pH results of inorganic flocculant treatment
As shown in FIGS. 2 to 3, the pH of the solution was 6 to 9, and the overall effect was the best.
Table 2: statistical table for adding results of different oxidants treated by inorganic flocculant
The measurement results are shown in fig. 4-5, and when the adding amount of the oxidizing agent is 0.5-1% of the volume of the slurry, the comprehensive effect is best.
Table 3: statistical table of adding results of stabilizing agents for treating different heavy metals by inorganic flocculating agents
The measurement results are shown in fig. 6-7, and when the addition amount of the heavy metal stabilizer is 2-5% of the volume of the slurry, the comprehensive effect is best.
Table 4: statistical table of different inorganic flocculant adding amount treatment results
The results are shown in FIGS. 8-9, where the inorganic flocculant concentration is 10 wt% to 20 wt%, the overall effect is the best.
Table 5: statistical table of different organic flocculant adding amount treatment results
The results are shown in FIGS. 10-11, and the combined effect is best when the concentration of the organic flocculant is 0.2 wt% to 0.5 wt%.
The above embodiments are only intended to illustrate the technical solution of the present invention and not to limit the same, and a person skilled in the art can modify the technical solution of the present invention or substitute the same without departing from the spirit and scope of the present invention, and the scope of the present invention should be determined by the claims.
Claims (10)
1. The method for treating the drilling waste sulfonated mud is characterized by comprising the following steps:
collecting waste sulfonated mud from drilling, and adjusting the pH value of the mud to 6-9 by using a pH regulator;
adding 30-50 wt% of oxidant into the slurry after pH adjustment, wherein the addition amount is 0.5-1% of the volume of the slurry, and oxidizing the slurry;
adding a heavy metal stabilizer with the concentration of 0.2-0.8 wt% into the oxidized slurry, wherein the addition amount is 2-5% of the volume of the slurry, so that heavy metal ions in the slurry form a stable complex;
adding 10-20 wt% inorganic flocculant or 0.2-0.5 wt% organic flocculant into the slurry to form stable complex, the addition amount is 10-20% of the volume of the slurry, performing gel breaking flocculation on the slurry, and performing solid-liquid separation.
2. The method of claim 1, wherein the drilling waste sulfonated mud is collected using a tank with a stirrer.
3. The method of claim 1, wherein the pH adjusting agent comprises citric acid, dilute sulfuric acid, dilute hydrochloric acid, hydrofluoric acid, sulfamic acid, tartaric acid, glycolic acid, or an organic phosphoric acid.
4. The method of claim 1, wherein the oxidizing agent comprises chlorate, perchlorate, permanganate, dichromate, inorganic peroxide, manganese dioxide, ferric chloride, nitrate, sodium hypochlorite, and two or more oxidizing agents selected from the group consisting of these are used in combination.
5. The method of claim 4, wherein the inorganic peroxide comprises sodium peroxide, potassium peroxide, magnesium peroxide, calcium peroxide, barium peroxide, or hydrogen peroxide.
6. The method of claim 1, wherein the heavy metal stabilizer comprises ethylenediaminetetraacetic acid, ethylenediaminetetramethylenephosphonic acid, polymaleic acid, polyacrylic acid, sodium thioantimonate, polyhydroxyacrylic acid, maleic acrylic acid copolymer, or polyacrylamide.
7. The method of claim 1, wherein the inorganic flocculant comprises ferrous sulfate, ferrous chloride, alum, polyaluminum chloride, aluminum chlorohydrate, aluminum sulfate, or calcium chloride.
8. The method of claim 1, wherein the organic flocculant comprises a polymeric flocculant.
9. The method of claim 8, wherein the polymeric flocculant comprises sodium polyacrylate, polyacrylamide, polystyrene sulfonate, or polyethylene oxide.
10. The method of claim 1, wherein the solid-liquid separation is performed using a vacuum belt filter, a centrifuge, a plate and frame filter press, or a screw filter press.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111946278A (en) * | 2020-08-19 | 2020-11-17 | 中国地质科学院探矿工艺研究所 | Harmless treatment method for geological core drilling waste flushing fluid |
| CN112759216A (en) * | 2020-12-17 | 2021-05-07 | 西安华盛坤泰能源环保科技有限公司 | Method and system for reducing, harmlessly and resourcefully treating waste drilling mud |
| CN115466036A (en) * | 2022-09-30 | 2022-12-13 | 安吉国千环境科技有限公司 | Biological flocculant, bottom sludge treatment method and ecological restoration system |
| CN115583770A (en) * | 2021-07-06 | 2023-01-10 | 北京中科润金环保工程股份有限公司 | Composite gel breaker for treating offshore waste drilling mud |
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| CN111946278A (en) * | 2020-08-19 | 2020-11-17 | 中国地质科学院探矿工艺研究所 | Harmless treatment method for geological core drilling waste flushing fluid |
| CN112759216A (en) * | 2020-12-17 | 2021-05-07 | 西安华盛坤泰能源环保科技有限公司 | Method and system for reducing, harmlessly and resourcefully treating waste drilling mud |
| CN115583770A (en) * | 2021-07-06 | 2023-01-10 | 北京中科润金环保工程股份有限公司 | Composite gel breaker for treating offshore waste drilling mud |
| CN115466036A (en) * | 2022-09-30 | 2022-12-13 | 安吉国千环境科技有限公司 | Biological flocculant, bottom sludge treatment method and ecological restoration system |
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Application publication date: 20200414 |